TWI741410B - Substrate processing device and substrate processing method - Google Patents

Abstract

The substrate processing apparatus of the present invention uses a mixture of sulfuric acid and hydrogen peroxide water, that is, SPM to process substrates; it includes: a substrate holding unit that holds the substrate; and a recovery pipe that is supplied to the substrate holding unit The held substrate flows in the liquid discharged from the substrate; the sulfuric acid-containing liquid production device, which is transported to the liquid that flows into the above-mentioned recovery pipe, is used to produce the first sulfuric acid-containing liquid containing sulfuric acid at a high temperature from the liquid; surface A supply unit for supplying SPM produced based on the high-temperature first sulfuric acid-containing liquid produced by the above-mentioned sulfuric acid-containing liquid production apparatus to the surface of the substrate held by the substrate holding unit; and a back surface supply unit , Which is used to supply the second sulfuric acid-containing liquid containing the high-temperature first sulfuric acid-containing liquid produced by the above-mentioned sulfuric acid-containing liquid production apparatus to the back surface of the substrate held by the substrate holding unit.

Description

Substrate processing device and substrate processing method

The present invention relates to a substrate processing apparatus and a substrate processing method. Examples of substrates to be processed include semiconductor wafers, substrates for liquid crystal display devices, organic EL (electroluminescence; electroluminescence) display devices, such as FPD (Flat Panel Display) substrates, and optical disc substrates. , Substrates for magnetic disks, substrates for optical magnetic disks, substrates for photomasks, ceramic substrates, substrates for solar cells, etc.

In the manufacturing steps of semiconductor devices, liquid crystal display devices, etc., a substrate processing apparatus that processes substrates such as semiconductor wafers or glass substrates for liquid crystal display devices can be used.

Patent Document 1 below discloses a single-piece substrate processing apparatus that processes substrates one at a time. The substrate processing apparatus is equipped with a rotary chuck that rotates while holding the substrate horizontally, and discharges SPM (mixed sulfuric acid and hydrogen peroxide water) toward the upper surface (surface) of the substrate held by the rotary chuck Liquid) nozzle.

[Prior Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2009-272548

Due to the environmental load, it is required to reduce the amount of sulfuric acid contained in the SPM. In addition, there is also the problem of the cost of sulfuric acid. Therefore, it is required to reduce the consumption of sulfuric acid.

The temperature of the SPM supplied to the surface of the substrate is high (100°C or higher). The processing rate (resist removal rate (efficiency)) performed by SPM depends on the temperature of the surface of the substrate. The surface temperature of the substrate held by the rotating chuck is the same temperature as room temperature before the supply of SPM. As the supply of high-temperature SPM to the surface of the substrate starts, the surface temperature of the substrate rises. Then, as the supply of SPM to the substrate continues, the surface temperature of the substrate will eventually reach the same temperature as the SPM after the continuous rise, and will be maintained at that temperature thereafter.

However, it takes a considerable amount of time until the surface temperature of the substrate rises to the same temperature as the liquid temperature of the SPM. Therefore, in order to use SPM to process the surface of the substrate well (remove the resist from the surface of the substrate well), there is a possibility that the processing period will become longer. If the processing period becomes longer, there will be a consumption of SPM. There is a possibility that the consumption of sulfuric acid will increase.

Therefore, one of the objectives of the present invention is to shorten the processing period of the SPM surface supply step, thereby providing a substrate processing apparatus and a substrate processing method that can reduce the consumption of sulfuric acid.

The present invention provides a substrate processing apparatus that uses a mixture of sulfuric acid and hydrogen peroxide water, that is, SPM to process substrates; it includes: a substrate holding unit that holds the substrate; and a recovery pipe that is supplied to the substrate The substrate held by the holding unit flows in the liquid discharged from the substrate; the sulfuric acid-containing liquid production device is transported to the liquid that flows into the above-mentioned recovery pipe to produce the first high-temperature sulfuric acid-containing liquid based on the liquid Sulfuric acid-containing liquid; a surface supply unit for supplying SPM produced based on the high-temperature first sulfuric acid-containing liquid produced by the above-mentioned sulfuric acid-containing liquid production device to the surface of the substrate held by the substrate holding unit And a back surface supply unit for supplying the second sulfuric acid-containing liquid containing the high-temperature first sulfuric acid-containing liquid produced by the above-mentioned sulfuric acid-containing liquid production device to the back surface of the substrate held by the substrate holding unit.

According to this structure, the second sulfuric acid-containing liquid including the first sulfuric acid-containing liquid that is high temperature and which is supplied to the surface of the substrate as a base for producing SPM is supplied to the back surface of the substrate. The substrate is heated by the high-temperature second sulfuric acid-containing liquid being supplied to the back surface of the substrate. Therefore, the SPM surface supply step can be performed on the substrate that has been sufficiently heated, or the SPM surface supply step can be performed while the substrate is well heated. In this case, the processing efficiency (resist removal efficiency) of the substrate surface by SPM can be improved. As a result, the processing period of the SPM surface supply step can be shortened, thereby reducing the consumption of SPM and even the consumption of sulfuric acid.

In addition, what is supplied to the back surface of the substrate is a second sulfuric acid-containing liquid including a first sulfuric acid-containing liquid produced from the liquid discharged from the substrate and recovered. By supplying such a second sulfuric acid-containing liquid to the back surface of the substrate, the substrate can be heated well without using new sulfuric acid.

In this way, the consumption of sulfuric acid can be reduced.

In an embodiment of the present invention, the substrate processing apparatus further includes a control device, and the control device controls the sulfuric acid-containing liquid production device, the surface supply unit, and the back surface supply unit, and the control device performs the following steps: The sulfuric acid-containing liquid production step is to produce the first sulfuric acid-containing liquid at a high temperature by the sulfuric acid-containing liquid production device based on the liquid flowing into the recovery pipe; the SPM surface supply step is based on the production of the sulfuric acid-containing liquid production device The first high-temperature sulfuric acid liquid produced The SPM is supplied to the surface of the substrate held by the substrate holding unit; and the sulfuric acid-containing liquid back surface supply step is performed before or in parallel with the SPM surface supply step to heat the substrate Hold the substrate held by the holding unit, and supply the second sulfuric acid-containing liquid containing the high-temperature first sulfuric acid-containing liquid produced by the above-mentioned sulfuric acid-containing liquid production apparatus to the back surface of the substrate held by the substrate holding unit .

According to this structure, before the SPM surface supply step or in parallel with the SPM surface supply step, the second sulfuric acid-containing liquid including the first sulfuric acid-containing liquid that will become a high-temperature base for producing SPM supplied to the substrate surface is supplied to The back of the substrate. The substrate is heated by the high-temperature second sulfuric acid-containing liquid being supplied to the back surface of the substrate. Therefore, it is possible to perform the SPM surface supply step on the substrate that has been sufficiently heated, or it is possible to perform the SPM surface supply step while the substrate is well heated.

In one embodiment of the present invention, the substrate processing apparatus further includes: a liquid discharge pipe for inflow of liquid supplied to the substrate held by the substrate holding unit and discharged from the substrate; and a switching unit, which The piping into which the liquid discharged from the substrate held by the substrate holding unit flows is switched between the liquid discharge piping and the recovery piping; the control device controls the switching unit, and the control device further executes the recovery step , And this recovery step is performed in parallel with the above-mentioned sulfuric acid-containing liquid back surface supply step, and the liquid discharged from the substrate held by the substrate holding unit is caused to flow into the above-mentioned recovery pipe by the above-mentioned switching unit.

According to this configuration, the recovery step is performed in parallel with the sulfuric acid-containing liquid back surface supply step. That is, the second sulfuric acid-containing liquid supplied to the back of the substrate for heating of the substrate is recovered by the recovery pipe, and based on the recovered second sulfuric acid-containing liquid, the first sulfuric acid-containing liquid is produced in the sulfuric acid-containing liquid production device Was made in. Therefore, it can be heated for the substrate The second sulfuric acid-containing liquid supplied to the back surface of the substrate is reused as a base for the production of SPM used in the SPM surface supply step. Thereby, heating of the substrate using the second sulfuric acid-containing liquid can be performed without increasing the consumption of sulfuric acid.

In one embodiment of the present invention, the control device executes the sulfuric acid-containing liquid back surface supply step before the SPM surface supply step, and the control device further executes the liquid discharge step, and the liquid discharge step is the same as the SPM surface supply step In parallel, the liquid discharged from the substrate held by the substrate holding unit is caused to flow into the liquid discharge pipe by the switching unit.

According to this configuration, the sulfuric acid-containing liquid back surface supply step is executed before the SPM surface supply step. Therefore, the SPM surface supply step can be started on the substrate that has been sufficiently heated. In this case, the processing efficiency (resist removal efficiency) of the substrate surface by SPM can be improved, and as a result, the processing period of the SPM surface supply step can be shortened.

In addition, the draining step is performed in parallel with the SPM surface supply step performed after the sulfuric acid-containing liquid back surface supply step and the recovery step are completed. In the short period after the start of the SPM surface supply step, there is a possibility that in the liquid discharged from the substrate, in addition to the SPM supplied to the surface of the substrate, a large amount of resist and the like removed from the surface of the substrate are included. foreign body. If such a liquid containing a large amount of foreign matter is used as a base to make the first sulfuric acid-containing liquid, it will be difficult to make a clean first sulfuric acid-containing liquid. In the fourth invention, by performing the liquid discharge step in parallel with the SPM surface supply step, a large amount of foreign matter liquid can be discharged, whereby the clean liquid can be used as a base to prepare the first sulfuric acid-containing liquid. Therefore, a clean first sulfuric acid-containing liquid can be produced in the sulfuric acid-containing liquid preparation step.

In one embodiment of the present invention, the control device executes the sulfuric acid-containing liquid back surface supply step in parallel with the SPM surface supply step.

According to this structure, the step of supplying the sulfuric acid liquid on the back and the surface supply of the SPM The steps are executed in parallel. Therefore, the SPM surface supply step can be performed while heating the substrate. In this case, the efficiency of surface treatment (resist removal efficiency) of the substrate by SPM can be improved, and as a result, the treatment period of the SPM surface supply step can be shortened.

In an embodiment of the present invention, the control device may also perform the following steps in the SPM surface supply step: a first surface supply step, which supplies SPM to the surface of the substrate held by the substrate holding unit; and 2 surface supply step, in the first surface supply step, after the supply of SPM is stopped, SPM is supplied to the surface of the substrate held by the substrate holding unit; the control device is parallel to the second surface supply step Preferably, the sulfuric acid-containing liquid back surface supply step is performed, and the control device executes the recovery step by the switching unit in parallel with the second surface supply step and the sulfuric acid liquid back surface supply step.

According to this configuration, the recovery step is executed in parallel with the second surface supply step. In the short period after the start of the SPM surface supply step, there is a possibility that in the liquid discharged from the substrate, in addition to the SPM supplied to the substrate surface, there is also a large amount of resist, etc., which is removed from the substrate surface. Foreign matter removed. If such a liquid containing a large amount of foreign matter is used as a base to make the first sulfuric acid-containing liquid, it will be difficult to make a clean first sulfuric acid-containing liquid. In the invention of claim 6, by performing the recovery step in parallel with the second surface supply step instead of in parallel with the first surface supply step, it is possible to recover the liquid while preventing the mixing of foreign matter. In this way, a clean liquid can be used as a base to make the first sulfuric acid-containing liquid. Therefore, a clean first sulfuric acid-containing liquid can be produced in the sulfuric acid-containing liquid preparation step.

In addition, the recovery step is performed in parallel with the sulfuric acid-containing liquid back surface supply step. That is, after the second sulfuric acid-containing liquid supplied to the back of the substrate for heating of the substrate is recovered by the recovery pipe, the second sulfuric acid-containing liquid is collected in the sulfuric acid-containing liquid production device based on the recovered second sulfuric acid liquid Was made in. Therefore, the substrate can be supplied to the substrate for heating The second sulfuric acid-containing liquid on the back of the board is reused as a base for the production of SPM used in the step of supplying the surface of the SPM. Thereby, heating of the substrate using the second sulfuric acid-containing liquid can be performed without increasing the consumption of sulfuric acid.

In one embodiment of the present invention, the control device further executes a liquid discharge step, and the liquid discharge step is performed in parallel with the first surface supply step by the switching unit to allow the substrate held by the substrate holding unit to be The discharged liquid flows into the above-mentioned discharge pipe.

According to this configuration, the liquid discharge step is executed in parallel with the first surface supply step included in the SPM surface supply step. Thereby, the liquid containing a large amount of foreign matter can be drained, and the clean liquid can be used as the base to make the first sulfuric acid-containing liquid. Therefore, a clean first sulfuric acid-containing liquid can be produced in the sulfuric acid-containing liquid preparation step.

In one embodiment of the present invention, the substrate processing apparatus further includes: a liquid discharge pipe for inflow of liquid supplied to the substrate held by the substrate holding unit and discharged from the substrate; and a switching unit, which The piping for the inflow of the liquid discharged from the substrate held by the substrate holding unit is switched between the discharge piping and the recovery piping; the control device controls the switching unit, and the control device is on the surface of the SPM In the supplying step, the following steps are performed: the first surface supplying step, which supplies SPM to the surface of the substrate held by the substrate holding unit; and the second surface supplying step, which is in the first surface supplying step, in the SPM After the supply of SPM is stopped, SPM is supplied to the surface of the substrate held by the substrate holding unit; the control device executes the sulfuric acid-containing liquid back surface supply step in parallel with the first surface supply step, and the control device further executes the discharge The liquid discharge step is parallel to the first surface supply step and the sulfuric acid-containing liquid back surface supply step. The switching unit allows the liquid discharged from the substrate held by the substrate holding unit to flow into The above-mentioned drain piping.

According to this configuration, the sulfuric acid-containing liquid back surface supply step is executed in parallel with the first surface supply step. In addition, the draining step is performed in parallel with the sulfuric acid-containing liquid back surface supply step. Therefore, the high-temperature second sulfuric acid-containing liquid can be supplied to the back surface of the substrate from the beginning of the SPM surface supply step. In this case, the resist can be removed from the substrate surface at an earlier stage after the start of the SPM surface supply step, thereby further shortening the processing period of the SPM surface supply step.

In one embodiment of the present invention, the sulfuric acid-containing liquid production apparatus includes: a first sulfuric acid-containing liquid production apparatus that supplies a high-temperature first sulfuric acid liquid to the surface supply unit without supplying the first sulfuric acid liquid to the back surface supply unit. Sulfuric acid liquid; and a second sulfuric acid-containing liquid production device that supplies a high-temperature first sulfuric acid liquid to the back surface supply unit without supplying the first sulfuric acid liquid to the surface supply unit.

According to this configuration, the first sulfuric acid-containing liquid production device supplies the high-temperature first sulfuric acid-containing liquid to the surface supply unit, and does not supply the first sulfuric acid-containing liquid to the back surface supply unit. In addition, the second sulfuric acid-containing liquid production device supplies the high-temperature first sulfuric acid-containing liquid to the back surface supply unit, and does not supply the first sulfuric acid-containing liquid to the surface supply unit. Therefore, the second sulfuric acid-containing liquid production device is a sulfuric acid-containing liquid production device exclusively for back supply. The second sulfuric acid solution used only for raising the temperature of the substrate has a looser standard of sulfuric acid concentration. Therefore, the lower limit concentration of the sulfuric acid concentration of the first sulfuric acid-containing liquid produced by the second sulfuric acid-containing liquid production device can be set to be low. Thereby, the discharge amount of the first sulfuric acid-containing liquid from the second sulfuric acid-containing liquid production device can be reduced. Therefore, it is possible to further reduce the consumption of sulfuric acid.

In one embodiment of the present invention, a sulfuric acid supply pipe is further included, and the sulfuric acid supply pipe is used when the sulfuric acid concentration of the first sulfuric acid-containing liquid produced by the above-mentioned first sulfuric acid-containing liquid production device is lower than a predetermined lower limit concentration.时，Since the first sulfur content above The acid liquid production device supplies the first sulfuric acid liquid to the second sulfuric acid liquid production device.

According to this configuration, when the sulfuric acid concentration of the first sulfuric acid-containing liquid produced by the first sulfuric acid-containing liquid production device is lower than the predetermined lower limit concentration, the first sulfuric acid-containing liquid is supplied from the first sulfuric acid-containing liquid production device to The second sulfuric acid-containing liquid production device. The sulfuric acid whose sulfuric acid concentration of the first sulfuric acid-containing liquid produced by the first sulfuric acid-containing liquid production device is lower than the lower limit concentration should originally be discharged. Such a first sulfuric acid-containing liquid is collected in the second sulfuric acid-containing liquid production device, and is used as the first sulfuric acid-containing liquid for back surface supply (for substrate heating). Therefore, it is possible to further reduce the consumption of sulfuric acid.

The second sulfuric acid-containing liquid supplied to the back surface of the substrate held by the substrate holding unit may be the first sulfuric acid-containing liquid.

The second sulfuric acid-containing liquid supplied to the back surface of the substrate held by the substrate holding unit may be SPM, which is a mixed liquid of the first sulfuric acid-containing liquid and hydrogen peroxide water.

The substrate processing method of the present invention is executed in a substrate processing apparatus and uses a mixture of sulfuric acid and hydrogen peroxide water, that is, SPM to process substrates. The substrate processing apparatus includes: a substrate holding unit; and a recovery pipe, It is supplied to the substrate held by the substrate holding unit and the liquid discharged from the substrate flows in; wherein the substrate processing method includes: a step of preparing a sulfuric acid-containing liquid based on the liquid flowing into the recovery pipe Preparing a first sulfuric acid-containing liquid containing sulfuric acid at a high temperature; an SPM surface supply step, which supplies SPM made according to the high-temperature first sulfuric acid-containing liquid that has been produced to the surface of the substrate held by the substrate holding unit; And the sulfuric acid-containing liquid back surface supply step, which before or in parallel with the above SPM surface supply step, in order to heat the substrate held by the substrate holding unit, the first high temperature containing the manufactured first The second sulfuric acid-containing liquid containing the sulfuric acid liquid is supplied to the back surface of the substrate held by the substrate holding unit.

According to this method, before the SPM surface supply step or in parallel with the SPM surface supply step, the second sulfuric acid-containing liquid including the high-temperature first sulfuric acid-containing liquid that becomes the base for the production of SPM supplied to the substrate surface is supplied to the substrate The back. The substrate is heated by the high-temperature second sulfuric acid-containing liquid being supplied to the back surface of the substrate. Therefore, it can be made to perform the SPM surface supplying step on the substrate that has been sufficiently heated, or it can be made to perform the SPM surface supplying step while raising the temperature of the substrate satisfactorily. Therefore, the efficiency (resist removal efficiency) of the surface of the substrate by SPM can be improved. As a result, the processing period of the SPM surface supply step can be shortened, thereby reducing the consumption of SPM and even the consumption of sulfuric acid.

