JP2020088208A - Substrate processing apparatus and substrate processing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a substrate processing apparatus and a substrate processing method capable of shortening a processing period of an SPM surface supply step and thereby reducing consumption of sulfuric acid. A high temperature sulfuric acid-containing liquid is prepared in a sulfuric acid preparation device based on SPM discharged from a substrate. The SPM created based on the created high temperature sulfuric acid-containing liquid is supplied to the surface of the substrate (SPM surface supply step S4). Prior to the SPM front surface supply step S4, the prepared high temperature sulfuric acid-containing liquid is supplied to the back surface of the substrate (sulfuric acid back surface supply step S3). This warms the substrate. Therefore, the SPM surface supply step can be performed on the substrate after the temperature is sufficiently raised, or the SPM surface supply step can be performed while the temperature of the substrate is sufficiently raised. In this case, the processing efficiency (resist removal efficiency) of the surface of the substrate by SPM can be improved. [Selection diagram] Fig. 5

Description

The present invention relates to a substrate processing apparatus and a substrate processing method. Examples of substrates to be processed are semiconductor wafers, substrates for liquid crystal display devices, FPD (Flat Panel Display) substrates for organic EL (electroluminescence) display devices, optical disk substrates, magnetic disk substrates, and magneto-optical disks. Substrates, photomask substrates, ceramic substrates, solar cell substrates, and the like are included.

A substrate processing apparatus for processing a semiconductor wafer or a substrate such as a glass substrate for a liquid crystal display device is used in a manufacturing process of a semiconductor device or a liquid crystal display device.
Patent Document 1 below discloses a single-wafer type substrate processing apparatus that processes substrates one by one. This substrate processing apparatus discharges SPM (mixed liquid of sulfuric acid and hydrogen peroxide solution) toward a top surface (front surface) of a substrate held by the spin chuck and a spin chuck that rotates the substrate while holding it horizontally. And a nozzle to do so.

JP, 2009-272548, A

Due to the problem of environmental load, it is required to reduce the drainage amount of sulfuric acid contained in SPM. There is also the problem of 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 (rate of resist removal (efficiency)) by SPM depends on the temperature of the surface of the substrate. The surface temperature of the substrate held by the spin chuck is the same as room temperature before the SPM is supplied. The surface temperature of the substrate rises as the supply of the high temperature SPM to the surface of the substrate starts. Then, by continuing the supply of SPM to the substrate, the surface temperature of the substrate eventually reaches the same temperature as that of SPM, and thereafter is kept at that temperature.

However, it takes a considerable time for the surface temperature of the substrate to rise to the same temperature as the liquid temperature of SPM. Therefore, in order to satisfactorily process the surface of the substrate using SPM (removing the resist from the surface of the substrate satisfactorily), there is a possibility that the processing period becomes long. However, the consumption of sulfuric acid may increase.
Therefore, one of the objects of the present invention is to provide a substrate processing apparatus and a substrate processing method capable of shortening the processing period of the SPM surface supply step and thereby reducing the consumption of sulfuric acid. That is.

In order to achieve the above object, the invention according to claim 1 is a substrate processing apparatus for processing a substrate by using SPM which is a mixed solution of sulfuric acid and hydrogen peroxide water, and a substrate holding unit for holding the substrate. And a recovery pipe into which the liquid supplied to the substrate held by the substrate holding unit and discharged from the substrate flows, and a liquid flowing into the recovery pipe are sent, and a high temperature containing sulfuric acid based on the liquid is sent. A sulfuric acid-containing liquid producing device for producing a first sulfuric acid-containing liquid, and an SPM produced based on the high-temperature first sulfuric acid-containing liquid produced in the sulfuric acid-containing liquid producing device, in the substrate holding unit. A surface supply unit for supplying to the surface of the substrate being held, and a second sulfuric acid-containing liquid containing the high-temperature first sulfuric acid-containing liquid prepared in the sulfuric acid-containing liquid preparing apparatus to the substrate holding unit. There is provided a substrate processing apparatus including a back surface supply unit for supplying the back surface of a held substrate.

According to this configuration, the second sulfuric acid-containing liquid containing the high-temperature first sulfuric acid-containing liquid serving as a base for producing the SPM supplied to the front surface of the substrate is supplied to the back surface of the substrate. The substrate is warmed by supplying the high temperature second sulfuric acid-containing liquid to the back surface of the substrate. Therefore, the SPM surface supply process can be performed on the substrate after the temperature is sufficiently raised, or the SPM surface supply process can be performed while the substrate is properly heated. In this case, the processing 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, which can reduce the consumption of SPM, and thus the consumption of sulfuric acid.

Further, what is supplied to the back surface of the substrate is the second sulfuric acid-containing liquid containing the first sulfuric acid-containing liquid created based on the liquid discharged and collected from the substrate. By supplying such a second sulfuric acid-containing liquid to the back surface of the substrate, it is possible to satisfactorily heat the substrate without using new sulfuric acid.
As described above, it is possible to reduce the consumption of sulfuric acid.