In addition, what is supplied to the back surface of the substrate is a second sulfuric acid-containing liquid containing a first sulfuric acid-containing liquid prepared from a liquid discharged from the substrate and recovered. By supplying such a second sulfuric acid-containing liquid to the back surface of the substrate, the substrate can be heated well without using new sulfuric acid.

In this way, the consumption of sulfuric acid can be reduced.

In one embodiment of the present invention, a recovery step is further included, and the recovery step is performed in parallel with the above-mentioned sulfuric acid-containing liquid back surface supply step, and the liquid discharged from the substrate held by the substrate holding unit flows into the above-mentioned recovery pipe By.

According to this method, the recovery step is performed in parallel with the sulfuric acid-containing liquid back surface supply step. That is, the second sulfuric acid-containing liquid supplied to the back of the substrate to heat the substrate is recovered by the recovery pipe, and based on the recovered second sulfuric acid-containing liquid, the first sulfuric acid-containing liquid is processed in the sulfuric acid-containing liquid production device. Make. Therefore, the second sulfuric acid-containing liquid supplied to the back surface of the substrate for heating the substrate can be reused as a base for the production of SPM used in the SPM surface supply step. Thereby, it is possible to heat the substrate using the second sulfuric acid-containing liquid without increasing the consumption of sulfuric acid.

In one embodiment of the present invention, the substrate processing apparatus further includes a liquid discharge pipe, and the liquid discharge pipe is supplied to the substrate held by the substrate holding unit and discharged from the substrate into which the liquid is discharged, The sulfuric acid-containing liquid back surface supply step is performed before the SPM surface supply step, the substrate processing method further includes a liquid discharge step, and the liquid discharge step is performed in parallel with the SPM surface supply step to free the substrate The liquid discharged from the substrate held by the holding unit flows into the liquid discharge pipe.

According to this method, the sulfuric acid-containing liquid back surface supply step is performed before the SPM surface supply step. Then, the draining step is performed in parallel with the SPM surface supply step performed after the sulfuric acid-containing liquid back surface supply step and the recovery step are completed. In the short period after the start of the SPM surface supply step, there is a possibility that in the liquid discharged from the substrate, in addition to the SPM supplied to the surface of the substrate, there is also a large amount of resist from the surface of the substrate. Foreign matter removed. If such a liquid containing a large amount of foreign matter is used as a base to make the first sulfuric acid-containing liquid, it will be difficult to make a clean first sulfuric acid-containing liquid. In the invention of claim 15, by performing the liquid discharge step in parallel with the SPM surface supply step, the liquid containing a large amount of foreign matter can be discharged, thereby making the first sulfuric acid liquid based on the clean liquid. Therefore, a clean first sulfuric acid-containing liquid can be produced in the sulfuric acid-containing liquid preparation step.

In one embodiment of the present invention, the above-mentioned sulfuric acid-containing liquid back surface supply step is performed in parallel with the above-mentioned SPM surface supply step.

According to this method, the sulfuric acid-containing liquid back surface supply step is performed in parallel with the SPM surface supply step. Therefore, the SPM surface supply step can be performed while heating the substrate. In this case, the efficiency (resist removal efficiency) of the surface of the substrate by SPM can be improved, and as a result, the processing period of the SPM surface supply step can be shortened.

In one embodiment of the present invention, the SPM surface supply step includes: a first surface supply step of supplying SPM to the surface of the substrate held by the substrate holding unit; and a second surface supply step of the first surface supply step. In the 1 surface supply step, after the supply of SPM is stopped, SPM is supplied to the surface of the substrate held by the substrate holding unit; the sulfuric acid-containing liquid back surface supply step is performed in parallel with the second surface supply step, and the recovery The step is executed in parallel with the second surface supply step and the sulfuric acid-containing liquid back surface supply step.

According to this method, the recovery step is performed in parallel with the second surface supply step. In the short period after the start of the SPM surface supply step, there is a possibility that in the liquid discharged from the substrate, in addition to the SPM supplied to the surface of the substrate, there is also a large amount of resist etc. from the surface of the substrate. Foreign matter removed. If such a liquid containing a large amount of foreign matter is used as a base to make the first sulfuric acid-containing liquid, it will be difficult to make a clean first sulfuric acid-containing liquid. In the invention of claim 17, by performing the recovery step in parallel with the second surface supply step instead of in parallel with the first surface supply step, it is possible to recover the liquid while preventing the mixing of foreign matter. In this way, a clean liquid can be used as a base to make the first sulfuric acid-containing liquid. Therefore, a clean first sulfuric acid-containing liquid can be produced in the sulfuric acid-containing liquid preparation step.

In addition, the recovery step is performed in parallel with the sulfuric acid-containing liquid back surface supply step. That is, after the second sulfuric acid-containing liquid supplied to the back surface of the substrate for heating the substrate is recovered by the recovery pipe, the first sulfuric acid-containing liquid is produced in the sulfuric acid-containing liquid based on the recovered second sulfuric acid liquid Was made in. Therefore, the second sulfuric acid-containing liquid supplied to the back surface of the substrate for heating the substrate can be reused as a base for the production of SPM used in the SPM surface supply step. Thereby, heating of the substrate using the second sulfuric acid-containing liquid can be performed without increasing the consumption of sulfuric acid.

The above-mentioned substrate processing apparatus further includes a drain pipe, and the drain pipe The piping system is supplied to the inflow of the liquid discharged from the substrate held by the substrate holding unit. The substrate processing method further includes a liquid discharge step, and the liquid discharge step is the same as the first surface supply The steps are performed in parallel to allow the liquid discharged from the substrate held by the substrate holding unit to flow into the liquid discharge pipe.

According to this method, the liquid discharge step is performed in parallel with the first surface supply step included in the SPM surface supply step. Thereby, the liquid containing a large amount of foreign matter can be discharged, and the clean liquid can be used as the base to make the first sulfuric acid-containing liquid. Therefore, a clean first sulfuric acid-containing liquid can be produced in the sulfuric acid-containing liquid preparation step.

In one embodiment of the present invention, the substrate processing apparatus further includes a liquid discharge pipe, and the liquid discharge pipe is supplied to the substrate held by the substrate holding unit and discharged from the substrate into which the liquid is discharged, The SPM surface supply step includes: a first surface supply step, which supplies SPM to the surface of the substrate held by the substrate holding unit; and a second surface supply step, in the first surface supply step, in the SPM After the supply of SPM is stopped, SPM is supplied to the surface of the substrate held by the substrate holding unit; the sulfuric acid-containing liquid back surface supply step is performed in parallel with the first surface supply step, and the substrate processing method further includes a liquid drain step The liquid discharge step is performed in parallel with the first surface supply step and the sulfuric acid-containing liquid back surface supply step, and the liquid discharged from the substrate held by the substrate holding unit flows into the liquid discharge pipe.

According to this method, the sulfuric acid-containing liquid back surface supply step is performed in parallel with the first surface supply step. In addition, the draining step is performed in parallel with the sulfuric acid-containing liquid back surface supply step. Therefore, the high-temperature second sulfuric acid-containing liquid can be supplied to the back surface of the substrate W from the beginning of the SPM surface supply step. In this case, the resist can be removed from the substrate surface at an earlier stage after the start of the SPM surface supply step, thereby further shortening the SPM surface supply step The processing period.

The second sulfuric acid-containing liquid supplied to the back surface of the substrate held by the substrate holding unit may be the first sulfuric acid-containing liquid.

The second sulfuric acid-containing liquid supplied to the back surface of the substrate held by the substrate holding unit may be SPM, which is a mixed liquid of the first sulfuric acid-containing liquid and hydrogen peroxide water.

The foregoing or other further objects, features, and effects of the present invention can be clarified by referring to the accompanying drawings and the description of the following embodiments.

1: Substrate processing equipment

2: Device body

3: Indexing unit

4: control device

5: Transfer room

6: Processing unit

7: Outer wall

8: Sulfuric acid liquid production equipment

11: The first reservoir

12: The second reservoir

13: SPM nozzle

13a: spit out

21: Recovery tank

22: 1st circulation slot

23: 1st cycle piping

24: 1st cycle heater

25: Sulfuric acid replenishment unit

26: Recycling and exporting piping

31: Induction piping

32: The first liquid feeding device

37: Capture filter

38: On-off valve

40: Return to piping

41: Return valve

42: divergent position

44: Sulfuric acid supplement piping

45: Sulfuric acid make-up valve

51: 2nd circulation slot

51A: 1st common piping

51B: 1st sulfuric acid-containing liquid circulation piping

52: 2nd cycle heater

53: 2nd cycle piping

54: No. 1 heater

56: The second liquid feeding device

57: No. 1 supply piping for sulfuric acid-containing liquid

59: The first sulfuric acid-containing liquid flow adjustment valve

60: The first sulfuric acid liquid valve

61: 1st return piping

63: 1st branch position

64: Sulfuric acid concentration meter

65: Liquid meter

71A: 2nd common piping

71B: 2nd sulfuric acid-containing liquid flow piping

72: 3rd cycle heater

73: 3rd loop piping

74: The second heater

76: 3rd liquid feeding device

77: The second sulfuric acid-containing liquid supply piping

78: The second flow meter

79: The second sulfuric acid-containing liquid flow adjustment valve

80: The second sulfuric acid liquid valve

81: The second return piping

83: 2nd branch position

91: bottom surface nozzle

91a: spit out

92: Bottom surface supply piping

93: Flushing fluid piping

94: Flushing fluid valve

100: pattern

101: Construct

107: Chamber

108: Rotating Chuck

110: flushing fluid supply unit

111: handle the cup

111a: upper end

112: Barrier

113: Exhaust duct

114: FFU

115: Rotation axis

116: Rotating base

116a: upper surface

117: Clamping member

119: nozzle arm

120: Nozzle moving unit

122: Hydrogen peroxide water supply unit

135: Hydrogen peroxide water piping

136: Hydrogen peroxide water valve

137: Hydrogen peroxide water flow regulating valve

140: Cylinder member

141: first cup

142: The second cup

143: first baffle

143a: inner wall

143b: outer wall

144: second baffle

144a: inner wall

145: 3rd baffle

146: baffle lift unit

147: Washing fluid nozzle

148: Flushing fluid piping

149: Flushing fluid valve

150: first ditch

151: Drain

152: Drainage piping

153: The second groove

154: Recovery Port

156: Recovery piping

163: lower end

164: cylindrical part

165: middle section

166: upper end

167: Cylinder

168: upper end

170: Cylinder

171: upper end

181: Resist

182: Hardened layer

183: Non-hardened layer

184: Gas

185: Crack

201: Substrate processing equipment

208A: The first sulfuric acid-containing liquid production device

208B: The second sulfuric acid liquid production device

209: Sulfuric acid liquid supply piping

210: On-off valve

A1: Rotation axis

C: carrier

CR1: The first substrate transfer robot

CR2: The second substrate transfer robot

IR: Indexing robot

LP: load port

M: Rotating motor

SP1: The first circulation space

SP2: Second circulation space

T: film thickness

T1~T7: time

W: substrate

W1: line width

W2: gap

Wa: surface

Wb: back

Fig. 1 is a schematic view of a substrate processing apparatus according to an embodiment of the present invention viewed from above.

Fig. 2 is a view of the sulfuric acid-containing liquid production device and the main body of the device shown in Fig. 1 viewed from a horizontal direction.

Fig. 3 is a schematic cross-sectional view for explaining a configuration example of the processing unit shown in Fig. 1.

FIG. 4A is a block diagram for explaining the electrical structure of the above-mentioned substrate processing apparatus.

4B is an enlarged cross-sectional view showing the surface of the substrate to be processed by the substrate processing apparatus.

Fig. 5 is a flowchart of a first substrate processing example executed by the above-mentioned processing unit.

Fig. 6 is a timing chart showing the operations of the first baffle and the second baffle in the first substrate processing example.

7A and 7B are diagrams for explaining the sulfuric acid-containing liquid back surface supply step and the first surface supply step (SPM surface supply step), respectively.

Fig. 7C is a diagram for explaining an illustration of the second surface supply step (SPM surface supply step).

Fig. 8 is a flowchart of a second substrate processing example executed by the above-mentioned processing unit.

FIG. 9 is a diagram for explaining the second surface supply step (SPM surface supply step) of the above-mentioned second substrate processing example.

Fig. 10 is a flowchart of a third substrate processing example executed by the above-mentioned processing unit.

FIG. 11 is a diagram for explaining an illustration of the first surface supply step (SPM surface supply step) in the third substrate processing example.

12A and 12B are diagrams for explaining the removal (stripping) of the resist formed on the surface of the substrate.

12C and 12D are diagrams showing the next step in FIG. 12B.

Fig. 13 is a schematic view of a substrate processing apparatus according to another embodiment of the present invention viewed from above.

Fig. 1 is a schematic view of a substrate processing apparatus 1 according to an embodiment of the present invention viewed from above.

The substrate processing apparatus 1 is a single-chip apparatus that processes a disc-shaped substrate W such as a semiconductor wafer one at a time. The substrate processing apparatus 1 includes an apparatus main body 2 arranged in a clean room, an indexing unit 3 coupled to the apparatus main body 2, a processing liquid supply device, and a control device 4 that controls the substrate processing apparatus 1.

The indexing unit 3 includes a plurality of load ports LP for holding a plurality of carriers C for accommodating the substrate W, and an indexing robot IR for transferring the substrate W to each carrier C.

The apparatus body 2 includes a transfer chamber 5 and a plurality of processing units 6 that process substrates W transferred from a plurality of load ports LP with a processing fluid such as a processing liquid or a processing gas. The plural processing units 6 are formed with 6 towers respectively arranged at 6 horizontally divided positions. Each tower includes a plurality of (for example, three) processing units 6 stacked on top and bottom. The six towers are arranged on both sides of the transfer chamber 5 with three each. The processing unit 6 is configured in The outer wall 7 of the device body 2 is surrounded by the outer wall 7.

The substrate processing apparatus 1 as a transfer robot includes a first substrate transfer robot CR1 and a second substrate transfer robot CR2 in addition to the indexing robot IR. The first substrate transfer robot CR1 and the second substrate transfer robot CR2 are arranged in the transfer chamber 5. The indexing robot IR transfers the substrate W between the load port LP and the first substrate transfer robot CR1. The indexing robot IR includes a robot arm supporting the substrate W. The first substrate transfer robot CR1 transfers the substrate W between the indexing robot IR and the processing units 6 included in the two towers on the load port LP side, and transfers the substrate W between the indexing robot IR and the second substrate transfer robot CR2 . The second substrate transfer robot CR2 transfers the substrate W between the indexing robot IR and the processing unit 6 included in the four towers on the side opposite to the load port LP side. The first substrate transfer robot CR1 and the second substrate transfer robot CR2 include a robot arm that supports the substrate W.

The processing liquid supply device supplies the processing liquid (sulfuric acid-containing liquid (first sulfuric acid-containing liquid. etching liquid or cleaning liquid)) to the processing unit 6. The processing liquid supply device includes a sulfuric acid-containing liquid production device 8 for producing a sulfuric acid-containing liquid (first sulfuric acid-containing liquid) to be used in the processing unit 6. The sulfuric acid-containing liquid production device 8 recovers the liquid discharged from the processing unit 6 and adjusts it as a sulfuric acid-containing liquid (first sulfuric acid-containing liquid), and supplies the adjusted sulfuric acid-containing liquid to the processing unit 6. As shown in FIG. 1, the sulfuric acid-containing liquid production device 8 is arranged on the outer side of the outer wall 7 in the clean room. In the example of FIG. 1, two sulfuric acid-containing liquid production devices 8 are provided.

Each sulfuric acid-containing liquid production device 8 corresponds to three towers arranged on one side of the transfer chamber 5. Each sulfuric acid-containing liquid production device 8 is supplied with the SPM discharged from the processing unit 6 included in the corresponding three towers. The sulfuric acid-containing liquid production device 8 includes: a first liquid reservoir 11 (refer to FIG. 2), which recovers the SPM discharged from the processing unit 6 and stores it as a sulfuric acid-containing liquid, and adjusts it to a predetermined state; and The second reservoir 12 (refer to FIG. 2). Sulfuric acid solution The manufacturing device 8 may not be arranged inside the clean room, but may be arranged outside the clean room (for example, the under-floor space of the clean room). In addition, the first liquid storage portion 11 and the second liquid storage portion 12 may be housed in a common frame, or may be housed and arranged in different frames.

In the sulfuric acid-containing liquid production apparatus 8, the sulfuric acid-containing liquid (the first sulfuric acid-containing liquid) is produced from the SPM discharged from the substrate W and recovered, instead of being produced as the SPM itself (sulfuric acid-containing liquid production step). The sulfuric acid-containing liquid produced by the sulfuric acid-containing liquid production device 8 (the sulfuric acid concentration and temperature have been adjusted) is supplied to the SPM nozzle (nozzle) 13 as an example of the surface supply unit of the processing unit 6 (refer to FIGS. 2 and 3) ). The hydrogen peroxide water is supplied to the SPM nozzle 13 from the hydrogen peroxide water supply unit 122 (refer to FIGS. 2 and 3). The sulfuric acid-containing liquid and hydrogen peroxide water supplied to the SPM nozzle 13 are mixed in the interior (mixing part) of the SPM nozzle 13, and SPM is generated thereby. Then, the SPM is discharged from the discharge port 13a (refer to FIG. 3) formed at the lower part of the SPM nozzle 13. The discharge port 13a communicates with the inside of the SPM nozzle 13. Then, in the processing unit 6, the SPM discharged from the discharge port 13a is supplied to the substrate W. Thereby, the resist is removed from the substrate W.

From the viewpoint of improving the removal ability of SPM, the sulfuric acid concentration of the produced sulfuric acid-containing liquid is required to be within a predetermined concentration range (above the predetermined concentration). Moreover, from the same point of view, the temperature of the produced sulfuric acid liquid is required to be within a predetermined temperature range.

FIG. 2 is a view of the sulfuric acid-containing liquid production device 8 and the device body 2 shown in FIG. 1 as viewed from a horizontal direction.

The sulfuric acid-containing liquid production device 8 includes a first liquid storage portion 11 and a second liquid storage portion 12.

The first reservoir 11 includes a first circulation tank 22, a first circulation pipe 23, a first circulation heater 24, and a sulfuric acid replenishing unit 25.