The invention according to claim 2 further includes a control device that controls the sulfuric acid-containing liquid preparation device, the front surface supply unit, and the back surface supply unit, wherein the control device is based on the liquid flowing into the recovery pipe. A sulfuric acid-containing liquid producing step of producing a high-temperature first sulfuric acid-containing liquid by a sulfuric acid-containing liquid producing device, and an SPM produced based on the high-temperature first sulfuric acid-containing liquid produced by the sulfuric acid-containing liquid producing device. Held by the substrate holding unit prior to the SPM surface supplying step or in parallel with the SPM surface supplying step, and an SPM surface supplying step of supplying the surface of the substrate held by the substrate holding unit. In order to heat the substrate, a second sulfuric acid-containing liquid containing the high-temperature first sulfuric acid-containing liquid prepared by the sulfuric acid-containing liquid preparing device is supplied to the back surface of the substrate held by the substrate holding unit. The substrate processing apparatus according to claim 1, further comprising: a sulfuric acid-containing liquid back surface supplying step.

According to this configuration, prior to the SPM surface supply step or in parallel with the SPM surface supply step, the second high-sulfuric acid-containing liquid serving as a base for producing the SPM supplied to the surface of the substrate is added. A sulfuric acid-containing liquid is supplied to the back surface of the substrate. The substrate is warmed by supplying the high temperature second sulfuric acid-containing liquid to the back surface of the substrate. Therefore, the SPM surface supply step can be executed on the substrate after the temperature is sufficiently raised, or the SPM surface supply step can be executed while the temperature of the substrate is sufficiently increased.

According to a third aspect of the present invention, a drainage pipe into which the liquid supplied to the substrate held by the substrate holding unit and discharged from the substrate flows, and a substrate held by the substrate holding unit are discharged. And a switching unit for switching the liquid inflowing pipe between the drainage pipe and the recovery pipe, wherein the control device controls the switching unit, and the control device includes the sulfuric acid-containing liquid. The substrate according to claim 2, further comprising a collecting step of causing the liquid discharged from the substrate held by the substrate holding unit to flow into the collecting pipe by the switching unit, in parallel with the liquid back surface supplying step. It is a processing device.

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 surface of the substrate for heating the substrate is recovered by the recovery pipe, and based on the recovered second sulfuric acid-containing liquid, the first sulfuric acid-containing liquid producing apparatus first A sulfuric acid-containing liquid is prepared. 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 producing the SPM used in the SPM front surface supplying step. Accordingly, the heating of the substrate using the second sulfuric acid-containing liquid can be performed without increasing the consumption amount of sulfuric acid.

In the invention according to claim 4, the control device executes the sulfuric acid-containing liquid back surface supply process prior to the SPM front surface supply process, and the control device performs in parallel with the SPM front surface supply process. The substrate processing apparatus according to claim 3, further comprising a draining step of causing the liquid discharged from the substrate held by the substrate holding unit to flow into the drain pipe by the switching unit.

According to this configuration, the sulfuric acid-containing liquid back surface supply step is executed prior to the SPM front surface supply step. Therefore, it is possible to start execution of the SPM surface supply step on the substrate after the temperature is sufficiently raised. In this case, the processing 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.
Further, the draining process is executed in parallel with the SPM front surface supplying process executed after the sulfuric acid-containing liquid back surface supplying process and the collecting process are completed. For a while after the start of the SPM surface supply step, the liquid discharged from the substrate may contain a large amount of foreign matter removed from the surface of the substrate such as resist, in addition to SPM supplied to the surface of the substrate. is there. If the first sulfuric acid-containing liquid is prepared based on such a liquid containing a large amount of foreign matter, it is difficult to prepare a clean first sulfuric acid-containing liquid. In Claim 4, the liquid containing many foreign matters can be discharged by executing the liquid discharging process in parallel with the SPM surface supplying process, whereby the first sulfuric acid-containing liquid is based on the clean liquid. Can be created. Therefore, a clean first sulfuric acid-containing liquid can be prepared in the sulfuric acid-containing liquid preparing step.

The invention according to claim 5 is the substrate processing apparatus according to claim 3, wherein the control device executes the sulfuric acid-containing liquid back surface supply step in parallel with the SPM front surface supply step.
According to this configuration, the sulfuric acid-containing liquid back surface supply step is executed in parallel with the SPM front surface supply step. Therefore, the SPM surface supply step can be executed while heating the substrate. In this case, the processing 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.

According to a sixth aspect of the present invention, in the SPM surface supplying step, the control device includes a first surface supplying step of supplying SPM to a surface of a substrate held by the substrate holding unit, and the first surface supplying step. A second surface supplying step of supplying SPM to the surface of the substrate held by the substrate holding unit after the supply of SPM is stopped in the surface supplying step; The liquid back surface supply step is executed in parallel with the second front surface supply step, and the controller is operated by the switching unit in parallel with the second surface supply step and the sulfuric acid-containing liquid back surface supply step. It is a substrate processing apparatus of Claim 5 which performs a collection process.

According to this configuration, the recovery process is executed in parallel with the second surface supply process. For a while after the start of the SPM surface supply step, the liquid discharged from the substrate may contain a large amount of foreign matter removed from the surface of the substrate such as resist, in addition to SPM supplied to the surface of the substrate. is there. If the first sulfuric acid-containing liquid is prepared based on such a liquid containing a large amount of foreign matter, it is difficult to prepare a clean first sulfuric acid-containing liquid. In 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 foreign matter from entering. This makes it possible to create the first sulfuric acid-containing liquid based on the clean liquid. Therefore, a clean first sulfuric acid-containing liquid can be prepared in the sulfuric acid-containing liquid preparing step.

Further, the collecting step is executed in parallel with the sulfuric acid-containing liquid back surface supplying step. That is, the second sulfuric acid-containing liquid supplied to the back surface of the substrate for heating the substrate is recovered by the recovery pipe, and then the sulfuric acid-containing liquid producing apparatus is based on the recovered second sulfuric acid-containing liquid. At, a second solution containing sulfuric acid is created. 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 producing the SPM used in the SPM front surface supplying step. Accordingly, the heating of the substrate using the second sulfuric acid-containing liquid can be performed without increasing the consumption amount of sulfuric acid.