The first liquid storage unit 11 stores SPM recovered from a total of 9 processing units 6 included in the corresponding 3 towers as a sulfuric acid-containing liquid. The first circulation tank 22 is connected to the downstream end of the recovery lead-out pipe 26 connected to the recovery pipe 156 described later. The SPM recovered by the processing cup 111 of each processing unit 6 is guided to the first circulation tank 22 through the recovery pipe 156 and the recovery and outlet pipe 26 and is stored in the first circulation tank 22.

The downstream ends of the three recovery and discharge pipes 26 corresponding to the three towers are connected to the first circulation tank 22. In Fig. 2, only one tower is shown in detail, and the other two towers are not shown.

A liquid guiding pipe 31 extending toward the second liquid storage portion 12 is connected to the first circulation tank 22. In the middle of the liquid guiding pipe 31, a first liquid feeding device 32 such as a pump for taking out the sulfuric acid-containing liquid in the first circulation tank 22 is interposed. In the middle of the liquid guide pipe 31, a trap filter 37 and an on-off valve 38 are interposed on the downstream side of the first liquid feeding device 32. The catching filter 37 is a filter for catching and removing small foreign substances contained in the sulfuric acid-containing liquid flowing through the liquid guiding pipe 31.

The on-off valve 38 is a valve for controlling the circulation and stopping of the sulfuric acid-containing liquid in the liquid guiding pipe 31.

In the liquid guiding pipe 31, a return pipe 40 is branched and connected between the on-off valve 38 and the trap filter 37. The downstream end of the return pipe 40 extends toward the first circulation groove 22. A return valve 41 is interposed in the middle of the return pipe 40. The first circulation pipe 23 is constituted by the downstream portion of the branch position 42 of the return pipe 40 in the liquid guide pipe 31 and the return pipe 40.

The sulfuric acid replenishment unit 25 is a unit that supplies new sulfuric acid (sulfuric acid that is not used in the processing of the substrate W) to the first circulation tank 22. The sulfuric acid replenishing unit 25 includes a sulfuric acid replenishing pipe 44 that replenishes the sulfuric acid-containing liquid to the first circulation tank 22, and the sulfuric acid replenishing pipe 44 The valve 45 is supplemented with open and closed sulfuric acid. The added sulfuric acid-containing liquid is unused sulfuric acid (for example, concentrated sulfuric acid), and its sulfuric acid concentration is higher than the sulfuric acid concentration in the sulfuric acid-containing liquid in the first circulation tank 22. The added sulfuric acid liquid is at room temperature (approximately 23℃~approximately 25℃).

During the operation of the substrate processing apparatus 1 (including the period during which the processing of the substrate W is stopped), the first liquid feeding device 32 and the first circulation heater 24 are constantly driven. Therefore, when the on-off valve 38 is closed and the return valve 41 is opened, the sulfuric acid-containing liquid taken out from the first circulation tank 22 flows to the branch position 42 in the liquid guiding pipe 31, and passes through the return pipe 40 from the branch position 42. It is returned to the first circulation tank 22. In other words, the sulfuric acid-containing liquid circulates in the first circulation tank 22 and the first circulation pipe 23 while the sulfuric acid-containing liquid is not sent to the second reservoir 12. Furthermore, when it is the time to deliver the sulfuric acid-containing liquid to the second reservoir 12, the sulfuric acid-containing liquid taken out from the first circulation tank 22 is opened by the on-off valve 38 and the return valve 41 is closed, and then passes through the liquid guide. The pipe 31 is supplied to the second reservoir 12.

The first circulation heater 24 is interposed on the upstream side of the first liquid feeding device 32 in the middle of the liquid guiding pipe 31. The first circulation heater 24 heats the sulfuric acid-containing liquid circulating in the first circulation tank 22 and the first circulation pipe 23. The heating temperature of the first circulation heater 24 is set to a predetermined first temperature (for example, about 120°C to about 130°C). By circulating the sulfuric acid-containing liquid in the first circulation tank 22 and the first circulation pipe 23, the sulfuric acid-containing liquid is adjusted to the first temperature. During the period when the sulfuric acid-containing liquid is not delivered to the second liquid storage part 12, the sulfuric acid-containing liquid is circulated first, so that the sulfuric acid-containing liquid adjusted to the first temperature can be stored in the first circulation tank 22 first. Furthermore, after the opening and closing valve 38 is opened, the sulfuric acid-containing liquid adjusted to the first temperature can be transported to the second reservoir 12.

The second reservoir 12 includes a second circulation tank 51.

The downstream end of the liquid guiding pipe 31 is connected to the second circulation tank 51. Sulfuric acid contained in the first liquid reservoir 11 whose temperature is adjusted to the first temperature (for example, about 120°C to about 130°C) The liquid is guided to the second circulation tank 51. Then, the introduced sulfuric acid-containing liquid is stored in the second circulation tank 51.

The second circulation tank 51 is equipped with a liquid meter 65 each having a sensor part at a plurality of positions with different heights, and the liquid level of the sulfuric acid-containing liquid stored in the second circulation tank 51 is determined by the liquid meters 65 Detected.

The first common pipe 51A is connected to the second circulation tank 51. A second circulation heater 52 is interposed in the middle of the first common pipe 51A. To the second circulation tank 51 and the first common pipe 51A, three first sulfuric acid-containing liquid circulation pipes 51B for supplying the sulfuric acid-containing liquid to the corresponding towers are connected. Specifically, the upstream and downstream ends of the three first sulfuric acid-containing liquid circulation pipes 51B are respectively connected to the downstream end of the first common pipe 51A and the second circulation tank 51 (in FIG. 2, only one is shown) The first sulfuric acid-containing liquid circulation pipe 51B). The second circulation pipe 53 is composed of a first common pipe 51A and a first sulfuric acid-containing liquid circulation pipe 51B.

In the middle of the first sulfuric acid-containing liquid circulation pipe 51B, a second liquid feeding device 56 such as a pump for taking out the sulfuric acid-containing liquid in the first common pipe 51A is interposed. The sulfuric acid-containing liquid taken out to the second circulation pipe 53 by the second liquid feeding device 56 circulates from the upstream end to the downstream end in the first sulfuric acid-containing liquid circulation pipe 51B, and returns to the second circulation tank 51. Thereby, the sulfuric acid-containing liquid circulates in the second circulation tank 51 and the second circulation pipe 53 (the first common pipe 51A and the first sulfuric acid-containing liquid circulation pipe 51B).

The second circulation heater 52 heats the sulfuric acid-containing liquid circulating in the second circulation tank 51 and the second circulation pipe 53 (the first common pipe 51A and the first sulfuric acid-containing liquid circulation pipe 51B). The heating temperature of the second circulation heater 52 is set to a predetermined second temperature (>the first temperature. For example, about 160°C). The sulfuric acid-containing liquid enters the second circulation tank 51 and the second circulation pipe 53 (the first common pipe 51A and the first sulfuric acid-containing liquid circulation pipe 51B) Circulates, and the sulfuric acid liquid is adjusted from the current first temperature to the second temperature.

The sulfuric acid-containing liquid production device 8 includes a first sulfuric acid-containing liquid branched from the second circulation pipe 53 to supply the sulfuric acid-containing liquid to a plurality of (for example, three) SPM nozzles 13 included in the corresponding tower 6 The supply piping 57, and the number of the first sulfuric acid-containing liquid supply piping 57 is the same as the number of the processing units 6 included in the tower.

A first heater 54 is interposed in the middle of each first sulfuric acid-containing liquid supply pipe 57. In the middle of each first sulfuric acid-containing liquid supply pipe 57, on the downstream side of the first heater 54, a second flow meter 78 and a first sulfuric acid-containing liquid flow rate are sequentially interposed from the first heater 54 side. The adjustment valve 59 and the first sulfuric acid-containing liquid valve 60. The second flow meter 78 is a flow meter that detects the flow rate of the sulfuric acid-containing liquid flowing in each of the first sulfuric acid-containing liquid supply pipes 57. The first sulfuric acid-containing liquid flow rate adjustment valve 59 is a valve for adjusting the opening degree of the first sulfuric acid-containing liquid supply pipe 57 to adjust the flow rate of the sulfuric acid-containing liquid supplied to the SPM nozzle 13. The first sulfuric acid-containing liquid flow adjustment valve 59 may also include a valve body in which a valve seat is provided, a valve body that opens and closes the valve seat, and an actuator that moves the valve body between an open position and a closed position. The composition. The same applies to other flow control valves.

The first sulfuric acid-containing liquid valve 60 is a valve for controlling the supply and stopping of the sulfuric acid-containing liquid to the SPM nozzle 13.

In the first sulfuric acid-containing liquid supply pipe 57, a first return pipe 61 is branched and connected between the first sulfuric acid-containing liquid valve 60 and the first sulfuric acid-containing liquid flow rate adjustment valve 59. The downstream end of the first return pipe 61 is connected to the first sulfuric acid-containing liquid circulation pipe 51B. The pressure loss in the upstream portion of the first branch position 63 in the first sulfuric acid-containing liquid supply pipe 57 is greater than the pressure loss in the first return pipe 61.

When supplying the sulfuric acid-containing liquid to the SPM nozzle 13, the control device 4 opens the first sulfuric acid-containing liquid valve 60. As a result, the pressure loss in the first return pipe 61 will be greater than that of the first The pressure loss at the downstream side portion of the first branch position 63 in the sulfuric acid-containing liquid supply pipe 57. Therefore, the sulfuric acid-containing liquid in the upstream portion of the first branch position 63 in the first sulfuric acid-containing liquid supply pipe 57 is supplied to the downstream portion of the first branch position 63 in the first sulfuric acid-containing liquid supply pipe 57, and It is supplied to the SPM nozzle 13 from this downstream side part. On the other hand, when the supply of the sulfuric acid-containing liquid to the SPM nozzle 13 is stopped, the control device 4 closes the first sulfuric acid-containing liquid valve 60. As a result, the pressure loss in the first return pipe 61 is smaller than the pressure loss in the downstream portion of the first branch position 63 in the first sulfuric acid-containing liquid supply pipe 57. Therefore, the sulfuric acid-containing liquid that has reached the first branch position 63 does not flow backward in the upstream portion of the first branch position 63 in the first sulfuric acid-containing liquid supply pipe 57, but is guided toward the first return pipe 61. The sulfuric acid-containing liquid guided to the first return pipe 61 is returned to the first sulfuric acid-containing liquid circulation pipe 51B, and flows through the second circulation tank 51 and the second circulation pipe 53 (the first common pipe 51A and the first sulfuric acid liquid circulation Piping 51B) circulates. The first heater 54 heats the sulfuric acid-containing liquid flowing through the first sulfuric acid-containing liquid supply pipe 57. The heating temperature of the first heater 54 is set to a predetermined third temperature (>the second temperature. For example, about 165°C). By flowing the sulfuric acid-containing liquid through the first sulfuric acid-containing liquid supply pipe 57, the sulfuric acid-containing liquid whose temperature has been adjusted to the second temperature so far is raised from the current second temperature to the third temperature.

During the operation of the substrate processing apparatus 1 (including the period during which the processing of the substrate W is stopped), the second liquid feeding device 56 and the second circulation heater 52 are constantly driven. Therefore, during the operation of the substrate processing apparatus 1, the sulfuric acid-containing liquid whose temperature is adjusted to the second temperature flows in the second circulation tank 51 and the second circulation pipe 53 (the first common pipe 51A and the first sulfuric acid-containing liquid circulation pipe 51B) Make a loop.

With the first sulfuric acid-containing liquid valve 60 closed, the sulfuric acid-containing liquid flowing through the second circulation pipe 53 flows from the second circulation pipe 53 to the first sulfuric acid-containing liquid supply pipe 57, and flows to the first branch position 63 The first return piping 61, and return the first sulfuric acid liquid Circulation piping 51B. Thereby, circulation is performed in the second circulation tank 51 and the second circulation pipe 53.

On the other hand, in a state where the first sulfuric acid-containing liquid valve 60 is opened, the sulfuric acid-containing liquid flowing through the first sulfuric acid-containing liquid circulation pipe 51B flows from the second circulation pipe 53 to the first sulfuric acid-containing liquid supply pipe 57, and It is supplied to the SPM nozzle 13. That is, the sulfuric acid-containing liquid adjusted to the third temperature is supplied to the SPM nozzle 13.

A second common pipe 71A is connected to the second circulation tank 51. A third circulation heater 72 is interposed in the middle of the second common pipe 71A. To the second circulation tank 51 and the second common pipe 71A, three second sulfuric acid-containing liquid circulation pipes 71B for supplying the sulfuric acid-containing liquid to the corresponding towers are connected. Specifically, the upstream end and the downstream end of the three second sulfuric acid-containing liquid circulation pipes 71B are connected to the downstream end of the second common pipe 71A and the second circulation tank 51, respectively. The third circulation pipe 73 is composed of a second common pipe 71A and a second sulfuric acid-containing liquid circulation pipe 71B.

In the middle of the second sulfuric acid-containing liquid flow pipe 71B, a third liquid feeding device 76 such as a pump for taking out the sulfuric acid-containing liquid in the second common pipe 71A is interposed. The sulfuric acid-containing liquid taken out to the third circulation pipe 73 by the third liquid feeding device 76 circulates from the upstream end to the downstream end in the second sulfuric acid-containing liquid circulation pipe 71B, and returns to the second circulation tank 51. Thereby, the sulfuric acid-containing liquid circulates in the second circulation tank 51 and the third circulation pipe 73 (the second common pipe 71A and the second sulfuric acid-containing liquid circulation pipe 71B).

The third circulation heater 72 heats the sulfuric acid-containing liquid circulating in the second circulation tank 51 and the third circulation pipe 73 (the second common pipe 71A and the second sulfuric acid-containing liquid circulation pipe 71B). The heating temperature of the third circulation heater 72 is set to the fourth temperature (>the first temperature. For example, about 160°C). By circulating the sulfuric acid-containing liquid in the second circulation tank 51 and the third circulation pipe 73 (the second common pipe 71A and the second sulfuric acid-containing liquid circulation pipe 71B), the sulfuric acid-containing liquid is adjusted from the current first temperature to the fourth temperature.

The sulfuric acid-containing liquid production device 8 includes a plurality of (e.g., three) processing units 6 branched from the third circulation pipe 73 for supplying sulfuric acid-containing liquid (first sulfuric acid-containing liquid) to the corresponding tower as the back side. An example of the supply unit is the second sulfuric acid-containing liquid supply pipe 77 of the lower surface nozzle 91, and the number of the second sulfuric acid-containing liquid supply pipe 77 is the same as the number of the processing units 6 included in the tower.

A second heater 74 is interposed in the middle of each second sulfuric acid-containing liquid supply pipe 77. In the middle of each second sulfuric acid-containing liquid supply pipe 77, on the downstream side of the second heater 74, a second flowmeter 78 and a second sulfuric acid-containing liquid flow rate are sequentially interposed from the second heater 74 side. The adjustment valve 79 and the second sulfuric acid-containing liquid valve 80. The second flow meter 78 is a flow meter that detects the flow rate of the sulfuric acid-containing liquid flowing in each of the second sulfuric acid-containing liquid supply pipes 77. The second sulfuric acid-containing liquid flow rate adjustment valve 79 is a valve for adjusting the opening degree of the second sulfuric acid-containing liquid supply pipe 77 to adjust the flow rate of the sulfuric acid-containing liquid supplied to the lower surface nozzle 91.

The second sulfuric acid-containing liquid valve 80 is a valve for controlling the supply and stop of the sulfuric acid-containing liquid to the lower surface nozzle 91.

In the second sulfuric acid-containing liquid supply pipe 77, a second return pipe 81 is branched and connected between the second sulfuric acid-containing liquid valve 80 and the second sulfuric acid-containing liquid flow control valve 79. The downstream end of the second return pipe 81 is connected to the second sulfuric acid-containing liquid circulation pipe 71B. The pressure loss in the upstream portion of the second branch position 83 in the second sulfuric acid-containing liquid supply pipe 77 is greater than the pressure loss in the second return pipe 81.

When supplying the sulfuric acid-containing liquid to the lower surface nozzle 91, the control device 4 opens the second sulfuric acid-containing liquid valve 80. As a result, the pressure loss in the second return pipe 81 is greater than the pressure loss in the downstream portion of the second branch position 83 in the second sulfuric acid-containing liquid supply pipe 77. Therefore, the sulfuric acid-containing liquid in the upstream portion of the second branch position 83 in the second sulfuric acid-containing liquid supply pipe 77 is supplied to the second branch position 83 in the second sulfuric acid-containing liquid supply pipe 77 The downstream side part of the tube is supplied to the lower surface nozzle 91 from the downstream side part. On the other hand, when the supply of the sulfuric acid-containing liquid to the lower surface nozzle 91 is stopped, the control device 4 closes the second sulfuric acid-containing liquid valve 80. As a result, the pressure loss in the second return pipe 81 is smaller than the pressure loss in the downstream portion of the second branch position 83 in the second sulfuric acid-containing liquid supply pipe 77. Therefore, the sulfuric acid-containing liquid that has reached the second branch position 83 does not flow backward in the upstream portion of the second branch position 83 in the second sulfuric acid-containing liquid supply pipe 77, but is guided toward the second return pipe 81. The sulfuric acid-containing liquid guided to the second return pipe 81 is returned to the second sulfuric acid-containing liquid circulation pipe 71B, and flows through the second circulation tank 51 and the third circulation pipe 73 (the second common pipe 71A and the second sulfuric acid liquid circulation Piping 71B) circulates. The second heater 74 heats the sulfuric acid-containing liquid flowing through the second sulfuric acid-containing liquid supply pipe 77. The heating temperature of the second heater 74 is set to a predetermined fifth temperature (>the fourth temperature. For example, about 165°C). As the sulfuric acid-containing liquid flows through the second sulfuric acid-containing liquid supply pipe 77, the temperature of the sulfuric acid-containing liquid adjusted to the fourth temperature is raised from the current fourth temperature to the fifth temperature.

During the operation of the substrate processing apparatus 1 (including the period during which the processing of the substrate W is stopped), the third liquid feeding device 76 and the third circulation heater 72 are constantly driven. Therefore, during the operation of the substrate processing apparatus 1, the sulfuric acid-containing liquid whose temperature is adjusted to the fourth temperature flows in the second circulation tank 51 and the third circulation pipe 73 (the second common pipe 71A and the second sulfuric acid-containing liquid circulation pipe 71B) Make a loop.

With the second sulfuric acid-containing liquid valve 80 closed, the sulfuric acid-containing liquid flowing through the third circulation pipe 73 flows from the third circulation pipe 73 to the second sulfuric acid-containing liquid supply pipe 77, and flows to the second branch position 83 The second return pipe 81 is returned to the second sulfuric acid-containing liquid circulation pipe 71B. Thereby, circulation is performed in the second circulation tank 51 and the third circulation pipe 73.

On the other hand, in the state where the second sulfuric acid-containing liquid valve 80 is opened, the sulfuric acid-containing liquid flowing through the second sulfuric acid-containing liquid circulation pipe 71B flows from the third circulation pipe 73 to the second 2The sulfuric acid-containing liquid supply pipe 77 is supplied to the lower surface nozzle 91. That is, the sulfuric acid-containing liquid adjusted to the fifth temperature is supplied to the lower surface nozzle 91.

With reference to the output of the liquid meter 65, the liquid amount of the sulfuric acid-containing liquid accumulated in the second circulation tank 51 is constantly monitored by the control device 4. Furthermore, if the amount of the sulfuric acid-containing liquid accumulated in the second circulation tank 51 becomes less than the lower limit liquid amount, the on-off valve 38 is opened, and the sulfuric acid-containing liquid passes from the first reservoir 11 through the liquid guiding pipe 31 Is supplied.

In the first sulfuric acid-containing liquid circulation pipe 51B and/or the second sulfuric acid-containing liquid circulation pipe 71B, the opposite is provided on the downstream side of the liquid feeding device (the second liquid feeding device 56 and/or the third liquid feeding device 76). A sulfuric acid concentration meter 64 for measuring the sulfuric acid concentration of the sulfuric acid-containing liquid circulating in the second circulation tank 51, the second circulation pipe 53 and the third circulation pipe 73. Furthermore, if the sulfuric acid concentration of the sulfuric acid-containing liquid circulating in the second circulation tank 51, the second circulation pipe 53 and the third circulation pipe 73 is lower than the lower limit concentration, the sulfuric acid supplement pipe 44 is opened and closed in the sulfuric acid supplement unit 25 The sulfuric acid replenishing valve 45 is opened, and the sulfuric acid-containing liquid is supplied to the first circulation tank 22. As a result, the sulfuric acid concentration of the sulfuric acid-containing liquid circulating in the second circulation tank 51, the second circulation pipe 53 and the third circulation pipe 73 will increase. Along with this, after a short period of time has elapsed thereafter, in the second The sulfuric acid concentration of the sulfuric acid-containing liquid circulated by the circulation tank 51, the second circulation pipe 53, and the third circulation pipe 73 becomes higher.

FIG. 3 is a schematic cross-sectional view for explaining a configuration example of the processing unit 6.

The processing unit 6 includes: a box-shaped chamber 107, which has an internal space; a rotating chuck (substrate holding unit) 108, which holds a substrate W in a horizontal position in the chamber 107 so that the substrate W is passed around The vertical axis of rotation A1 at the center of the substrate W rotates; the SPM nozzle 13 is used to supply SPM to the upper surface of the substrate W (the surface Wa of the substrate W (see FIG. 4B)) held by the rotating chuck 108; rinse liquid The supply unit 110 is used to align the upper surface of the substrate W held by the rotating chuck 108 (the surface Wa of the substrate W (see 4B)) supply the rinse liquid; the lower surface nozzle 91, which discharges the processing liquid toward the center of the lower surface of the substrate W held by the spin chuck 108 (the back surface Wb of the substrate W (refer to Fig. 7A)); and a cylinder A processing cup 111 in a shape that surrounds the rotating chuck 108.

The chamber 107 includes: a box-shaped partition wall 112; FFU (fan, filter, unit) 114, which serves as an air supply unit that delivers clean air from the upper part of the partition wall 112 to the partition wall 112 (equivalent to the inside of the chamber 107) ; And an exhaust device (not shown), which exhausts the gas in the chamber 107 from the lower part of the partition wall 112. The FFU 114 is disposed above the partition wall 112 and is installed on the ceiling of the partition wall 112. The FFU 114 transports clean air into the chamber 107 from the ceiling of the partition wall 112. An exhaust device (not shown) is connected to the bottom of the processing cup 111 via an exhaust duct 113 connected to the processing cup 111, and sucks the gas in the processing cup 111 from the bottom of the processing cup 111. With the FFU 114 and an exhaust device (not shown), a downflow (downflow) is formed in the chamber 107.

As the rotary chuck 108, a clamping chuck which clamps the substrate W in the horizontal direction and holds the substrate W horizontally is used. Specifically, the rotating chuck 108 includes: a rotating motor (rotating unit) M; a rotating shaft 115 integrated with the drive shaft of the rotating motor M; and a disc-shaped rotating base 116 that is substantially horizontal It is mounted on the upper end of the rotating shaft 115.

The rotating base 116 includes a circular upper surface 116a having an outer diameter that is larger than the outer diameter of the substrate W and a level. On the upper surface 116a, a plurality of (three or more, for example, six) clamping members 117 are arranged on the peripheral edge portion of the upper surface 116a. The plurality of clamping members 117 are arranged on the periphery of the upper surface of the rotating base 116 at appropriate intervals on the circumference corresponding to the outer peripheral shape of the substrate W.

The SPM nozzle 13 is, for example, a direct-flow nozzle that discharges SPM in a continuous flow state. The SPM nozzle 13 is installed at the front end of the nozzle arm 119. The SPM nozzle 13 is for example The nozzle arm 119 is attached to the nozzle arm 119 in a vertical posture in which the processing liquid (SPM) is discharged to the upper surface (surface Wa) of the substrate W in the vertical direction. The nozzle arm 119 extends in the horizontal direction. In addition, the nozzle arm 119 is coupled with a nozzle moving unit 120 that moves the SPM nozzle 13 by moving the nozzle arm 119. The nozzle moving unit 120 includes an electric motor.

The nozzle moving unit 120 horizontally moves the nozzle arm 119 around a vertical swing axis set around the processing cup 111 to move the SPM nozzle 13 horizontally. The nozzle moving unit 120 moves the SPM nozzle 13 horizontally between the processing position and the retreat position. The processing position is the position where the SPM discharged from the SPM nozzle 13 impinges on the upper surface (surface Wa) of the substrate W, and the retreat The position is the position where the SPM nozzle 13 is located around the rotating chuck 108 when viewed from above. In the present embodiment, the processing position is, for example, the center position of the SPM discharged from the SPM nozzle 13 on the upper surface (surface Wa) of the substrate W in the center of the center portion.

The processing liquid supply device further includes a hydrogen peroxide water supply unit 122 that supplies _{hydrogen peroxide water (H 2} O _{2) to the SPM nozzle 13.} The hydrogen peroxide water supply unit 122 includes: a hydrogen peroxide water pipe 135 connected to the SPM nozzle 13; a hydrogen peroxide water valve 136 for opening and closing the hydrogen peroxide water pipe 135; and hydrogen peroxide water The flow rate adjusting valve (mixing ratio changing unit) 137 adjusts the opening degree of the hydrogen peroxide water valve 136 to adjust the flow rate of the hydrogen peroxide water flowing through the hydrogen peroxide water valve 136. The hydrogen peroxide water flow adjustment valve 137 may also be a valve body that includes a valve seat inside, a valve body that opens and closes the valve seat, and an actuator that moves the valve body between an open position and a closed position. constitute. The hydrogen peroxide water of about normal temperature (about 23° C. to about 25° C.), which is not temperature-adjusted, is supplied to the hydrogen peroxide water pipe 135 from a hydrogen peroxide water supply source (not shown).

If the first sulfuric acid-containing liquid valve 60 and hydrogen peroxide water valve 136 are opened, the high-temperature (about 165°C) sulfuric acid liquid from the second sulfuric acid-containing liquid supply pipe 77 and hydrogen peroxide from the hydrogen peroxide water pipe 135 The water is supplied toward the housing (not shown) of the SPM nozzle 13, and is sufficiently mixed (stirred) in the housing. By this mixing, the sulfuric acid-containing liquid and the hydrogen peroxide water are uniformly mixed with each other, and a mixed liquid of the sulfuric acid-containing liquid and the hydrogen peroxide water is generated by the reaction of the sulfuric acid-containing liquid contained in the sulfuric acid liquid and the hydrogen peroxide water (SPM). SPM contains peroxymonosulfuric acid (H ₂ SO ₅ ), which has strong oxidizing power, and is heated to a higher temperature (for example, About 190℃~about 220℃). The generated high-temperature SPM is discharged from the discharge port opened at the front end (for example, the lower end) of the housing of the SPM nozzle 13. The flow rate of the sulfuric acid-containing liquid supplied to the SPM nozzle 13 is changed by the second sulfuric acid-containing liquid flow rate adjustment valve 79. The flow rate of the hydrogen peroxide water supplied to the SPM nozzle 13 is changed by the hydrogen peroxide water flow rate adjustment valve 137. Therefore, the mixing ratio of the sulfuric acid-containing liquid and the hydrogen peroxide water is changed by the second sulfuric acid-containing liquid flow rate adjustment valve 79 and the hydrogen peroxide water flow rate adjustment valve 137.

The rinsing liquid supply unit 110 includes a rinsing liquid nozzle 147 that discharges the rinsing liquid toward the upper surface (surface Wa) of the substrate W. The flushing liquid nozzle 147 is, for example, a direct-flow nozzle that discharges liquid in a continuous flow state. The flushing liquid nozzle 147 is a fixed nozzle that is fixed relative to the partition wall 112 of the chamber 107. The discharge port of the rinse liquid nozzle 147 is directed toward the center of the upper surface (surface Wa) of the substrate W. The flushing liquid nozzle 147 may also be a scanning nozzle that can move in the chamber 107. That is, the rinsing liquid supply unit 110 may also be provided with a position of the rinsing liquid on the upper surface (surface Wa) of the substrate W on the upper surface (surface Wa) of the substrate W by moving the rinsing liquid nozzle 147. The nozzle moving unit that moves inside.

The rinsing liquid nozzle 147 is connected to a rinsing liquid piping 148 that guides the rinsing liquid from the rinsing liquid supply source. In the middle of the rinsing liquid pipe 148, a rinsing liquid valve 149 for switching the supply/stop of the rinsing liquid from the rinsing liquid nozzle 147 is interposed. If the flushing fluid valve 149 is opened, the flushing fluid is supplied from the flushing fluid pipe 148 to the flushing fluid. The washing liquid nozzle 147 is discharged from a discharge port provided at the lower end of the washing liquid nozzle 147.

When the flushing fluid valve 149 is closed, the supply of flushing fluid from the flushing fluid pipe 148 to the flushing fluid nozzle 147 is stopped. The rinsing fluid is, for example, DIW (Deionized Water), but it is not limited to DIW, and can also be carbonated water, electrolyzed ionized water, hydrogen water, ozone water, ammonia water, and dilution concentrations (for example, about 10 ppm to 100 ppm). Any of hydrochloric acid in water. The rinsing liquid may be at room temperature (20-40° C.), or it may be heated before being supplied to the substrate W.

The bottom surface nozzle 91 has a single discharge port 91a facing the center portion of the bottom surface (back surface Wb) of the substrate W held by the spin chuck 108. The discharge port 91a discharges the liquid vertically upward. The discharged liquid is incident substantially perpendicularly to the center portion of the back surface Wb of the substrate W held by the rotating chuck 108. The lower surface supply pipe 92 is connected to the lower surface nozzle 91. The lower surface supply pipe 92 is inserted into the inside of the rotating shaft 115 constituted by a hollow shaft arranged vertically. The second sulfuric acid-containing liquid supply pipe 77 and the rinse liquid pipe 93 are respectively connected to the lower surface supply pipe 92.

A flushing fluid valve 94 for opening and closing the flushing fluid piping 93 is interposed in the flushing fluid piping 93. The rinsing liquid supplied to the rinsing liquid piping 93 is, for example, water at room temperature (approximately 23° C. to approximately 25° C.). In this embodiment, any one of water system pure water (deionized water), carbonated water, electrolyzed ionized water, hydrogen water, ozone water, and ammonia water with a dilution concentration (for example, about 10 to 100 ppm).

If the second sulfuric acid-containing liquid valve 80 is opened with the flushing liquid valve 94 closed, the high-temperature (about 165°C) sulfuric acid liquid from the second sulfuric acid-containing liquid supply pipe 77 will pass through the lower surface supply pipe 92. It is supplied into the casing (not shown) of the nozzle 91 toward the lower surface. The high-temperature sulfuric acid liquid supplied to the lower surface nozzle 91 is discharged substantially vertically upward from the discharge port 91a. The high-temperature sulfuric acid liquid discharged from the nozzle 91 on the lower surface (the second containing The sulfuric acid solution) is incident substantially perpendicularly to the center portion of the back surface Wb of the substrate W held by the rotating chuck 108.

If the rinsing liquid valve 94 is opened with the second sulfuric acid-containing liquid valve 80 closed, the rinsing liquid from the rinsing liquid supply source is supplied to the lower surface nozzle 91 via the rinsing liquid pipe 93 and the lower surface supply pipe 92. The rinsing liquid supplied to the lower surface nozzle 91 is discharged substantially vertically upward from the discharge port 91a. The rinse liquid discharged from the lower surface nozzle 91 enters the center portion of the back surface Wb of the substrate W held by the spin chuck 108 substantially perpendicularly.

The processing cup 111 is arranged on the outer side (the direction away from the rotation axis A1) than the substrate W held by the rotating chuck 108. The processing cup 111 surrounds the side of the rotating base 116. When the rotating chuck 108 rotates the substrate W, if the processing liquid is supplied to the substrate W, the processing liquid supplied to the substrate W will be thrown away from the periphery of the substrate W. When the processing liquid is supplied to the substrate W, the upper end 111 a of the processing cup 111 opened upward is arranged above the spin base 116. Therefore, the processing liquid such as chemical liquid or water discharged to the periphery of the substrate W is received by the processing cup 111. Then, the processing liquid received by the processing cup 111 is transported to the first circulation tank 22 of the first reservoir 11, or is transported to the waste liquid device (not shown) via the cooling unit (not shown).

The processing cup 111 includes a plurality of cylindrical baffles (the first, second, and third baffles 143, 144, 145), which receive the processing liquid (chemical solution or rinse liquid) scattered around the substrate W ); a plurality of ring-shaped cups (the first cup 141 and the second cup 142), which are supported by a plurality of baffles (the first, second and third baffles 143, 144, 145) And the cylindrical member 140, which surrounds a plurality of baffles (the first, second and third baffles 143, 144, 145) and a plurality of cups (the first cup 141 and the second cup) Body 142).

The processing cup 111 further includes a baffle lifting unit (switching unit Yuan) 146, the baffle lifting unit 146 is a device that lifts and lowers each baffle (the first, second, and third baffles 143, 144, 145) independently. The baffle lifting unit 146 includes, for example, an electric motor, which generates power, and a ball screw mechanism, which transmits the power of the electric motor to any baffle (the first, second, or third baffle 143, 144, 145) . If the barrier lifting unit 146 lifts at least one of the three barriers (the first, second, and third barriers 143, 144, 145), the state of the processing cup 111 is switched.

As described later, the state of the processing cup 111 will be switched to any one of the following states: the upper ends of all baffles (the first, second, and third baffles 143, 144, 145) are arranged on the substrate The retracted state below W (the state shown in FIG. 5); the first facing state where the first baffle 143 faces the peripheral end of the substrate W; the second baffle 144 faces the peripheral end of the substrate W The second opposing state; and the third opposing state where the third baffle 145 faces the peripheral end of the substrate W.

The first cup 141 surrounds the rotating chuck 108 inside the cylindrical member 140. The first cup 141 partitions a ring-shaped first groove 150 into which a processing liquid used for processing the substrate W flows. At the lowest part of the bottom of the first groove 150, a drain port 151 is opened, and a drain pipe 152 is connected to the drain port 151. The treatment liquid introduced into the drain pipe 152 is sent to a waste liquid device (not shown) via a cooling unit (not shown), and is processed by the waste liquid device.

The second cup 142 surrounds the first cup 141 inside the cylindrical member 140. The second cup 142 partitions a ring-shaped second groove 153 into which the processing liquid used for processing the substrate W flows. A recovery port 154 is opened at the lowest part of the bottom of the second groove 153, and the upstream end of the recovery pipe 156 is connected to the recovery port 154. The recovery pipe 156 is connected to the first circulation tank 22 of the first reservoir 11 via the recovery and discharge pipe 26.

The innermost first baffle 143 surrounds the rotating chuck 108 inside the cylindrical member 140. The first baffle 143 includes: a cylindrical lower end 163, which surrounds the rotating clamp Around the head 108; the cylindrical portion 164, which extends outward from the upper end of the lower end 163 (from the direction away from the rotation axis A1 of the substrate W); the cylindrical middle section 165, which extends from the upper end of the cylindrical portion 164 It extends vertically upward; and the annular upper end 166 extends diagonally upward from the upper end of the middle section 165 toward the inward direction (the direction close to the rotation axis A1 of the substrate W).

The lower end 163 of the first baffle 143 is located on the first groove 150 of the first cup 141. The inner peripheral end of the upper end portion 166 of the first baffle 143 has a circular shape with a larger diameter than the substrate W held by the rotating chuck 108 in a plan view. As shown in FIG. 5, the cross-sectional shape of the upper end 166 of the first baffle 143 is linear. The cross-sectional shape of the upper end portion 166 may be a shape other than a linear shape such as an arc.

The second baffle 144 second from the inside surrounds the first baffle 143 inside the cylindrical member 140. The second baffle plate 144 has a cylindrical portion 167 that surrounds the first baffle plate 143, and an annular upper end portion 168 that extends from the upper end of the cylindrical portion 167 to the center side (in the direction close to the rotation axis A1 of the substrate W ) Extend diagonally upward. The cylindrical portion 167 of the second baffle plate 144 is located on the second groove 153 of the second cup body 142.

The inner peripheral end of the upper end 168 of the second baffle plate 144 has a circular shape with a larger diameter than the substrate W held by the rotating chuck 108 in a plan view. The cross-sectional shape of the upper end 168 of the second baffle 144 is linear. The cross-sectional shape of the upper end 168 may be a shape other than a linear shape such as an arc. The upper end 168 of the second baffle 144 overlaps the upper end 166 of the first baffle 143 in the vertical direction. The upper end 168 of the second baffle 144 is formed to approach the upper end 166 of the first baffle 143 while maintaining a slight gap in a state where the first baffle 143 and the second baffle 144 are closest.

The third baffle 145 which is the third from the inside surrounds the second baffle 144 inside the cylindrical member 140. The third baffle 145 has a cylindrical portion 170 that surrounds the second baffle 144; and the annular upper end portion 171, which extends diagonally upward from the upper end of the cylindrical portion 170 on the central side (the direction approaching the rotation axis A1 of the substrate W). The inner peripheral end of the upper end portion 171 has a circular shape with a larger diameter than the substrate W held by the rotating chuck 108 in a plan view. The cross-sectional shape of the upper end 171 is linear. The cross-sectional shape of the upper end 171 may be a shape other than a linear shape such as an arc.