In the invention according to claim 7, in parallel with the first surface supply step, the control device causes the liquid discharged from the substrate held by the substrate holding unit to be discharged by the switching unit. The substrate processing apparatus according to claim 6, further comprising a draining step of causing the liquid to flow into the pipe.
According to this configuration, the drainage process is executed in parallel with the first surface supply process included in the SPM surface supply process. As a result, the liquid containing a large amount of foreign matter can be drained, whereby the first sulfuric acid-containing liquid can be created based on the clean liquid. Therefore, a clean first sulfuric acid-containing liquid can be prepared in the sulfuric acid-containing liquid preparing step.

The invention according to claim 8 is a drainage pipe into which a liquid supplied to the substrate held by the substrate holding unit and discharged from the substrate flows,
Further comprising a switching unit for switching a pipe into which the liquid discharged from the substrate held by the substrate holding unit flows, between the drainage pipe and the recovery pipe,
The control device controls the switching unit,
In the SPM surface supply step, the controller stops the first surface supply step of supplying SPM to the surface of the substrate held by the substrate holding unit, and stops the supply of SPM in the first surface supply step. And a second front surface supplying step of supplying SPM to the front surface of the substrate held by the substrate holding unit, and the controller performs the sulfuric acid-containing liquid back surface supplying step in the first step. Of the substrate held by the substrate holding unit in parallel with the first surface feeding step and the sulfuric acid-containing liquid back surface feeding step. The substrate processing apparatus according to claim 2, further comprising a draining step of causing liquid to flow into the drainage pipe by the switching unit.

According to this configuration, the sulfuric acid-containing liquid back surface supply step is performed in parallel with the first front surface supply step. Further, the drainage process is executed in parallel with the sulfuric acid-containing liquid back surface supply process. Therefore, it is possible to supply the high temperature second sulfuric acid-containing liquid to the back surface of the substrate from the start of the SPM front surface supply step. In this case, the resist can be removed from the surface of the substrate at an early stage after the start of the SPM surface supply process, and thus the processing period of the SPM surface supply process can be further shortened.

In the invention according to claim 9, the sulfuric acid-containing liquid producing apparatus supplies the high-temperature first sulfuric acid-containing liquid to the front surface supply unit and does not supply the first sulfuric acid-containing liquid to the back surface supply unit. And a second sulfuric acid-containing liquid preparation device that supplies a 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 front surface supply unit. It is a substrate processing apparatus containing any one of Claims 1-8.

According to this configuration, the first sulfuric acid-containing liquid producing apparatus supplies the high-temperature first sulfuric acid-containing liquid to the front surface supply unit and does not supply the first sulfuric acid-containing liquid to the back surface supply unit. Further, the second sulfuric acid-containing solution producing device supplies the high-temperature first sulfuric acid-containing solution to the back surface supply unit and does not supply the first sulfuric acid-containing solution to the front surface supply unit. Therefore, the second sulfuric acid-containing liquid preparation device is a sulfuric acid-containing liquid preparation device dedicated to the backside supply. The second sulfuric acid-containing liquid used exclusively for raising the temperature of the substrate has a looser sulfuric acid concentration standard. Therefore, it is possible to set the lower limit concentration of the sulfuric acid concentration of the first sulfuric acid-containing liquid produced in the second sulfuric acid-containing liquid producing device to be low. Thereby, the amount of the first sulfuric acid-containing liquid discharged from the second sulfuric acid-containing liquid producing apparatus can be reduced. Therefore, the consumption of sulfuric acid can be further reduced.

According to a tenth aspect of the present invention, when the sulfuric acid concentration of the first sulfuric acid-containing liquid prepared by the first sulfuric acid-containing liquid preparing device is below a predetermined lower limit concentration, the first sulfuric acid-containing liquid preparing process is performed. The substrate processing apparatus according to claim 9, further comprising a sulfuric acid supply pipe that supplies a first sulfuric acid-containing liquid from the apparatus to the second sulfuric acid-containing liquid producing apparatus.
According to this configuration, when the sulfuric acid concentration of the first sulfuric acid-containing liquid produced by the first sulfuric acid-containing liquid producing device falls below a predetermined lower limit concentration, the first sulfuric acid-containing liquid producing device produces A first sulfuric acid-containing liquid is supplied to the sulfuric acid-containing liquid producing device. Sulfuric acid whose sulfuric acid concentration of the first sulfuric acid-containing liquid prepared in the first sulfuric acid-containing liquid preparation device is lower than the lower limit concentration should be originally drained. Such a first sulfuric acid-containing liquid is collected in the second sulfuric acid-containing liquid producing apparatus and is utilized as the first sulfuric acid-containing liquid for supplying the back surface (for heating the substrate). Therefore, the consumption of sulfuric acid can be further reduced.

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 as in the invention of claim 11.
The second sulfuric acid-containing liquid supplied to the back surface of the substrate held by the substrate holding unit is a mixed liquid of the first sulfuric acid-containing liquid and hydrogen peroxide solution as in the invention according to claim 12. It may be some SPM.