The first groove 150 of the first cup 141, the inner wall 143a of the first baffle 143, and the outer periphery of the housing of the rotating chuck 108 separate the first groove where the chemical solution used in the processing of the substrate W is guided. The circulation space (in other words, the drainage space) SP1. The second groove 153 of the second cup 142, the outer wall 143b of the first baffle plate 143, and the inner wall 144a of the second baffle plate 144 separate the second flow through which the chemical solution used in the processing of the substrate W is guided Space (in other words, reclaimed space) SP2. The first circulation space SP1 and the second circulation space SP2 are separated from each other by the first baffle 143.

The baffle lift unit 146 positions each baffle (the first baffle 143, the second baffle 144, and the third baffle 145) on the upper end of the baffle at an upper position higher than the substrate W and the upper end of the baffle at It moves up and down between the lower positions below the substrate W. The barrier lifting unit 146 can hold each barrier (the first barrier 143, the second barrier 144, and the third barrier 145) at any position between the upper position and the lower position. The supply of the processing liquid toward the substrate W is performed in a state where any one of the baffles (the first baffle 143, the second baffle 144, or the third baffle 145) faces the peripheral end of the substrate W.

In the first opposing state of the processing cup 111 facing the innermost first baffle 143 and the peripheral end of the substrate W, the first baffle 143, the second baffle 144, and the third baffle 145 are all It is arranged at the upper position (processing height position). In the second opposing state of the processing cup 111 facing the peripheral end of the substrate W with the second baffle 144 second from the inside, the second baffle 144 and the third baffle 145 are arranged at Up position, and the first baffle 143 It is placed in the lower position. In the third facing state where the outermost third baffle 145 and the peripheral end of the substrate W face the processing cup 111, the third baffle 145 is arranged at the upper position, and the first baffle 143 and The second baffle 144 is arranged at the lower position. In the retracted state (see FIG. 5) in which all the baffles (the first baffle 143, the second baffle 144, and the third baffle 145) are retracted from the peripheral end surface of the substrate W, the first baffle 143 and the second baffle The plate 144 and the third baffle 145 are all arranged in the lower position.

FIG. 4A is a block diagram for explaining the electrical configuration of the substrate processing apparatus 1.

The control device 4 is, for example, a computer. The control device 4 has a calculation unit such as a CPU (Central Processing Unit), a storage unit such as a fixed memory device, a hard disk drive, and the like, and an input/output unit for input and output of information. The storage unit includes a computer-readable recording medium that records a computer program executed by the arithmetic unit. A group of steps for causing the control device 4 to execute the resist removal process described later is incorporated in the recording medium.

The control device 4 controls the rotation motor M, the nozzle moving unit 120, the flap lifting unit 146, the first liquid feeding device 32, the second liquid feeding device 56, the third liquid feeding device 76, and the first circulation in accordance with a predetermined program. Operations of the heater 24, the second circulation heater 52, the first heater 54, the third circulation heater 72, the second heater 74, and the like. In addition, the control device 4 controls the on-off valve 38, the return valve 41, the sulfuric acid replenishing valve 45, the first sulfuric acid-containing liquid valve 60, the second sulfuric acid-containing liquid valve 80, the flushing liquid valve 94, and hydrogen peroxide in accordance with a predetermined program. The opening and closing operations of the water valve 136, the flushing liquid valve 149, and the like. In addition, the control device 4 adjusts the opening degrees of the first sulfuric acid-containing liquid flow rate adjustment valve 59, the second sulfuric acid-containing liquid flow rate adjustment valve 79, and the hydrogen peroxide water flow rate adjustment valve 137 in accordance with a predetermined program. The measurement values of the sulfuric acid concentration meter 64 and the liquid meter 65 are respectively input to the control device 4.

FIG. 4B is an enlarged view showing the substrate to be processed by the substrate processing apparatus 1 Sectional view of the surface Wa of W. The substrate W to be processed is, for example, a silicon wafer, and the pattern 100 is formed on the surface Wa that is the pattern formation surface. The pattern 100 is, for example, a fine pattern. As shown in FIG. 4B, the pattern 100 may be a structure in which the structures 101 having a convex shape (columnar shape) are arranged in rows and columns. In this case, the line width W1 of the structure 101 is set to, for example, about 10 nm to 45 nm, and the gap W2 of the pattern 100 is set to, for example, about 10 nm to several μm. The film thickness T of the pattern 100 is, for example, about 1 μm. In addition, the aspect ratio of the pattern 100 (the ratio of the film thickness T to the line width W1) may be, for example, about 5 to 500 (typically, about 5 to 50).

In addition, the pattern 100 may be a linear pattern formed by fine grooves repeatedly arranged. In addition, the pattern 100 can also be formed by providing a plurality of micropores (voids or pores) in the film.

The pattern 100 includes, for example, an insulating film. In addition, the pattern 100 may include a conductive film. More specifically, the pattern 100 may be formed of a laminated film in which a plurality of layers of films are laminated, and may include an insulating film and a conductive film. The pattern 100 may also be a pattern composed of a single layer film. The insulating film may also be a silicon oxide film (SiO ₂ film) or a silicon nitride film (SiN film). In addition, the conductive film may be an amorphous silicon film introduced with impurities for lowering resistance, or a metal film (for example, a metal wiring film).

In addition, the pattern 100 may be a hydrophilic film. As the hydrophilic film, TEOS film (a kind of silicon oxide film) can be exemplified.

FIG. 5 is a flowchart of a first substrate processing example executed by the processing unit 6.

Hereinafter, referring to FIGS. 1 to 5, a first substrate processing example, which is an example of the processing of the substrate W, will be described. An example of the treatment of the substrate W is a resist removal treatment for removing the resist from the upper surface (main surface) of the substrate W. The resist is, for example, a photoresist formed of a compound containing carbon. The substrate W has not been subjected to a process for ashing the resist.

When the substrate W is processed by the substrate processing apparatus 1, the control device 4 retreats from above all the nozzles from the rotating chuck 108 and all the baffles (the first baffle 143, the second baffle 144, and the third baffle 145) are located In the lower position, the first substrate transfer robot CR1 (refer to FIG. 1) and the second substrate transfer robot CR2 ( Refer to the manipulator of FIG. 1) to enter the inside of the chamber 107. Thereby, the substrate W is transferred to the rotating chuck 108 with the surface thereof facing up, and is held by the rotating chuck 108.

After the substrate W is held by the rotating chuck 108, the control device 4 causes the rotating motor M to start rotating. Thereby, the rotation of the substrate W is started (S2 in FIG. 5). The rotation speed of the substrate W is increased to a predetermined liquid processing speed (within the range of 300 to 1500 rpm, for example, 300 rpm), and is maintained at the liquid processing speed. Then, the rotation speed of the substrate W reaches the liquid processing speed.

After the rotation speed of the substrate W reaches the liquid processing speed, the control device 4 performs a sulfuric acid-containing liquid back surface supply step of supplying a high-temperature (about 165° C.) sulfuric acid liquid to the back surface Wb of the substrate W (S3 in FIG. 5). The sulfuric acid-containing liquid back surface supply step S3 is executed before the start of the SPM surface supply step S4 described below.

Specifically, the control device 4 opens the second sulfuric acid-containing liquid valve 80. Thereby, the high-temperature (about 165°C) sulfuric acid-containing liquid from the second sulfuric acid-containing liquid supply pipe 77 is supplied to the lower surface nozzle 91 through the lower surface supply pipe 92, and is substantially vertical from the discharge port 91a of the lower surface nozzle 91 Spit upwards. Thereby, the high-temperature sulfuric acid-containing liquid (the second sulfuric acid-containing liquid) enters the center portion of the back surface Wb of the substrate W approximately perpendicularly. The sulfuric acid-containing liquid supplied to the center portion of the back surface Wb of the substrate W receives the centrifugal force generated by the rotation of the substrate W, and spreads to the entire area of the back surface Wb of the substrate W. Thereby, the sulfuric acid-containing liquid is supplied to the entire area of the back surface Wb of the substrate W. Sulfur-containing moving on the back side Wb of the substrate W The acid liquid scatters from the peripheral edge of the substrate W toward the side of the substrate W.

Next, the control device 4 executes the SPM surface supply step (S4 in FIG. 5).

Specifically, the control device 4 controls the nozzle moving unit 120 to move the SPM nozzle 13 from the retracted position to the processing position. In addition, the control device 4 opens the first sulfuric acid-containing liquid valve 60 and the hydrogen peroxide water valve 136 simultaneously. Thereby, the sulfuric acid-containing liquid is supplied to the SPM nozzle 13 through the second sulfuric acid-containing liquid supply pipe 77, and the hydrogen peroxide water is supplied to the SPM nozzle 13 through the hydrogen peroxide water pipe 135. The sulfuric acid-containing liquid and the hydrogen peroxide water are mixed inside the SPM nozzle 13 to generate SPM at a high temperature (for example, 190 to 220° C.). The SPM is discharged from the discharge port of the SPM nozzle 13 and is deposited on the center portion of the upper surface (surface Wa) of the substrate W.

After the SPM discharged from the SPM nozzle 13 reaches the surface Wa of the substrate W, it flows outward along the surface Wa of the substrate W by centrifugal force. Therefore, SPM is supplied to the entire area of the surface Wa of the substrate W, and a liquid film of SPM covering the entire area of the surface Wa of the substrate W is formed on the substrate W. Thereby, the resist chemically reacts with the SPM, and the resist on the substrate W is removed from the substrate W by the SPM. The SPM scatters from the peripheral edge of the substrate W toward the side of the substrate W.

Furthermore, the control device 4 can also control the nozzle moving unit 120 in the SPM surface supply step S4 so that the SPM nozzle 13 is positioned at the peripheral position opposite to the peripheral edge of the surface Wa of the substrate W, and at the center of the surface Wa of the substrate W Move between the opposite central positions. In this case, since the spotting position of the SPM on the upper surface of the substrate W passes through the entire area of the surface Wa of the substrate W, the entire spot of the surface Wa of the substrate W will be scanned by the spotting position of the SPM. Thereby, the entire area of the surface Wa of the substrate W will be uniformly processed.

If a predetermined period (e.g. about 27 Sec), the control device 4 closes the first sulfuric acid-containing liquid valve 60 and the hydrogen peroxide water valve 136, and stops the discharge of SPM from the SPM nozzle 13. With this, the SPM surface supply step S4 ends. After that, the control device 4 controls the nozzle moving unit 120 (refer to FIG. 4) to return the SPM nozzle 13 to the retracted position. As described later, the SPM surface supply step S4 includes a first surface supply step S41 and a second surface supply step S42 to be executed after the first surface supply step S41 is completed.

Next, a rinsing step of supplying rinsing liquid to the substrate W is performed (S5 in FIG. 5). Specifically, the control device 4 opens the rinsing liquid valve 149 to cause the rinsing liquid nozzle 147 to discharge the rinsing liquid toward the center of the surface Wa of the substrate W. The rinsing liquid discharged from the rinsing liquid nozzle 147 is deposited on the center portion of the surface Wa of the substrate W covered by the SPM. The rinsing liquid impinging on the central part of the surface Wa of the substrate W is subjected to the centrifugal force generated by the rotation of the substrate W and flows on the upper surface of the substrate W toward the peripheral edge of the substrate W. Thereby, the SPM on the substrate W will be pushed and flowed outward by the flushing liquid, and then discharged toward the periphery of the substrate W. As a result, the SPM and the resist are washed away from all areas of the surface Wa of the substrate W. If a predetermined period has elapsed since the start of the flushing step S5, the control device 4 will close the flushing liquid valve 149 to stop the flushing liquid nozzle 147 from discharging the flushing liquid.

Next, a drying step (S6 in FIG. 5) for drying the substrate W is performed. Specifically, the control device 4 controls the rotation motor M to accelerate the substrate W to a drying rotation speed ( For example, thousands of rpm), and the substrate W is rotated at a dry rotation speed. As a result, the liquid that is applied to the substrate W by a large centrifugal force, and the liquid attached to the substrate W will be thrown away from the periphery of the substrate W. In this way, the liquid is removed from the substrate W, and the substrate W is dried. Then, if a predetermined period of time has elapsed since the high-speed rotation of the substrate W was started, the control device 4 stops the rotation motor M, and the rotation chuck The rotation of the substrate W performed by 108 is stopped (S7 in FIG. 5).

Next, the substrate W is carried out from the chamber 107 (S8 in FIG. 5). Specifically, the control device 4 makes the first substrate transfer robot CR1 and the second substrate transfer robot CR1 and the second substrate transfer robot in a state where all the baffles (the first baffle 143, the second baffle 144, and the third baffle 145) are in the lower position. The CR2 manipulator enters the chamber 107. Then, the control device 4 causes the robot arms of the first substrate transfer robot CR1 and the second substrate transfer robot CR2 to hold the substrate W on the rotating chuck 108. After that, the control device 4 causes the robot arms of the first substrate transfer robot CR1 and the second substrate transfer robot CR2 to evacuate from the chamber 107. Thereby, the substrate W from which the resist has been removed from the surface Wa (for example, the device forming surface) is carried out from the chamber 107.

Next, in the SPM surface supply step (S4 in FIG. 5), the supply flow rate of the sulfuric acid solution toward the upper and lower surfaces of the substrate W and the supply flow rate of the hydrogen peroxide water toward the upper surface of the substrate W, and the first baffle The operation of 143 and the second baffle 144 will be described.

FIG. 6 is a timing chart showing the operations and the like of the first baffle 143 and the second baffle 144 in the first substrate processing example. In FIG. 6, the recovery ON indicates that the liquid (sulfuric acid-containing liquid or SPM) discharged from the substrate W flows into the recovery pipe 156 through the second baffle 144, and the recovery OFF indicates the liquid discharged from the substrate W ( When the sulfuric acid-containing liquid or SPM is stopped from flowing into the recovery pipe 156. In FIG. 6, the discharge ON indicates that the liquid (sulfuric acid-containing liquid or SPM) discharged from the substrate W flows into the discharge pipe 152 through the first baffle 143, and the discharge OFF indicates the discharge from the substrate W. When the liquid (containing sulfuric acid or SPM) is stopped flowing into the drain pipe 152.

FIG. 7A is a diagram for explaining a diagram of the step S3 of supplying the sulfuric acid-containing liquid backside. 7B and 7C are diagrams for explaining the diagram of the SPM surface supply step S4.

Hereinafter, refer to FIGS. 3 to 6. Refer to Figures 7A to 7C as appropriate. The following operations and the like are executed by the control device 4 controlling the substrate processing apparatus 1. In other words, the control device 4 is programmed to perform the following actions and the like.

As shown in FIG. 6, the processing cup 111 is set to have three baffles (first baffle 143, second baffle 143, The second baffle 144 in the middle of the baffle 144 and the third baffle 145) faces a second opposite state with the peripheral end of the substrate W.

If the second sulfuric acid-containing liquid valve 80 is opened at the time T1 shown in FIG. 6, as shown in FIG. The liquid is discharged from the lower surface nozzle 91 toward the back surface Wb of the substrate W (the sulfuric acid-containing liquid back surface supply step S3 in FIG. 5). As a result, as shown in FIG. 7A, the entire area of the back surface Wb of the substrate W is covered by the liquid film containing the sulfuric acid solution. The substrate W is heated by the high temperature liquid film containing sulfuric acid solution.

As shown in FIG. 7A, the sulfuric acid-containing liquid discharged from the substrate W is received by the inner wall 144 a of the second baffle 144 and guided by the second cup 142. Then, the sulfuric acid-containing liquid in the second cup body 142 is sent to the first circulation tank 22 of the first liquid storage portion 11 via the recovery pipe 156. Thereby, the sulfuric acid-containing liquid supplied to the substrate W is recovered (recovery step. Recovery shown in FIG. 6 is ON). If a predetermined period has passed since the second sulfuric acid-containing liquid valve 80 was opened (a sufficient period required to heat the entire substrate W to the same temperature as the liquid temperature of the sulfuric acid-containing liquid. For example, about 5 seconds), the first 2 The sulfuric acid-containing liquid valve 80 will be closed at the time T2 shown in FIG. 6.

The shutter lifting unit 146 raises the first shutter 143 to the upper position after the second sulfuric acid-containing liquid valve 80 is closed. Therefore, the processing cup 111 is switched from the second facing state to the first facing state in which the first baffle 143 faces the peripheral end of the substrate W.

Thereafter, if the first sulfuric acid-containing liquid valve 60 and hydrogen peroxide water valve 136 are opened at the time T3 shown in FIG. 6, the sulfuric acid-containing liquid and hydrogen peroxide water are supplied to the SPM nozzle 13 (the first of FIG. 5 Surface supply step S41). The sulfuric acid liquid and the hydrogen peroxide water are mixed in the SPM nozzle 13, and SPM is produced in the SPM nozzle 13. The produced SPM is ejected from the SPM nozzle 13 toward the upper surface of the substrate W. As a result, a liquid film of SPM covering the entire area of the surface Wa of the substrate W is formed. Then, the resist is removed from the surface Wa of the substrate W by the liquid film of the SPM. Since the SPM surface supply step S4 is started to be performed on the substrate W that has been sufficiently heated, the SPM resist removal efficiency is high. Because the resist removal efficiency is high, even if the processing period of the SPM surface supply step S4 (more specifically, the processing period of the first surface supply step S41) is not set to a long period, the surface Wa of the substrate W SPM is almost completely removed. Therefore, during the processing period of the SPM surface supply step S4 (more specifically, the processing period of the first surface supply step S41), the resist can be roughly removed from the surface Wa of the substrate W as much as possible. The ground is set for a short period of time (for example, about 12 seconds).

The SPM discharged from the substrate W is received by the inner wall 143 a of the first baffle 143 and guided by the first cup 141. Then, the SPM in the first cup 141 is discharged to the drain pipe 152 (the drain is turned on as shown in FIG. 6, the drain step).

During the predetermined period after the start of the SPM surface supply step S4, the SPM discharged from the substrate W contains a large amount of resist. If such a SPM containing a large amount of resist is used as a substrate to produce a sulfuric acid liquid, it will be difficult to produce a clean sulfuric acid liquid. Therefore, the SPM discharged from the substrate W during this period is not reused (not recycled) but discharged (discarded) from the unused place (non-recycling place), thereby preventing the SPM containing a large amount of resist from being When it is supplied to the sulfuric acid-containing liquid production device 8. Thereby, a clean sulfuric acid-containing liquid can be produced in the sulfuric acid-containing liquid production device 8.