The invention according to claim 13 for achieving the above object comprises a substrate holding unit, and a recovery pipe into which a liquid supplied to the substrate held by the substrate holding unit and discharged from the substrate flows. A method of processing a substrate, which is carried out in a substrate processing apparatus and uses SPM, which is a mixed solution of sulfuric acid and hydrogen peroxide solution, to treat a substrate at a high temperature containing sulfuric acid based on the liquid flowing into the recovery pipe. Sulfuric acid-containing liquid producing step of producing a first sulfuric acid-containing liquid, and SPM produced based on the produced high-temperature first sulfuric acid-containing liquid are supplied to the surface of the substrate held by the substrate holding unit. SPM surface supplying step for performing, and prior to the SPM surface supplying step or in parallel with the SPM surface supplying step, a first high-temperature created for heating the substrate held in the substrate holding unit. And a second sulfuric acid-containing liquid containing a sulfuric acid-containing liquid is supplied to the back surface of the substrate held by the substrate holding unit.

According to this method, prior to the SPM surface supplying step or in parallel with the SPM surface supplying step, a second high-sulfuric acid-containing liquid serving as a base for producing SPM supplied to the surface of the substrate is used as the second solution. A sulfuric acid-containing liquid is supplied to the back surface of the substrate. The substrate is warmed by supplying the high temperature second sulfuric acid-containing liquid to the back surface of the substrate. Therefore, the SPM surface supply step can be executed on the substrate after the temperature is sufficiently raised, or the SPM surface supply step can be executed while the temperature of the substrate is sufficiently increased. Therefore, the processing 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, which can reduce the consumption of SPM, and thus the consumption of sulfuric acid.

Further, what is supplied to the back surface of the substrate is the second sulfuric acid-containing liquid containing the first sulfuric acid-containing liquid created based on the liquid discharged and collected from the substrate. By supplying such a second sulfuric acid-containing liquid to the back surface of the substrate, it is possible to satisfactorily heat the substrate without using new sulfuric acid.
As described above, it is possible to reduce the consumption of sulfuric acid.

The invention according to claim 14 further includes a recovery step of causing the liquid discharged from the substrate held by the substrate holding unit to flow into the recovery pipe in parallel with the sulfuric acid-containing liquid back surface supply step. The substrate processing method according to claim 13.
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 surface of the substrate for heating the substrate is recovered by the recovery pipe, and based on the recovered second sulfuric acid-containing liquid, the first sulfuric acid-containing liquid producing apparatus first A sulfuric acid-containing liquid is prepared. 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 producing the SPM used in the SPM front surface supplying step. Accordingly, the heating of the substrate using the second sulfuric acid-containing liquid can be performed without increasing the consumption amount of sulfuric acid.

According to a fifteenth aspect of the present invention, the substrate processing apparatus further includes a drainage pipe into which the liquid supplied to the substrate held by the substrate holding unit and discharged from the substrate flows, The supply step is executed prior to the SPM surface supply step, and in parallel with the SPM surface supply step, the liquid discharged from the substrate held by the substrate holding unit is caused to flow into the drain pipe. The substrate processing method according to claim 14, further comprising a liquid process.

According to this method, the sulfuric acid-containing liquid back surface supply step is executed prior to the SPM front surface supply step. Then, the drainage process is performed in parallel with the SPM front surface supply process that is performed after the sulfuric acid-containing liquid back surface supply process and the recovery process are completed. For a while after the start of the SPM surface supply step, the liquid discharged from the substrate may contain a large amount of foreign matter removed from the surface of the substrate such as resist, in addition to SPM supplied to the surface of the substrate. is there. If the first sulfuric acid-containing liquid is prepared based on such a liquid containing a large amount of foreign matter, it is difficult to prepare a clean first sulfuric acid-containing liquid. The liquid containing a large amount of foreign matter can be discharged by executing the liquid discharging process in parallel with the SPM surface supplying process according to claim 15, whereby the first sulfuric acid-containing liquid is based on the clean liquid. Can be created. Therefore, a clean first sulfuric acid-containing liquid can be prepared in the sulfuric acid-containing liquid preparing step.

The invention according to claim 16 is the substrate processing method according to claim 14, wherein the sulfuric acid-containing liquid back surface supply step is executed in parallel with the SPM front surface supply step.
According to this method, the sulfuric acid-containing liquid back surface supply step is executed in parallel with the SPM front surface supply step. Therefore, the SPM surface supply step can be executed while heating the substrate. In this case, the processing 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 the invention according to claim 17, the SPM surface supplying step includes a first surface supplying step of supplying SPM to a surface of a substrate held by the substrate holding unit, and an SPM in the first surface supplying step. Second surface supply step of supplying SPM to the front surface of the substrate held by the substrate holding unit after the supply of the second surface is stopped, and the sulfuric acid-containing solution back surface supply step comprises the second surface. The substrate processing method according to claim 16, wherein the recovery step is performed in parallel with the supply step, and the recovery step is performed in parallel with the second front surface supply step and the sulfuric acid-containing liquid back surface supply step.

According to this method, the recovery process is executed in parallel with the second surface supply process. For a while after the start of the SPM surface supply step, the liquid discharged from the substrate may contain a large amount of foreign matter removed from the surface of the substrate such as resist, in addition to SPM supplied to the surface of the substrate. is there. If the first sulfuric acid-containing liquid is prepared based on such a liquid containing a large amount of foreign matter, it is difficult to prepare a clean first sulfuric acid-containing liquid. In claim 17, by performing the collecting step in parallel with the second surface supplying step rather than in parallel with the first surface supplying step, it is possible to collect the liquid while preventing foreign matter from being mixed. This makes it possible to create the first sulfuric acid-containing liquid based on the clean liquid. Therefore, a clean first sulfuric acid-containing liquid can be prepared in the sulfuric acid-containing liquid preparing step.

Further, the collecting step is executed in parallel with the sulfuric acid-containing liquid back surface supplying step. That is, the second sulfuric acid-containing liquid supplied to the back surface of the substrate for heating the substrate is recovered by the recovery pipe, and then the sulfuric acid-containing liquid producing step is performed based on the recovered second sulfuric acid-containing liquid. At, a first sulfuric acid-containing liquid is created. 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 producing the SPM used in the SPM front surface supplying step. Accordingly, the heating of the substrate using the second sulfuric acid-containing liquid can be performed without increasing the consumption amount of sulfuric acid.

The invention according to claim 18 is characterized in that the substrate processing apparatus further includes a drainage pipe into which the liquid supplied to the substrate held by the substrate holding unit and discharged from the substrate flows in, the first surface The substrate processing method according to claim 17, further comprising a draining step of causing a liquid discharged from the substrate held by the substrate holding unit to flow into the drainage pipe in parallel with the supplying step.

According to this method, the drainage process is executed in parallel with the first surface supply process included in the SPM surface supply process. As a result, the liquid containing a large amount of foreign matter can be drained, whereby the first sulfuric acid-containing liquid can be created based on the clean liquid. Therefore, a clean first sulfuric acid-containing liquid can be prepared in the sulfuric acid-containing liquid preparing step.
The invention according to claim 19 is characterized in that the substrate processing apparatus further includes a drainage pipe into which a liquid supplied from a substrate held by the substrate holding unit and discharged from the substrate flows in, and the SPM surface supplying step. A first surface supplying step of supplying SPM to the surface of the substrate held by the substrate holding unit, and holding the substrate holding unit after SPM supply is stopped in the first surface supplying step. A second front surface supply step of supplying SPM to the front surface of the substrate, wherein the sulfuric acid-containing liquid back surface supply step is performed in parallel with the first front surface supply step, and the substrate processing method In parallel with the first front surface supplying step and the sulfuric acid-containing liquid rear surface supplying step, a draining step of causing a liquid discharged from the substrate held by the substrate holding unit to flow into the drainage pipe is further provided. The substrate processing method according to claim 13, further comprising:

According to this method, the sulfuric acid-containing liquid back surface supply step is performed in parallel with the first front surface supply step. Further, the drainage process is executed in parallel with the sulfuric acid-containing liquid back surface supply process. Therefore, it is possible to supply the high temperature second sulfuric acid-containing liquid to the back surface of the substrate W from the start of the SPM front surface supply step. In this case, the resist can be removed from the surface of the substrate at an early stage after the start of the SPM surface supply process, and thus the processing period of the SPM surface supply process can be further shortened.

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 as in the invention of claim 20.
The second sulfuric acid-containing liquid supplied to the back surface of the substrate held by the substrate holding unit is a mixed liquid of the first sulfuric acid-containing liquid and hydrogen peroxide solution as in the invention of claim 21. It may be some SPM.

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 horizontal view of the sulfuric acid-containing liquid producing apparatus and the apparatus main body shown in FIG. FIG. 3 is a schematic sectional view for explaining a configuration example of the processing unit shown in FIG. FIG. 4A is a block diagram for explaining an electrical configuration of the substrate processing apparatus. FIG. 4B is an enlarged sectional view showing the surface of the substrate to be processed by the substrate processing apparatus. FIG. 5 is a flow chart of a first substrate processing example executed by the processing unit. FIG. 6 is a timing chart showing the operation and the like of the first guard and the second guard in the first substrate processing example. 7A and 7B are schematic diagrams for explaining the sulfuric acid-containing liquid back surface supply step and the first front surface supply step (SPM front surface supply step), respectively. FIG. 7C is a schematic diagram for explaining the second surface supply step (SPM surface supply step). FIG. 8 is a flowchart of a second substrate processing example executed by the processing unit. FIG. 9 is a schematic diagram for explaining the second surface supply step (SPM surface supply step) according to the second substrate processing example. FIG. 10 is a flowchart of a third substrate processing example executed by the processing unit. FIG. 11 is a schematic view for explaining the first surface supply step (SPM surface supply step) according to the third substrate processing example. 12A-12B are schematic diagrams for explaining removal (peeling) of the resist formed on the surface of the substrate. 12C to 12D are views showing the next step of FIG. 12B. FIG. 13 is a schematic view of a substrate processing apparatus according to another embodiment of the present invention seen from above.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.
FIG. 1 is a schematic view of a substrate processing apparatus 1 according to an embodiment of the present invention as viewed from above.
The substrate processing apparatus 1 is a single-wafer processing apparatus that processes disk-shaped substrates W such as semiconductor wafers one by one. The substrate processing apparatus 1 includes an apparatus main body 2 arranged in a clean room, an indexer 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 indexer unit 3 includes a plurality of load ports LP that respectively hold a plurality of carriers C that accommodate the substrates W, and an indexer robot IR that conveys the substrates W to each carrier C.
The apparatus main body 2 includes a transfer chamber 5 and a plurality of processing units 6 that process a substrate W transferred from a plurality of load ports LP with a processing fluid such as a processing liquid or a processing gas. The plurality of processing units 6 form six towers respectively arranged at six horizontally separated positions. Each tower includes a plurality (for example, three) of processing units 6 stacked one above the other. The six towers are arranged three on each side of the transfer chamber 5. The processing unit 6 is arranged in the outer wall 7 of the apparatus main body 2, that is, surrounded by the outer wall 7.