On the other hand, from the viewpoint of environmental considerations, it is preferable to minimize the discharge (disposal) of SPM. Therefore, as long as the SPM discharged from the substrate W no longer contains a resist, it is better to recover the SPM and reuse it.

If a predetermined period has elapsed since the first sulfuric acid-containing liquid valve 60 and the hydrogen peroxide water valve 136 were started (it is a period in which the SPM discharged from the substrate W hardly contains resist. For example, about 12 seconds), stop The plate lifting unit 146 lowers the first flap 143 to the lower position at the time T5 shown in FIG. 6. Therefore, the processing cup 111 is switched to the second facing state in which the second baffle 144 faces the peripheral end of the substrate W. The SPM discharged from the substrate W is received by the inner wall 144a of the second baffle 144 and guided by the second cup 142 (the second surface supply step S42 in FIG. 5). Then, the SPM in the second cup body 142 is transported to the first circulation tank 22 of the first reservoir 11 via the recovery pipe 156. In this way, the SPM supplied to the substrate W is recovered (recovery step). In addition, the SPM surface supply step performed when the processing cup 111 is in the first opposed state in the SPM surface supply step S4 is referred to as the first surface supply step.

If a predetermined period (for example, about 15 seconds) has elapsed since the treatment cup 111 was switched to the second facing state, the first sulfuric acid-containing liquid valve 60 and the hydrogen peroxide water valve 136 will be at the time shown in FIG. 6 When T6 is turned off, the discharge of SPM from the SPM nozzle 13 will be stopped.

After the discharge of SPM from the SPM nozzle 13 is stopped at the time T6 shown in FIG. 6, the flap raising and lowering unit 146 causes the first flap 143 to rise from the lower position, and at the time T7 shown in FIG. It rises to the upper position. Thereby, the processing cup 111 is switched to the first baffle 143 facing the peripheral end of the substrate W in a state where the SPM nozzle 13 stops the discharge of SPM and the entire area of the upper surface of the substrate W is covered by the liquid film of SPM. The first opposite state. In this state, a rinse step of supplying a rinse liquid to the substrate W is performed (S5 in Figure 5). The drying step (S6 in FIG. 5) for drying the substrate W is performed in a state where the processing cup 111 is set to a third facing state where the third baffle plate 145 faces the peripheral end of the substrate W.

According to the above-mentioned present embodiment, the high-temperature sulfuric acid-containing liquid that becomes the base for the production of SPM supplied to the surface Wa of the substrate W is supplied to the back surface Wb of the substrate W (sulfuric acid-containing liquid back surface supply step S3). Since the high-temperature sulfuric acid liquid is supplied to the back surface Wb of the substrate W before the SPM surface supply step S4, the substrate W can be heated before the start of the SPM surface supply step S4. Therefore, it is possible to perform the SPM surface supply step S4 on the substrate W that has been sufficiently heated. Thereby, the resist removal efficiency of SPM can be improved. Since the resist removal efficiency is high, even if the processing period of the SPM surface supply step S4 (more specifically, the processing period of the first surface supply step S41) is set to be short, the resistance can be removed from the surface Wa of the substrate W. The etching agent is roughly removed. In this way, the consumption of SPM can be reduced, and even the consumption of sulfuric acid-containing liquid can be reduced.

In addition, the recovery step is executed in parallel with the sulfuric acid-containing liquid back surface supply step S3. That is, the sulfuric acid-containing liquid supplied to the back surface Wb of the substrate W for heating the substrate W is recovered by the recovery pipe 156, and based on the recovered sulfuric acid-containing liquid, the sulfuric acid-containing liquid is used in the sulfuric acid-containing liquid production device 8 Be made (making step of containing sulfuric acid liquid). Therefore, the sulfuric acid-containing liquid supplied to the back surface Wb of the substrate W for heating the substrate W can be reused as a base for the production of the SPM used in the SPM surface supply step S4. Thereby, heating of the substrate W using the sulfuric acid-containing liquid can be performed without increasing the consumption of the sulfuric acid-containing liquid.

In addition, the temperature of the substrate W immediately after being held by the spin chuck 108 is room temperature. If the sulfuric acid-containing liquid back surface supply step S3 is not executed before the SPM surface supply step S4 and a high temperature (for example, about 190°C to about 220°C) SPM is supplied to the substrate W at room temperature, the surface temperature of the substrate W will rise sharply, and There is a pair formed on the surface Wa of the substrate W The pattern 100 may cause the possibility of heat shock. The thermal shock system may be one of the reasons for the collapse of the pattern 100.

However, in this first substrate processing example, the sulfuric acid-containing liquid back surface supply step S3 is executed before the SPM surface supply step S4, thereby increasing the temperature of the substrate W before the SPM surface supply step S4 starts. Therefore, the substrate W can be started to perform the SPM surface supply step S4 in a state where the temperature of the substrate W has risen more than that immediately after being held by the spin chuck 108. Therefore, the occurrence of thermal shock caused by the supply of SPM can be suppressed, thereby suppressing or preventing damage to the pattern 100 formed on the surface Wa of the substrate W.

Moreover, in the first substrate processing example, as shown in FIG. 6, the mixing ratio (sulfuric acid flow rate/H ₂ O ₂ flow rate) is changed in the middle of the SPM surface supply step S4.

If the first sulfuric acid-containing liquid valve 60 and the hydrogen peroxide water valve 136 are opened at the time T3 shown in FIG. 6, the sulfuric acid-containing liquid is supplied to the SPM nozzle 13 at the first sulfuric acid-containing liquid flow rate, and the hydrogen peroxide water is It is supplied to the SPM nozzle 13 at the first H ₂ O _{2 flow rate.} Therefore, the sulfuric acid-containing liquid and the hydrogen peroxide water are mixed in the SPM nozzle 13 at the first mixing ratio (first sulfuric acid-containing liquid flow rate/first H ₂ O ₂ flow rate). Thereby, the first SPM is produced in the SPM nozzle 13 and discharged from the SPM nozzle 13 toward the upper surface of the substrate W (first surface supply step S41 in FIG. 5). As a result, the first SPM liquid film covering the entire area of the upper surface of the substrate W is formed.

Then, if a predetermined period has elapsed since the first sulfuric acid-containing liquid valve 60 and the hydrogen peroxide water valve 136 were opened, at least one of the second sulfuric acid-containing liquid flow rate adjustment valve 79 and the hydrogen peroxide water flow rate adjustment valve 137 The opening degree will be changed at the time T4 shown in Figure 6, and the sulfuric acid-containing liquid and hydrogen peroxide water will have a second mixing ratio greater than the first mixing ratio (the second sulfuric acid-containing liquid flow rate/the second H ₂ The O ₂ flow rate) is mixed in the SPM nozzle 13. FIG. 6 shows an example in which the opening degrees of both the first sulfuric acid-containing liquid flow rate adjustment valve 59 and the hydrogen peroxide water flow rate adjustment valve 137 are changed. Thereby, the second SPM is produced in the SPM nozzle 13, and is ejected from the SPM nozzle 13 toward the upper surface of the substrate W (the second surface supply step S42 in FIG. 5). As a result, the first SPM liquid film covering the entire area of the upper surface of the substrate W is replaced with the second SPM liquid film covering the entire area of the upper surface of the substrate W.

In the example shown in FIG. 6, the sulfuric acid-containing liquid is supplied to the SPM nozzle 13 at a flow rate of the second sulfuric acid-containing liquid that is larger than the flow rate of the first sulfuric acid-containing liquid, and the hydrogen peroxide water is supplied to the SPM nozzle 13 at a flow rate that is higher than that of the first H ₂ O ₂ flow rate. The smaller second H ₂ O ₂ flow rate is supplied to the SPM nozzle 13. The second sulfuric acid-containing liquid flow rate and the second H ₂ O ₂ flow rate can be set so that the flow rate of the SPM discharged from the SPM nozzle 13 can be maintained even if the mixing ratio (the ratio of the sulfuric acid liquid to the hydrogen peroxide water) is changed To be fixed, it can also be set to increase or decrease the flow rate of SPM discharged from the SPM nozzle 13. The mixing ratio can be continuously changed from the first mixing ratio to the second mixing ratio. Therefore, the SPM supplied to the upper surface of the substrate W continuously changes from a state where the concentration of hydrogen peroxide is high to a state where the concentration of the sulfuric acid-containing liquid is high.

Such a concentration change is not limited to the first substrate processing example, and may be performed in the second substrate processing example or the third substrate processing example described later.

FIG. 8 is a flowchart of a second example of substrate processing executed by the processing unit 6.

The difference between the second substrate processing example and the first substrate processing example is that the sulfuric acid-containing liquid back surface supply step S13 is not performed before the SPM surface supply step S4, but the sulfuric acid-containing liquid back surface supply step is performed in parallel with the SPM surface supply step S4. S13. In the second substrate processing example, the sulfuric acid-containing liquid back surface supply step S13 is performed in parallel with the second surface supply step S42.

After the substrate W is held by the rotating chuck 108, the control device 4 causes the rotating motor M to start rotating. Thereby, the rotation of the substrate W is started, and the rotation speed of the substrate W is increased to a predetermined liquid processing speed (S2 in FIG. 8).

After the rotation speed of the substrate W reaches the liquid processing speed, the control device 4 executes the first surface supply step S41 (see FIG. 8). In a state where the SPM nozzle 13 is arranged at the processing position, the control device 4 simultaneously opens the first sulfuric acid-containing liquid valve 60 and the hydrogen peroxide water valve 136. Thereby, the sulfuric acid-containing liquid and hydrogen peroxide water are supplied to the SPM nozzle 13, and high temperature (for example, about 190 to about 220° C.) SPM is generated inside the SPM nozzle 13. The SPM is discharged from the discharge port of the SPM nozzle 13 and supplied to the upper surface (surface Wa) of the substrate W.

In addition, in the first surface supply step S41, the processing cup 111 is set to the first facing state. Therefore, the SPM discharged from the substrate W is received by the inner wall 143 a of the first baffle 143 and guided by the first cup 141. Then, the SPM in the first cup 141 is discharged to the drain pipe 152 (the drain step).

If a predetermined period (for example, about 12 seconds) has passed since the first sulfuric acid-containing liquid valve 60 and the hydrogen peroxide water valve 136 were opened (if the SPM discharged from the substrate W contains almost no resist), the first 2Surface supply step S42 starts to be executed. That is, the shutter lifting unit 146 lowers the first shutter 143 to the lower position. Thereby, as shown in FIG. 9, the processing cup 111 is switched to the second facing state in which the second baffle 144 faces the peripheral end of the substrate W. As a result, the SPM discharged from the substrate W is received by the inner wall 144 a of the second baffle 144 and guided by the second cup 142.

As shown in FIG. 9, the sulfuric acid-containing liquid discharged from the substrate W is received by the inner wall 144 a of the second baffle 144 and guided by the second cup 142.

In addition, the sulfuric acid-containing liquid back surface supply step S13 is executed in parallel with the second surface supply step S42 (see FIG. 8). After the processing cup 111 is switched to the second facing state, the control device 4 opens the second sulfuric acid-containing liquid valve 80. Thereby, as shown in FIG. 9, a high-temperature (for example, about 165°C) sulfuric acid-containing liquid is supplied to the lower surface nozzle 91, and the high-temperature sulfuric acid-containing liquid (the second sulfur-containing liquid The acid solution is discharged from the lower surface nozzle 91 toward the back surface Wb of the substrate W (sulfuric acid-containing solution back surface supply step S13). As a result, as shown in FIG. 9, the entire area of the back surface Wb of the substrate W is covered by the liquid film containing the sulfuric acid solution. The substrate W is heated by a liquid film containing a high-temperature sulfuric acid solution.

12A to 12D are diagrams for explaining the removal (stripping) of the resist 181 formed on the surface Wa of the substrate W.

As shown in FIG. 12A, a predetermined pattern 100 is formed on the surface of the substrate W, and a resist 181 is formed to selectively cover the pattern 100. On the surface of the resist 181, there is a hardened layer 182 that has been altered by ion implantation as a pretreatment. That is, the resist 181 formed on the surface Wa of the substrate W includes a hardened layer 182 and a non-hardened layer 183 that has not been altered.

In the second surface supply step S42, at the same time that SPM having a high temperature of, for example, about 190°C to about 220°C is supplied to the surface Wa of the substrate W, a sulfuric acid solution having a high temperature of, for example, about 165°C is supplied to the back surface of the substrate W. Wb. Due to the supply of the sulfuric acid-containing liquid toward the back surface Wb of the substrate W, the substrate W is heated, and along with this, the entire area of the resist 181 including the bottom surface is heated. The resist 181 is efficiently heated by heating from the bottom surface of the resist 181. As a result, as shown in FIG. 12B, a gas 184 is generated in the non-hardened layer 183, and the generated gas 184 fills the non-hardened layer 183. Then, the pressure in the non-hardened layer 183 rises, thereby, as shown in FIG. 12C, cracks 185 are generated in the hardened layer 182.

Then, the cracks 185 formed in the hardened layer 182 of SPM enter the inside of the hardened layer 182. The entered SPM acts on the non-hardened layer 183 as shown in FIG. 12D, and the non-hardened layer 183 is removed from the surface Wa of the substrate W.

In the second surface supply step S42, SPM and the sulfuric acid-containing liquid are supplied to the second cup 142. Then, the SPM and the sulfuric acid-containing liquid in the second cup 142 are recovered and prepared. The pipe 156 is conveyed to the first circulation tank 22 of the first reservoir 11. Thereby, the SPM and the sulfuric acid-containing liquid supplied to the substrate W are recovered (recovery step).

If a predetermined period has passed since the second sulfuric acid-containing liquid valve 80 was opened (a sufficient period required for the entire substrate W to be heated to the same temperature as the liquid temperature of the sulfuric acid-containing liquid. For example, about 5 seconds), the control device 4, the second sulfuric acid-containing liquid valve 80 is closed, and the discharge of the sulfuric acid-containing liquid from the nozzle 91 on the lower surface is stopped. After that, if a predetermined period (for example, about 15 seconds) has elapsed since the first flap 143 is lowered, the control device 4 closes the first sulfuric acid-containing liquid valve 60 and the hydrogen peroxide water valve 136, and stops the flow from the SPM nozzle 13 The spit out of SPM.

According to the second substrate processing example, the high-temperature sulfuric acid-containing liquid used as a base for the production of SPM supplied to the surface Wa of the substrate W is supplied to the back surface Wb of the substrate W (sulfuric acid-containing liquid back surface supply step S13). The high-temperature sulfuric acid liquid is supplied to the back surface Wb of the substrate W in parallel with the second surface supply step S42 included in the SPM surface supply step S4, whereby the substrate W can be heated while the SPM surface supply step S4 is performed. Therefore, it is possible to cause the substrate W to perform the SPM surface supply step S4 on the substrate W while sufficiently raising the temperature of the substrate W. Thereby, the resist removal efficiency of SPM can be improved. Since the resist removal efficiency is high, even if the processing period of the SPM surface supply step S4 (more specifically, the processing period of the first surface supply step S41) is set to be short, the resist can be removed from the surface Wa of the substrate W. The etching agent is roughly removed. In this way, the consumption of SPM can be reduced, and even the consumption of sulfuric acid-containing liquid can be reduced.

In addition, in the second surface supply step S42, at the same time as the high-temperature SPM is supplied to the surface Wa of the substrate W, the high-temperature sulfuric acid liquid is supplied to the back surface Wb of the substrate W. The SPM can enter the non-hardened layer 183 from the cracks 185 of the hardened layer 182 generated by the heating of the resist 181, thereby improving the resist removal efficiency. Therefore, the SPM can be shortened The processing period of the surface supply step S4 (more specifically, the processing period of the first surface supply step S41).

In addition, the recovery step is executed in parallel with the sulfuric acid-containing liquid back surface supply step S13. That is, the sulfuric acid-containing liquid supplied to the back surface Wb of the substrate W for heating the substrate W is recovered by the recovery pipe 156, and based on the recovered sulfuric acid-containing liquid, the sulfuric acid-containing liquid is used in the sulfuric acid-containing liquid production device 8 Be made (making step of containing sulfuric acid liquid). Therefore, the sulfuric acid-containing liquid supplied to the back surface Wb of the substrate W for heating the substrate W can be reused as a base for the production of the SPM used in the SPM surface supply step S4. Thereby, heating of the substrate W using the sulfuric acid-containing liquid can be performed without increasing the consumption of the sulfuric acid-containing liquid.

In addition, by performing the second surface supply step S42 in parallel with the first surface supply step S41, and the sulfuric acid-containing liquid back surface supply step S13 performed in parallel with the recovery step, it is possible to avoid recovering a large amount of resist. SPM realizes the recovery of sulfuric acid liquid. Thereby, it is possible to use the sulfuric acid-containing liquid to heat the substrate W while preventing an increase in the consumption of the sulfuric acid-containing liquid without recovering the SPM containing a large amount of resist.

FIG. 10 is a flowchart of a third substrate processing example executed by the processing unit 6.

The difference between the third substrate processing example and the first substrate processing example is that the sulfuric acid-containing liquid back surface supply step S23 is not performed before the SPM surface supply step S4, but the sulfuric acid-containing liquid back surface supply step is performed in parallel with the SPM surface supply step S4. S23. In the third substrate processing example, the sulfuric acid-containing liquid back surface supply step S3 is performed in parallel with the first surface supply step S41.

After the substrate W is held by the rotating chuck 108, the control device 4 causes the rotating motor M to start rotating. Thereby, the rotation of the substrate W is started, and the rotation speed of the substrate W is increased to a predetermined liquid processing speed (S2 in FIG. 10).

After the rotation speed of the substrate W reaches the liquid processing speed, the control device 4 executes the first surface supply step S41 (see FIG. 10). In a state where the SPM nozzle 13 is arranged at the processing position, the control device 4 simultaneously opens the first sulfuric acid-containing liquid valve 60 and the hydrogen peroxide water valve 136. Thereby, the sulfuric acid-containing liquid and hydrogen peroxide water are supplied to the SPM nozzle 13, and high temperature (for example, about 190 to about 220° C.) SPM is generated inside the SPM nozzle 13. The SPM is discharged from the discharge port of the SPM nozzle 13 and supplied to the upper surface (surface Wa) of the substrate W.

In addition, in the first surface supply step S41, the processing cup 111 is set to the first facing state. Therefore, the SPM discharged from the substrate W is received by the inner wall 143 a of the first baffle 143 and guided by the first cup 141.