The substrate processing apparatus 1 includes, as transfer robots, a first substrate transfer robot CR1 and a second substrate transfer robot CR2 in addition to the indexer robot IR. The first substrate transfer robot CR1 and the second substrate transfer robot CR2 are arranged in the transfer chamber 5. The indexer robot IR transfers the substrate W between the load port LP and the first substrate transfer robot CR1. The indexer robot IR includes a hand that supports the substrate W. The first substrate transfer robot CR1 transfers the substrate W between the indexer robot IR and the processing units 6 included in the two towers on the load port LP side, and at the same time, the indexer robot IR and the second substrate transfer robot CR2. And the substrate W is transported between and. The second substrate transfer robot CR2 transfers the substrate W between the indexer robot IR and the processing units 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 hand that supports the substrate W.

The processing liquid supply device supplies a processing liquid (sulfuric acid-containing liquid (first sulfuric acid-containing liquid; etching liquid or cleaning liquid)) to the processing unit 6. The treatment liquid supply device includes a sulfuric acid-containing liquid producing device 8 that produces the sulfuric acid-containing liquid (first sulfuric acid-containing liquid) used in the treatment unit 6. The sulfuric acid-containing liquid preparation device 8 collects 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 producing device 8 is arranged outside the outer wall 7 in the clean room. In the example of FIG. 1, two sulfuric acid-containing liquid producing devices 8 are provided.

Each sulfuric acid-containing liquid preparation device 8 corresponds to three towers arranged on one side of the transfer chamber 5. The SPM discharged from the processing units 6 included in the corresponding three columns is supplied to each sulfuric acid-containing liquid preparation device 8. The sulfuric acid-containing liquid producing device 8 collects the SPM discharged from the processing unit 6 and stores the SPM as a sulfuric acid-containing liquid to adjust the SPM to a predetermined state. And a liquid storage portion 12 (see FIG. 2). The sulfuric acid-containing liquid preparation device 8 may be arranged outside the clean room (for example, a downstairs space of the clean room) instead of being arranged inside the clean room. Further, 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 separate frames.

In the sulfuric acid-containing liquid preparation device 8, not the SPM itself but the sulfuric acid-containing liquid (first sulfuric acid-containing liquid) is prepared based on the SPM discharged and collected from the substrate W (sulfuric acid-containing liquid preparing step). The sulfuric acid-containing liquid (adjusted in sulfuric acid concentration and temperature) produced by the sulfuric acid-containing liquid producing device 8 is an SPM nozzle (nozzle) 13 (see FIGS. 2 and 3) as an example of a surface supply unit of the processing unit 6. ) Is supplied to. Hydrogen peroxide solution is supplied from the hydrogen peroxide solution supply unit 122 (see FIGS. 2 and 3) to the SPM nozzle 13. The sulfuric acid-containing liquid and the hydrogen peroxide solution supplied to the SPM nozzle 13 are mixed inside the SPM nozzle 13 (mixing section), and thereby SPM is generated. Then, SPM is ejected from the ejection port 13a (see FIG. 3) formed in the lower portion 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. By this, the resist is removed from the substrate W.

From the viewpoint of enhancing the SPM removal capability, the sulfuric acid concentration of the sulfuric acid-containing liquid to be produced is required to be within a predetermined concentration range (equal to or higher than a predetermined concentration). From the same viewpoint, the temperature of the sulfuric acid-containing liquid to be created is required to be within a predetermined temperature range.
FIG. 2 is a horizontal view of the sulfuric acid-containing liquid producing device 8 and the device body 2 shown in FIG.

The sulfuric acid-containing liquid preparation device 8 includes a first liquid storage unit 11 and a second liquid storage unit 11.
The first liquid storage unit 11 includes a first circulation tank 22, a first circulation pipe 23, a first circulation heater 24, and a sulfuric acid replenishment unit 25.
The first liquid storage unit 11 stores the SPMs collected from a total of nine processing units 6 included in the corresponding three towers as a sulfuric acid-containing liquid. The first circulation tank 22 is connected to a downstream end of a recovery outlet pipe 26 connected to a recovery pipe 156 described later. The SPM collected in the processing cup 111 of each processing unit 6 is guided to the first circulation tank 22 through the collection pipe 156 and the collection outlet pipe 26, and is stored in the first circulation tank 22.

The first circulation tank 22 is connected to the downstream ends of the three recovery/delivery pipes 26 corresponding to the three towers. 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 unit 12 is connected to the first circulation tank 22. A first liquid sending device 32 such as a pump for pumping out the sulfuric acid-containing liquid in the first circulation tank 22 is provided in the middle of the liquid introducing pipe 31. A capture filter 37 and an opening/closing valve 38 are provided downstream of the first liquid delivery device 32 in the middle of the liquid introducing pipe 31. The capture filter 37 is a filter for capturing and removing relatively small foreign matter contained in the sulfuric acid-containing liquid flowing through the liquid guiding pipe 31.

The open/close valve 38 is a valve for controlling the flow of the sulfuric acid-containing liquid in the liquid guiding pipe 31 and the stop thereof.
A return pipe 40 is branched and connected to the liquid guide pipe 31 between the opening/closing valve 38 and the capture filter 37. The downstream end of the return pipe 40 extends to the first circulation tank 22. A return valve 41 is provided in the middle of the return pipe 40. A first circulation pipe 23 is configured by the return pipe 40 and the downstream side portion of the branch pipe 42 of the return pipe 40 in the liquid guide pipe 31.

The sulfuric acid replenishing unit 25 is a unit that supplies fresh sulfuric acid (unused sulfuric acid for processing the substrate W) to the first circulation tank 22. The sulfuric acid replenishment unit 25 includes a sulfuric acid replenishment pipe 44 that replenishes the first circulation tank 22 with a sulfuric acid-containing liquid, and a sulfuric acid replenishment valve 45 that opens and closes the sulfuric acid replenishment pipe 44. The sulfuric acid-containing liquid to be replenished 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 sulfuric acid-containing liquid to be replenished is at room temperature (about 23°C to about 25°C).

During the operation of the substrate processing apparatus 1 (including the period in 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, the opening/closing valve 38 is closed and the return valve 41 is opened, so that the sulfuric acid-containing liquid pumped from the first circulation tank 22 flows through the liquid guiding pipe 31 to the branch position 42 and returns from the branch position 42. It is returned to the first circulation tank 22 through the pipe 40. That is, while the sulfuric acid-containing liquid is not sent to the second liquid storage unit 12, the sulfuric acid-containing liquid circulates in the first circulation tank 22 and the first circulation pipe 23. Then, at the timing of sending the sulfuric acid-containing liquid to the second liquid storage unit 12, the opening/closing valve 38 is opened and the return valve 41 is closed, so that the sulfuric acid-containing liquid pumped out from the first circulation tank 22 becomes It is supplied to the second liquid storage section 12 through the liquid guiding pipe 31.

The first circulation heater 24 is provided upstream of the first liquid delivery 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 through the first circulation tank 22 and the first circulation pipe 23, the sulfuric acid-containing liquid is adjusted to the first temperature. The sulfuric acid-containing liquid adjusted to the first temperature is stored in the first circulation tank 22 by circulating the sulfuric acid-containing liquid while the sulfuric acid-containing liquid is not sent to the second liquid storage unit 12. be able to. Further, after the opening/closing valve 38 is opened, the sulfuric acid-containing liquid adjusted to the first temperature can be sent to the second liquid storage section 12.

The second liquid storage section 12 includes a second circulation tank 51.
The downstream end of the liquid guiding pipe 31 is connected to the second circulation tank 51. The sulfuric acid-containing liquid whose temperature is adjusted to the first temperature (for example, about 120° C. to about 130° C.) in the first liquid storage unit 11 is introduced into 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 provided with liquid level meters 65 each having a sensor unit at a plurality of positions having different heights, and these liquid level meters 65 store the liquid level meters 65 in the second circulation tank 51. The liquid surface height of the sulfuric acid-containing liquid is detected.
A first common pipe 51A is connected to the second circulation tank 51. A second circulation heater 52 is provided in the middle of 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 to the second circulation tank 51 and the first common pipe 51A. Specifically, the upstream end and the downstream end of the three first sulfuric acid-containing liquid circulation pipes 51B are connected to the downstream end of the first common pipe 51A and the second circulation tank 51, respectively (FIG. 2). Then, only one first sulfuric acid-containing liquid circulation pipe 51B is shown). A second circulation pipe 53 is configured by the first common pipe 51A and the first sulfuric acid-containing liquid circulation pipe 51B.

A second liquid sending device 56 such as a pump for pumping out the sulfuric acid-containing liquid in the first common pipe 51A is provided in the middle of the first sulfuric acid-containing liquid circulation pipe 51B. The sulfuric acid-containing liquid pumped out to the second circulation pipe 53 by the second liquid feeding device 56 flows through the first sulfuric acid-containing liquid circulation pipe 51B from the upstream end to the downstream end, and then flows into the second circulation tank 51. Return. As a result, 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 through 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 (>first temperature, for example, about 160° C.). By circulating the sulfuric acid-containing liquid through 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 sulfuric acid-containing liquid becomes The temperature of 1 is adjusted to the second temperature.

The sulfuric acid-containing liquid producing apparatus 8 is branched from the second circulation pipe 53 to supply the sulfuric acid-containing liquid to the SPM nozzles 13 of the plurality (for example, three) of the processing units 6 included in the corresponding tower. The sulfuric acid-containing liquid supply pipe 57 is included in the same number as the processing units 6 included in the tower.
A first heater 54 is provided in the middle of each first sulfuric acid-containing liquid supply pipe 57. In addition, in the middle of each first sulfuric acid-containing liquid supply pipe 57, on the downstream side of the first heater 54, the second flowmeter 78 and the first sulfuric acid-containing liquid are sequentially arranged from the first heater 54 side. A flow rate adjusting valve 59 and a first sulfuric acid-containing liquid valve 60 are provided. The second flow meter 78 is a flow meter that detects the flow rate of the sulfuric acid-containing liquid flowing through each first sulfuric acid-containing liquid supply pipe 57. The first sulfuric acid-containing liquid flow rate adjusting 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 rate adjusting valve 59 includes a valve body having a valve seat provided therein, 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. May be included. The same applies to the other flow rate adjusting valves.