In addition, the sulfuric acid-containing liquid back surface supply step S23 is executed in parallel with the first surface supply step S41 (see FIG. 10). When the processing cup 111 is in the first opposed state, the control device 4 opens the second sulfuric acid-containing liquid valve 80. As a result, as shown in FIG. 11, a high-temperature (for example, about 165°C) sulfuric acid-containing liquid (second sulfuric acid-containing liquid) is supplied to the lower surface nozzle 91, and the high-temperature sulfuric acid liquid is directed from the lower surface nozzle 91 toward the substrate W. The back surface Wb is discharged (sulfuric acid-containing liquid back surface supply step S23). As a result, as shown in FIG. 11, the entire area of the back surface Wb of the substrate W is covered by the liquid film containing the sulfuric acid solution. The substrate W is heated by a high-temperature liquid film containing sulfuric acid solution. As shown in FIG. 11, the sulfuric acid-containing liquid discharged from the substrate W is received by the inner wall 143 a of the first baffle 143 and guided by the first cup 141.

As shown in FIG. 9, the sulfuric acid-containing liquid discharged from the substrate W is received by the inner wall 144 a of the second baffle 144 and guided by the second cup 142.

In addition, the sulfuric acid-containing liquid back surface supply step S13 is executed in parallel with the second surface supply step S42 (see FIG. 8). After the processing cup 111 is switched to the second facing state, the control device 4 opens the second sulfuric acid-containing liquid valve 80. With this, as shown in Figure 9, the high temperature (for example (About 165° C.) sulfuric acid-containing liquid is supplied to the lower surface nozzle 91, and the high-temperature sulfuric acid-containing liquid is discharged from the lower surface nozzle 91 toward the back surface Wb of the substrate W (sulfuric acid-containing liquid back surface supply step S13). As a result, as shown in FIG. 9, the entire area of the back surface Wb of the substrate W is covered by the liquid film containing the sulfuric acid solution. The substrate W is heated by a high-temperature liquid film containing sulfuric acid solution.

In the first surface supply step S41, at the same time that SPM having a high temperature of, for example, about 190°C to about 220°C is supplied to the surface Wa of the substrate W, a sulfuric acid solution having a high temperature of, for example, about 165°C is supplied to the substrate W. Wb on the back. The substrate W is heated by the supply of the sulfuric acid-containing liquid toward the back surface Wb of the substrate W, and along with this, the entire area of the resist 181 including the bottom surface is heated. The resist 181 is effectively heated by heating from the bottom surface of the resist 181, and the gas 184 generated in the non-hardened layer 183 fills the non-hardened layer 183. Then, the pressure in the non-hardened layer 183 increases, and as a result, cracks 185 are generated in the hardened layer 182. Then, the SPM that has entered the inside of the hardened layer 182 from the cracks 185 formed by the hardened layer 182 acts on the non-hardened layer 183 to remove the non-hardened layer 183 from the surface Wa of the substrate W (refer to FIGS. 12A to 12D).

In the first surface supply step S41, SPM and the sulfuric acid-containing liquid are supplied to the first cup 141. Then, the SPM and the sulfuric acid-containing liquid in the first cup 141 are discharged to the liquid discharge pipe 152 (liquid discharge step).

If a predetermined period has passed since the second sulfuric acid-containing liquid valve 80 was opened (a sufficient period required for the entire substrate W to be heated to the same temperature as the liquid temperature of the sulfuric acid-containing liquid. For example, about 5 seconds), the control device 4, the second sulfuric acid-containing liquid valve 80 is closed, and the discharge of the sulfuric acid-containing liquid from the nozzle 91 on the lower surface is stopped.

After that, if a predetermined period has elapsed since the first sulfuric acid-containing liquid valve 60 and the hydrogen peroxide water valve 136 were opened (it becomes a period during which the SPM discharged from the substrate W contains almost no resist. For example, about 12 seconds) ), the second surface supply step S42 is started. That is, the shutter lifting unit 146 lowers the first shutter 143 to the lower position. Thereby, the processing cup 111 is switched to the second facing state in which the second baffle 144 faces the peripheral end of the substrate W. As a result, the SPM discharged from the substrate W is received by the inner wall 144 a of the second baffle 144 and guided by the second cup 142. Then, the SPM in the second cup 142 is transported to the first circulation tank 22 of the first reservoir 11 via the recovery pipe 156. In this way, the SPM supplied to the substrate W is recovered (recovery step).

In addition, if a predetermined period (for example, about 15 seconds) has passed since the first flap 143 descended, the control device 4 closes the first sulfuric acid-containing liquid valve 60 and the hydrogen peroxide water valve 136, and stops the flow from the SPM nozzle 13 SPM's spit out.

According to the third substrate processing example, the high-temperature sulfuric acid-containing liquid that becomes the base for the production of SPM supplied to the surface Wa of the substrate W is supplied to the back surface Wb of the substrate W (sulfuric acid-containing liquid back surface supply step S23). The high-temperature sulfuric acid liquid is supplied to the back surface Wb of the substrate W in parallel with the first surface supply step S41 included in the SPM surface supply step S4, whereby the substrate W can be heated while performing the SPM surface supply step S4. Therefore, it is possible to perform the SPM surface supply step S4 on the substrate W while sufficiently raising the temperature of the substrate W. Thereby, the resist removal efficiency of SPM can be improved. Since the resist removal efficiency is high, even if the processing period of the SPM surface supply step S4 (more specifically, the processing period of the first surface supply step S41) is set to be short, the resist can be removed from the surface Wa of the substrate W. The etching agent is roughly removed. In this way, the consumption of SPM can be reduced, and even the consumption of sulfuric acid-containing liquid can be reduced.

In addition, in the second surface supply step S42, the high-temperature sulfuric acid solution and the high-temperature SPM are supplied to the surface Wa of the substrate W at the same time, and are supplied to the back surface Wb of the substrate W. The SPM can enter the non-hardened layer 183 from the cracks 185 of the hardened layer 182 generated by heating of the resist 181, thereby improving the resist removal efficiency. Therefore, it can be shortened The processing period of the SPM surface supply step S4 (more specifically, the processing period of the first surface supply step S41).

In particular, from the start of the SPM surface supply step S4, a high-temperature sulfuric acid solution is supplied to the back surface Wb of the substrate W. In this way, SPM can enter the non-hardened layer 183 at an earlier stage after the start of the SPM surface supply step S4. Thereby, the resist 181 can be removed from the surface Wa of the substrate W at an earlier stage after the start of the SPM surface supply step S4, thereby further shortening the processing period of the SPM surface supply step S4 (more Specifically, it is the processing period of the first surface supply step S41).

FIG. 13 is a schematic view of a substrate processing apparatus 201 according to another embodiment of the present invention viewed from above.

The difference between the substrate processing apparatus 201 of this embodiment and the embodiment shown in FIGS. 1 to 12D is that the processing liquid supply device, as the sulfuric acid-containing liquid production device, is provided with a second sulfuric acid-containing liquid produced in the processing unit 6 1 sulfuric acid-containing liquid production apparatus 208A, and two sulfuric acid production apparatuses for producing the second sulfuric acid-containing liquid production apparatus 208B of the sulfuric acid-containing liquid used in the processing unit 6. In the example of FIG. 13, two pairs of the first sulfuric acid-containing liquid production device 208A and the second sulfuric acid-containing liquid production device 208B are each provided in two pairs.

Each first sulfuric acid-containing liquid production device 208A corresponds to three towers arranged on one side of the transfer chamber 5. The first sulfuric acid-containing liquid production device 208A has the same configuration as the above-mentioned sulfuric acid-containing liquid production device 8. The SPM discharged from the processing unit 6 included in the corresponding three towers is supplied to each first sulfuric acid-containing liquid production device 208A. Each first sulfuric acid-containing liquid production device 208A supplies high-temperature sulfuric acid-containing liquid to all the surface supply units (SPM nozzles 13) included in the processing unit 6 included in the corresponding three towers. However, each first sulfuric acid-containing liquid production apparatus 208A does not supply the sulfuric acid-containing liquid (lower surface nozzle 91) to the back surface supply unit included in the processing unit 6 included in the corresponding three towers. That is, the first sulfuric acid-containing liquid is produced The device 208A is a special sulfuric acid liquid production device for surface supply. Each first sulfuric acid-containing liquid production device 208A includes a first liquid storage portion 11 and a second liquid storage portion 12.

Each second sulfuric acid-containing liquid production device 208B corresponds to three towers arranged on one side of the transfer chamber 5. The second sulfuric acid-containing liquid production device 208B has the same configuration as the aforementioned sulfuric acid-containing liquid production device 8. The SPM discharged from the processing unit 6 included in the corresponding three towers is supplied to each second sulfuric acid-containing liquid production device 208B. Each second sulfuric acid-containing liquid production device 208B supplies high-temperature sulfuric acid-containing liquid to all the back surface supply units (lower surface nozzle 91) included in the processing unit 6 included in the corresponding three towers. However, each second sulfuric acid-containing liquid production device 208B does not supply the sulfuric acid-containing liquid to the surface supply unit (SPM nozzle 13) included in the processing unit 6 included in the corresponding three towers. That is, the second sulfuric acid-containing liquid production device 208B is a sulfuric acid-containing liquid production device exclusively for surface supply. Each second sulfuric acid-containing liquid production device 208B includes a first liquid storage portion 11 and a second liquid storage portion 12.

Between the first sulfuric acid-containing liquid production device 208A and the second sulfuric acid-containing liquid production device 208B, there is connected a sulfuric acid-containing liquid for supplying sulfuric acid liquid from the first sulfuric acid-containing liquid production device 208A to the second sulfuric acid-containing liquid production device 208B. Liquid supply piping 209. The sulfuric acid-containing liquid supply pipe 209 is provided with an on-off valve 210 for opening and closing the sulfuric acid-containing liquid supply pipe 209. The sulfuric acid-containing liquid supply piping 209 connects the liquid storage part (the first liquid storage part 11 and/or the second liquid storage part 12) of the first sulfuric acid liquid production device 208A and the liquid storage part of the second sulfuric acid liquid production device 208B ( The first liquid storage portion 11 and/or the second liquid storage portion 12) are connected.

The sulfuric acid-containing liquid produced by the first sulfuric acid-containing liquid producing apparatus 208A is supplied to the surface Wa of the substrate W. That is, the sulfuric acid-containing liquid is specifically designed to remove the sulfuric acid used in the resist, and not only the temperature, but also the sulfuric acid concentration has a relatively high standard. In this embodiment, the lower limit concentration of the sulfuric acid concentration of the sulfuric acid-containing liquid produced by the first sulfuric acid-containing liquid producing device 208A is set to, for example, the first lower limit concentration (for example, 92%). If the sulfuric acid is concentrated The threshold value of the degree becomes lower than the first lower limit concentration, and the control device 4 opens the on-off valve 210 to supply the sulfuric acid-containing liquid stored in the first sulfuric acid-containing liquid production device 208A to the second sulfuric acid-containing liquid production device 208B. And the sulfuric acid replenishing valve 45 is opened to replenish the new sulfuric acid-containing liquid from the sulfuric acid replenishing unit 25 to the first sulfuric acid-containing liquid production device 208A.

Then, if the sulfuric acid concentration of the sulfuric acid-containing liquid circulating in the second circulation tank 51, the second circulation pipe 53 and the third circulation pipe 73 becomes lower than the first lower limit concentration, the sulfuric acid supply valve that opens and closes the sulfuric acid supply pipe 44 45 is turned on, and the sulfuric acid-containing liquid is supplied to the first circulation tank 22. As a result, the sulfuric acid concentration of the sulfuric acid-containing liquid circulating in the second circulation tank 51, the second circulation pipe 53 and the third circulation pipe 73 becomes higher. Along with this, after a short period of time thereafter, in the second circulation The sulfuric acid concentration of the sulfuric acid-containing liquid circulating in the tank 51, the second circulation pipe 53, and the third circulation pipe 73 becomes higher.

The sulfuric acid-containing liquid produced by the second sulfuric acid-containing liquid producing apparatus 208B is supplied to the back surface Wb of the substrate W. That is, the sulfuric acid-containing liquid is a sulfuric acid-containing liquid specially used for raising the temperature of the substrate W, and the standard of the sulfuric acid concentration is looser than that of the first sulfuric acid-containing liquid production device 208A. In this embodiment, the lower limit concentration of the sulfuric acid concentration produced by the second sulfuric acid-containing liquid producing device 208B is set to, for example, the second lower limit concentration (for example, 85%). If the threshold value of the sulfuric acid concentration is lower than the second lower limit concentration, the sulfuric acid-containing liquid stored in the liquid storage part (the first liquid storage part 11 and/or the second liquid storage part 12) of the second sulfuric acid liquid production device 208B Will be discharged. At this time, the new sulfuric acid-containing liquid from the sulfuric acid replenishing unit 25 may be replenished to the second sulfuric acid-containing liquid production device 208B, or may not be replenished.

According to this embodiment, in addition to the functions and effects of the embodiments shown in FIGS. 1 to 12, the following functions and effects can be exerted.

That is, the second sulfuric acid-containing liquid production device 208B is a sulfuric acid-containing liquid production device exclusively for back supply. The sulfuric acid solution used specifically for raising the temperature of the substrate, the sulfuric acid The concentration standard is loose. Therefore, the lower limit concentration of the sulfuric acid concentration of the second sulfuric acid-containing liquid preparation device 208B can be set low. Thereby, the discharge amount of the sulfuric acid-containing liquid from the second sulfuric acid-containing liquid production device 208B can be reduced. Therefore, it is possible to further reduce the consumption of the sulfuric acid-containing liquid.

Also, when the sulfuric acid concentration of the sulfuric acid-containing liquid produced by the first sulfuric acid-containing liquid production device 208A is lower than the predetermined lower limit concentration, the sulfuric acid-containing liquid is supplied to the second sulfuric acid-containing liquid from the first sulfuric acid-containing liquid production device 208A Production device 208B. In the first sulfuric acid-containing liquid production device 208A, the sulfuric acid-containing liquid whose sulfuric acid concentration is lower than the lower limit concentration should originally be discharged. However, such a sulfuric acid-containing liquid is collected in the second sulfuric acid-containing liquid production device 208B, and used as a sulfuric acid exclusively for back supply. Therefore, it is possible to further reduce the consumption of the sulfuric acid-containing liquid.

Although the two embodiments and three substrate processing examples of the present invention have been described above, the present invention can be further implemented in other forms.

In addition, in the first reservoir 11, although the SPM recovered from the recovery and discharge pipe 26 is temporarily recovered to the recovery tank 21 and thereafter stored in the first circulation tank 22, it has been described, but it may not be passed through The tank 21 is recovered and stored directly in the first circulation tank 22. In this case, the recovery tank 21 may be eliminated.

In addition, although the case of using the nozzle mixing method in which the sulfuric acid-containing liquid and the hydrogen peroxide water are mixed inside the SPM nozzle 13 has been described, it is also possible to use the sulfuric acid-containing liquid and the hydrogen peroxide water to be connected to the nozzle. In-pipe mixing method in which mixing is carried out in the processing liquid piping or in the mixing piping connected to the processing liquid piping.

In addition, one sulfuric acid-containing liquid production device 8 (or a pair of the first sulfuric acid-containing liquid production device 208A and the second sulfuric acid-containing liquid production device 208B) may not be supplied to the processing units 6 included in the plural (3) towers. Those containing sulfuric acid liquid, and only correspond to the area contained in 1 tower 理 unit 6.

In addition, the sulfuric acid-containing liquid (that is, the second sulfuric acid-containing liquid) supplied to the back surface Wb of the substrate W is not limited to the sulfuric acid-containing liquid, and may be SPM. In this case, the SPM for heating the back Wb can be mixed with the hydrogen peroxide water from the hydrogen peroxide water supply unit by the sulfuric acid-containing liquid production device 8 (the first sulfuric acid-containing liquid production device 208A, the second sulfuric acid-containing liquid production device 208A, and the second The sulfuric acid-containing liquid production device 208B) is produced, and it can also replace the sulfuric acid-containing liquid production device 8 (the first sulfuric acid-containing liquid production device 208A, the second sulfuric acid-containing liquid production device 208B), and the installation is based on the recovered SPM to produce SPM's SPM production device.

In addition, in each of the foregoing embodiments, although the case where the substrate processing apparatus 1, 201 is an apparatus for processing a substrate W composed of a semiconductor wafer has been described, the substrate processing apparatus may also be a liquid crystal display device. FPD (Flat Panel Display) substrates, substrates for organic EL (electroluminescence) display devices, substrates for optical discs, substrates for magnetic discs, substrates for optical magnetic discs, substrates for photomasks, ceramic substrates, substrates for solar cells, etc. A device for processing substrates.

This application corresponds to Japanese Patent Application No. 2018-221639 filed to the Japan Patent Office on November 27, 2018, and all the disclosures of this application are incorporated into this specification by reference.

Claims (17)

A substrate processing device that uses a mixture of sulfuric acid and hydrogen peroxide water, that is, SPM to process substrates; it includes: a substrate holding unit that holds the substrate; and a recovery pipe that is supplied to the substrate holding unit The substrate is held and the liquid discharged from the substrate flows in; the sulfuric acid-containing liquid production device, which is sent to the liquid that flows into the above-mentioned recovery pipe, is used to produce the first sulfuric acid-containing liquid containing sulfuric acid at a high temperature from the liquid; surface supply A unit for supplying SPM produced based on the high-temperature first sulfuric acid-containing liquid produced by the above-mentioned sulfuric acid-containing liquid production apparatus to the surface of the substrate held by the substrate holding unit; a backside supply unit, which Used to supply the second sulfuric acid-containing liquid containing the high-temperature first sulfuric acid-containing liquid produced by the above-mentioned sulfuric acid-containing liquid production apparatus to the back surface of the substrate held by the substrate holding unit; The liquid supplied to the substrate held by the substrate holding unit and discharged from the substrate flows in; the switching unit which supplies the piping for the liquid discharged from the substrate held by the substrate holding unit to flow into the piping in the discharge Switching between the liquid piping and the recovery piping; and a control device that controls the sulfuric acid-containing liquid production device, the surface supply unit, the back surface supply unit, and the switching unit; the control device performs the following steps: sulfuric acid-containing liquid The production step is to produce a high-temperature first sulfuric acid-containing liquid by the above-mentioned sulfuric acid-containing liquid production device based on the liquid flowing into the recovery pipe; the SPM surface supply step is to be produced by the above-mentioned sulfuric acid-containing liquid production device The SPM made by the first high-temperature sulfuric acid-containing liquid is supplied to the surface of the substrate held by the substrate holding unit; the sulfuric acid-containing liquid back surface supply step is before the SPM surface supply step or is in conjunction with the SPM surface supply step In parallel, in order to heat the substrate held by the above-mentioned substrate holding unit, a second sulfuric acid-containing liquid containing a high-temperature first sulfuric acid-containing liquid produced by the above-mentioned sulfuric acid-containing liquid producing apparatus is supplied to the substrate The back surface of the substrate held by the substrate holding unit; and the recovery step, which is performed in parallel with the sulfuric acid-containing liquid back surface supply step. The switching unit allows the liquid discharged from the substrate held by the substrate holding unit to flow into the above Recovery piping; the control device performs the sulfuric acid-containing liquid back supply step before the SPM surface supply step, and the control device further performs the draining step, and the draining step is parallel to the SPM surface supplying step by The switching unit allows the liquid discharged from the substrate held by the substrate holding unit to flow into the liquid discharge pipe. A substrate processing device that uses a mixture of sulfuric acid and hydrogen peroxide water, that is, SPM to process substrates; it includes: a substrate holding unit that holds the substrate; and a recovery pipe that is supplied to the substrate holding unit The substrate is held and the liquid discharged from the substrate flows in; the sulfuric acid-containing liquid production device, which is sent to the liquid that flows into the above-mentioned recovery pipe, is used to produce the first sulfuric acid-containing liquid containing sulfuric acid at a high temperature from the liquid; surface supply Unit for supplying SPM produced based on the high-temperature first sulfuric acid-containing liquid produced by the above-mentioned sulfuric acid-containing liquid production device to the substrate holding unit The surface of the substrate to be held; the back surface supply unit for supplying the second sulfuric acid-containing liquid containing the high-temperature first sulfuric acid-containing liquid produced by the above-mentioned sulfuric acid-containing liquid production apparatus to the substrate holding unit The back surface of the substrate; the liquid discharge pipe for the inflow of liquid discharged from the substrate which is supplied to the substrate held by the substrate holding unit; the switching unit, which is supplied from the substrate held by the substrate holding unit The pipe into which the discharged liquid flows is switched between the discharge pipe and the recovery pipe; and a control device that controls the sulfuric acid-containing liquid production device, the surface supply unit, the back surface supply unit, and the switching unit; The control device executes the following steps: a sulfuric acid-containing liquid production step, which uses the sulfuric acid-containing liquid production device to produce a high-temperature first sulfuric acid liquid based on the liquid flowing into the recovery pipe; the SPM surface supply step, which will be based on the The SPM produced by the high-temperature first sulfuric acid-containing liquid produced by the above-mentioned sulfuric acid-containing liquid production apparatus is supplied to the surface of the substrate held by the substrate holding unit; the sulfuric acid-containing liquid back surface supply step is on the surface of the SPM Before the supply step or in parallel with the above-mentioned SPM surface supply step, in order to heat the substrate held by the above-mentioned substrate holding unit, the first sulfuric acid-containing liquid containing a high temperature produced by the above-mentioned sulfuric acid-containing liquid production apparatus is prepared. 2 The sulfuric acid-containing liquid is supplied to the back surface of the substrate held by the substrate holding unit; and the recovery step is performed in parallel with the sulfuric acid-containing liquid back surface supply step, and the switching unit allows the substrate holding unit to pass through The liquid discharged from the held substrate flows into the above-mentioned recovery piping; The control device executes the sulfuric acid-containing liquid back surface supply step in parallel with the SPM surface supply step. The control device executes the following steps in the SPM surface supply step: the first surface supply step is performed by the substrate holding unit SPM is supplied to the surface of the substrate held by the substrate; and a second surface supply step in which, in the first surface supply step, after the supply of SPM is stopped, SPM is supplied to the surface of the substrate held by the substrate holding unit; The control device executes the sulfuric acid-containing liquid back surface supply step in parallel with the second surface supply step. The control device executes the sulfuric acid-containing liquid back surface supply step in parallel with the second surface supply step and the sulfuric acid-containing liquid back surface supply step by the switching unit. Recycling steps. The substrate processing apparatus of claim 2, wherein the control device further executes a liquid discharge step, and the liquid discharge step is held by the substrate holding unit by the switching unit in parallel with the first surface supply step The liquid discharged from the substrate flows into the above-mentioned discharge pipe. A substrate processing device that uses a mixture of sulfuric acid and hydrogen peroxide water, that is, SPM to process substrates; it includes: a substrate holding unit that holds the substrate; and a recovery pipe that is supplied to the substrate holding unit The substrate is held and the liquid discharged from the substrate flows in; the sulfuric acid-containing liquid production device, which is sent to the liquid that flows into the above-mentioned recovery pipe, is used to produce the first sulfuric acid-containing liquid containing sulfuric acid at a high temperature from the liquid; surface supply Unit for supplying SPM produced based on the high-temperature first sulfuric acid-containing liquid produced by the above-mentioned sulfuric acid-containing liquid production device to the substrate holding unit The surface of the substrate to be held; the back surface supply unit for supplying the second sulfuric acid-containing liquid containing the high-temperature first sulfuric acid-containing liquid produced by the above-mentioned sulfuric acid-containing liquid production apparatus to the substrate holding unit The back surface of the substrate; the liquid discharge pipe for the inflow of the liquid discharged from the substrate which is supplied to the substrate held by the substrate holding unit; and the switching unit, which is supplied from the substrate held by the substrate holding unit The pipe into which the liquid discharged from the substrate flows is switched between the liquid discharge pipe and the recovery pipe; and a control device that controls the sulfuric acid-containing liquid production device, the surface supply unit, the back surface supply unit, and the switching unit The control device executes the following steps: a sulfuric acid-containing liquid production step, which uses the sulfuric acid-containing liquid production device to produce a high-temperature first sulfuric acid liquid based on the liquid flowing into the recovery pipe; the SPM surface supply step, which will be based on The SPM produced by the high-temperature first sulfuric acid-containing liquid produced by the above-mentioned sulfuric acid-containing liquid production apparatus is supplied to the surface of the substrate held by the substrate holding unit; and the sulfuric acid-containing liquid back surface supply step is performed in the above Before the SPM surface supply step or in parallel with the above SPM surface supply step, in order to heat the substrate held by the substrate holding unit, the first sulfuric acid-containing liquid containing the high temperature produced by the sulfuric acid-containing liquid producing device The second sulfuric acid-containing liquid is supplied to the back surface of the substrate held by the substrate holding unit; the control device performs the following steps in the SPM surface supply step: the first surface supply step is for the substrate held by the substrate SPM is supplied to the surface of the substrate held by the unit; and The second surface supply step, in the first surface supply step, after the supply of SPM is stopped, supply SPM to the surface of the substrate held by the substrate holding unit; the control device is parallel to the first surface supply step Wherein, the sulfuric acid-containing liquid back surface supply step is performed, and the control device further executes a liquid draining step, and the liquid draining step is performed in parallel with the first surface supply step and the sulfuric acid-containing liquid back surface supply step by the switching unit The liquid discharged from the substrate held by the substrate holding unit flows into the liquid discharge pipe. A substrate processing device that uses a mixture of sulfuric acid and hydrogen peroxide water, that is, SPM to process substrates; it includes: a substrate holding unit that holds the substrate; and a recovery pipe that is supplied to the substrate holding unit The substrate is held and the liquid discharged from the substrate flows in; the sulfuric acid-containing liquid production device, which is sent to the liquid that flows into the above-mentioned recovery pipe, is used to produce the first sulfuric acid-containing liquid containing sulfuric acid at a high temperature from the liquid; surface supply A unit for supplying SPM produced based on the high-temperature first sulfuric acid-containing liquid produced by the above-mentioned sulfuric acid-containing liquid production device to the surface of the substrate held by the substrate holding unit; and a back surface supply unit, It is used for supplying a second sulfuric acid-containing liquid containing a high-temperature first sulfuric acid-containing liquid produced by the above-mentioned sulfuric acid-containing liquid producing apparatus to the back surface of a substrate held by the substrate holding unit; the above-mentioned sulfuric acid-containing liquid producing apparatus It includes: a first sulfuric acid-containing liquid production device that supplies high-temperature first sulfuric acid-containing liquid to the surface supply unit without supplying the first sulfuric acid-containing liquid to the back surface supply unit; and The second sulfuric acid-containing liquid production device supplies a high-temperature first sulfuric acid-containing liquid to the back surface supply unit without supplying the first sulfuric acid-containing liquid to the surface supply unit. The substrate processing apparatus of claim 5, which further includes a sulfuric acid supply pipe, and the sulfuric acid supply pipe has a sulfuric acid concentration lower than a predetermined lower limit in the first sulfuric acid-containing liquid produced by the above-mentioned first sulfuric acid-containing liquid production device In the case of the concentration, the first sulfuric acid-containing liquid is supplied from the first sulfuric acid-containing liquid production device to the second sulfuric acid-containing liquid production device. A substrate processing device that uses a mixture of sulfuric acid and hydrogen peroxide water, that is, SPM to process substrates; it includes: a substrate holding unit that holds the substrate; and a recovery pipe that is supplied to the substrate holding unit The substrate is held and the liquid discharged from the substrate flows in; the sulfuric acid-containing liquid production device, which is sent to the liquid that flows into the above-mentioned recovery pipe, is used to produce the first sulfuric acid-containing liquid containing sulfuric acid at a high temperature from the liquid; surface supply A unit for supplying SPM produced based on the high-temperature first sulfuric acid-containing liquid produced by the above-mentioned sulfuric acid-containing liquid production device to the surface of the substrate held by the substrate holding unit; and a back surface supply unit, It is used to supply the second sulfuric acid-containing liquid containing the high-temperature first sulfuric acid-containing liquid produced by the above-mentioned sulfuric acid-containing liquid production apparatus to the back surface of the substrate held by the substrate holding unit; The second sulfuric acid-containing liquid on the back surface of the substrate held by the substrate holding unit is a mixture of the first sulfuric acid-containing liquid and hydrogen peroxide water, that is, SPM. The substrate processing apparatus of claim 5 or 7, wherein it further includes a control device, and the control device controls the above-mentioned sulfuric acid-containing liquid production device and the above-mentioned For the surface supply unit and the back surface supply unit, the control device executes the following steps: a sulfuric acid-containing liquid preparation step, which produces a high-temperature first sulfuric acid-containing liquid by the sulfuric acid-containing liquid preparation device based on the liquid flowing into the recovery pipe SPM surface supply step, which will be based on the high-temperature first sulfuric acid-containing liquid produced by the above-mentioned sulfuric acid-containing liquid production apparatus to supply the SPM produced by the above-mentioned substrate holding unit to the surface of the substrate held by the substrate holding unit; and The sulfuric acid liquid back surface supply step includes heating the substrate held by the substrate holding unit before the SPM surface supply step or in parallel with the above-mentioned SPM surface supply step. The manufactured high-temperature first sulfuric acid-containing liquid and the second sulfuric acid-containing liquid are supplied to the back surface of the substrate held by the substrate holding unit. The substrate processing apparatus according to claim 8, which further includes: a discharge pipe for inflow of liquid supplied to the substrate held by the substrate holding unit and discharged from the substrate; and a switching unit, which The piping into which the liquid discharged from the substrate held by the substrate holding unit flows is switched between the liquid discharge piping and the recovery piping; the control device controls the switching unit, and the control device further executes the recovery step And this recovery step is performed in parallel with the above-mentioned sulfuric acid-containing liquid back surface supply step, and the liquid discharged from the substrate held by the substrate holding unit is caused to flow into the above-mentioned recovery pipe by the above-mentioned switching unit. The substrate processing apparatus according to any one of claims 1 to 6, wherein the second sulfuric acid-containing material is supplied to the back surface of the substrate held by the substrate holding unit The liquid is the first sulfuric acid-containing liquid. A substrate processing method that is executed in a substrate processing device and uses a mixture of sulfuric acid and hydrogen peroxide water, that is, SPM to process substrates. The substrate processing device includes: a substrate holding unit; and a recovery pipe for The liquid supplied to the substrate held by the substrate holding unit and discharged from the substrate flows in; wherein the substrate processing method includes: a step of preparing a sulfuric acid-containing liquid based on the liquid flowing into the recovery piping. The high-temperature first sulfuric acid-containing liquid of sulfuric acid; SPM surface supply step, which supplies SPM made from the high-temperature first sulfuric acid-containing liquid that has been produced to the surface of the substrate held by the substrate holding unit; sulfuric acid The liquid back surface supply step, which precedes the SPM surface supply step or in parallel with the SPM surface supply step, in order to heat the substrate held by the substrate holding unit, and heat the first sulfuric acid-containing liquid containing the high temperature that has been produced The second sulfuric acid-containing liquid is supplied to the back surface of the substrate held by the substrate holding unit; and the recovery step is performed in parallel with the sulfuric acid-containing liquid back surface supply step to make the substrate held by the substrate holding unit The discharged liquid flows into the recovery pipe; the substrate processing apparatus further includes a liquid discharge pipe, and the liquid discharge pipe is supplied to the substrate held by the substrate holding unit and the liquid discharged from the substrate flows in The above-mentioned sulfuric acid-containing liquid back surface supply step is performed before the above-mentioned SPM surface supply step, the above-mentioned substrate processing method further includes a liquid discharge step, and the above-mentioned liquid discharge step is parallel to the above-mentioned SPM surface supply step, so that the substrate The liquid discharged from the substrate held by the holding unit flows into the liquid discharge pipe. A substrate processing method is executed in a substrate processing device, And using a mixture of sulfuric acid and hydrogen peroxide water, that is, SPM to process substrates, and the substrate processing apparatus includes: a substrate holding unit; and a recovery pipe for being supplied to the substrate held by the substrate holding unit The liquid discharged from the substrate flows in; wherein, the substrate processing method includes: a sulfuric acid-containing liquid preparation step of preparing a first sulfuric acid-containing liquid containing sulfuric acid at a high temperature based on the liquid flowing into the recovery pipe; SPM surface supply step , Which supplies the SPM made according to the high-temperature first sulfuric acid-containing liquid that has been made to the surface of the substrate held by the substrate holding unit; the sulfuric acid-containing liquid back surface supply step is before or before the SPM surface supply step In parallel with the above-mentioned SPM surface supply step, in order to heat the substrate held by the substrate holding unit, the second sulfuric acid-containing liquid containing the produced high-temperature first sulfuric acid-containing liquid is supplied to the substrate holding unit The back surface of the held substrate; and the recovery step, which is performed in parallel with the above-mentioned sulfuric acid-containing liquid back surface supply step, allowing the liquid discharged from the substrate held by the substrate holding unit to flow into the above-mentioned recovery pipe; the above-mentioned sulfuric acid-containing liquid back surface The supplying step is performed in parallel with the SPM surface supplying step. The SPM surface supplying step includes: a first surface supplying step of supplying SPM to the surface of the substrate held by the substrate holding unit; and a second surface supplying step In the first surface supply step, after the supply of SPM is stopped, SPM is supplied to the surface of the substrate held by the substrate holding unit; the sulfuric acid-containing liquid back surface supply step is parallel to the second surface supply step When executed, the recovery step is executed in parallel with the second surface supply step and the sulfuric acid-containing liquid back surface supply step. The substrate processing method of claim 12, wherein the substrate processing apparatus further includes a liquid discharge pipe, and the liquid discharge pipe is for supplying the liquid discharged from the substrate to the substrate held by the substrate holding unit In the case of inflow, the substrate processing method further includes a liquid discharge step, and the liquid discharge step is performed in parallel with the first surface supply step to allow the liquid discharged from the substrate held by the substrate holding unit to flow into the liquid discharge pipe By. A substrate processing method that is executed in a substrate processing device and uses a mixture of sulfuric acid and hydrogen peroxide water, that is, SPM to process substrates. The substrate processing device includes: a substrate holding unit; and a recovery pipe for The liquid supplied to the substrate held by the substrate holding unit and discharged from the substrate flows in; wherein the substrate processing method includes: a step of preparing a sulfuric acid-containing liquid based on the liquid flowing into the recovery piping. The first sulfuric acid-containing liquid at a high temperature of sulfuric acid; an SPM surface supply step of supplying SPM made according to the high-temperature first sulfuric acid-containing liquid that has been produced to the surface of the substrate held by the substrate holding unit; and The sulfuric acid liquid back surface supply step, which precedes the SPM surface supply step or is parallel to the SPM surface supply step, in order to heat the substrate held by the substrate holding unit, and heat the first sulfuric acid containing high temperature that has been produced The second sulfuric acid-containing liquid is supplied to the back surface of the substrate held by the substrate holding unit; the substrate processing apparatus further includes a drain piping, and the drain piping is supplied to the substrate held by the substrate holding unit. For those who hold the substrate and the liquid discharged from the substrate flows in, the above-mentioned SPM surface supply step includes: The first surface supply step, which supplies SPM to the surface of the substrate held by the substrate holding unit; and the second surface supply step, which in the first surface supply step, after the supply of SPM is stopped, The surface of the substrate held by the substrate holding unit is supplied with SPM; the sulfuric acid-containing liquid back surface supply step is performed in parallel with the first surface supply step, the substrate processing method further includes a liquid discharge step, and the liquid discharge step is the same as In parallel, the first surface supply step and the sulfuric acid-containing liquid back surface supply step allow the liquid discharged from the substrate held by the substrate holding unit to flow into the liquid discharge pipe. A substrate processing method that is executed in a substrate processing device and uses a mixture of sulfuric acid and hydrogen peroxide water, that is, SPM to process substrates. The substrate processing device includes: a substrate holding unit; and a recovery pipe for The liquid supplied to the substrate held by the substrate holding unit and discharged from the substrate flows in; wherein the substrate processing method includes: a step of preparing a sulfuric acid-containing liquid based on the liquid flowing into the recovery piping. The first sulfuric acid-containing liquid at a high temperature of sulfuric acid; an SPM surface supply step of supplying SPM made according to the high-temperature first sulfuric acid-containing liquid that has been produced to the surface of the substrate held by the substrate holding unit; and The sulfuric acid liquid back surface supply step, which precedes the SPM surface supply step or is parallel to the SPM surface supply step, in order to heat the substrate held by the substrate holding unit, and heat the first sulfuric acid containing high temperature that has been produced The second sulfuric acid-containing liquid is supplied to the back surface of the substrate held by the substrate holding unit; the second sulfuric acid-containing liquid supplied to the back surface of the substrate held by the substrate holding unit is the first sulfuric acid-containing liquid and The mixture of hydrogen peroxide and water is SPM. Such as the substrate processing method of claim 15, wherein it further comprises There is a recovery step, and this recovery step is performed in parallel with the above-mentioned sulfuric acid-containing liquid back surface supply step, and the liquid discharged from the substrate held by the above-mentioned substrate holding unit flows into the above-mentioned recovery pipe. The substrate processing method according to any one of claims 11 to 14, wherein the second sulfuric acid-containing liquid supplied to the back surface of the substrate held by the substrate holding unit is a first sulfuric acid-containing liquid.

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