The first sulfuric acid-containing liquid valve 60 is a valve for controlling the supply of the sulfuric acid-containing liquid to the SPM nozzle 13 and its stop.
A first return pipe 61 is branched and connected to the first sulfuric acid-containing liquid supply pipe 57 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 larger 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 becomes larger than the pressure loss in the downstream side portion of the first branch position 63 in the first sulfuric acid-containing liquid supply pipe 57. Therefore, the sulfuric acid-containing liquid in the upstream portion of the first branching position 63 in the first sulfuric acid-containing liquid supply pipe 57 is transferred to the downstream portion of the first branching position 63 in the first sulfuric acid-containing liquid supply pipe 57. It is supplied and is supplied to the SPM nozzle 13 from this downstream side portion. On the other hand, when stopping the supply of the sulfuric acid-containing liquid to the SPM nozzle 13, 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 becomes 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 flows to the first return pipe 61 without flowing backward in the upstream side portion of the first sulfuric acid-containing liquid supply pipe 57 of the first branch position 63. Be guided. The sulfuric acid-containing liquid guided to the first return pipe 61 returns to the first sulfuric acid-containing liquid circulation pipe 51B, and again, the second circulation tank 51 and the second circulation pipe 53 (first common pipe 51A and It circulates through the first sulfuric acid-containing liquid circulation pipe 51B). 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 (>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 until then is changed from the second temperature until then to the third temperature. Raise the temperature.

During the operation of the substrate processing apparatus 1 (including the period in 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 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) are heated to the second temperature. The adjusted sulfuric acid-containing liquid is circulating.

In the state where the first sulfuric acid-containing liquid valve 60 is closed, the sulfuric acid-containing liquid flowing in the second circulation pipe 53 flows from the second circulation pipe 53 to the first sulfuric acid-containing liquid supply pipe 57, and It flows through the branch position 63 to the first return pipe 61, and returns to the first sulfuric acid-containing liquid flow pipe 51B. This circulates through the second circulation tank 51 and the second circulation pipe 53.
On the other hand, in the 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 flow pipe 51B is supplied from the second circulation pipe 53 to the first sulfuric acid-containing liquid supply pipe 57. And 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 provided in the middle of the second common pipe 71A. The second circulation tank 51 and the second common pipe 71A are connected to three second sulfuric acid-containing liquid circulation pipes 71B for supplying the sulfuric acid-containing liquid to the corresponding towers. 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. A third circulation pipe 73 is configured by the second common pipe 71A and the second sulfuric acid-containing liquid circulation pipe 71B.

A third liquid sending device 76 such as a pump for pumping out the sulfuric acid-containing liquid in the second common pipe 71A is provided in the middle of the second sulfuric acid-containing liquid circulation pipe 71B. The sulfuric acid-containing liquid pumped out to the third circulation pipe 73 by the third liquid sending device 76 flows from the upstream end to the downstream end of the second sulfuric acid-containing liquid circulation pipe 71B, and then flows into the second circulation tank 51. Return. As a result, 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 through 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 becomes The temperature of 1 is adjusted to the fourth temperature.

The sulfuric acid-containing liquid preparation device 8 branches from the third circulation pipe 73 and is supplied to the lower surface nozzle 91 as an example of the back surface supply unit of the plurality (for example, three) of the processing units 6 included in the corresponding towers. The second sulfuric acid-containing liquid supply pipe 77 for supplying the (first sulfuric acid-containing liquid) is included in the same number as that of the processing units 6 included in the tower.
A second heater 74 is provided in the middle of each second sulfuric acid-containing liquid supply pipe 77. In addition, in the middle of each second sulfuric acid-containing liquid supply pipe 77, on the downstream side of the second heater 74, in order from the second heater 74 side, a second flow meter 78 and a second sulfuric acid-containing liquid are provided. A flow rate adjusting valve 79 and a second sulfuric acid-containing liquid valve 80 are provided. The second flow meter 78 is a flow meter that detects the flow rate of the sulfuric acid-containing liquid flowing in each second sulfuric acid-containing liquid supply pipe 77. The second sulfuric acid-containing liquid flow rate adjusting 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 of the sulfuric acid-containing liquid to the lower surface nozzle 91 and the stop thereof.
A second return pipe 81 is branched and connected to the second sulfuric acid-containing liquid supply pipe 77 between the second sulfuric acid-containing liquid valve 80 and the second sulfuric acid-containing liquid flow rate adjusting 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 larger 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 becomes larger than the pressure loss in the downstream side 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 side portion of the second branch position 83 in the second sulfuric acid-containing liquid supply pipe 77 is transferred to the downstream side portion of the second branch position 83 in the second sulfuric acid-containing liquid supply pipe 77. It is supplied and is supplied to the lower surface nozzle 91 from this downstream side portion. On the other hand, when stopping the supply of the sulfuric acid-containing liquid to the lower surface nozzle 91, 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 becomes smaller than the pressure loss in the downstream side 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 back into the second sulfuric acid-containing liquid supply pipe 77 on the upstream side of the second branch position 83, and flows to the second return pipe 81. Be guided. The sulfuric acid-containing liquid guided to the second return pipe 81 returns to the second sulfuric acid-containing liquid circulation pipe 71B, and again, the second circulation tank 51 and the third circulation pipe 73 (the second common pipe 71A and It circulates through the second sulfuric acid-containing liquid circulation pipe 71B). 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 (>fourth temperature, for example, about 165° C.). By flowing the sulfuric acid-containing liquid through the second sulfuric acid-containing liquid supply pipe 77, the sulfuric acid-containing liquid whose temperature has been adjusted to the fourth temperature rises from the fourth temperature until then to the fifth temperature. ..

During the operation of the substrate processing apparatus 1 (including the period in 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 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) are heated to the fourth temperature. The adjusted sulfuric acid-containing liquid is circulating.

In the state where the second sulfuric acid-containing liquid valve 80 is 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 It flows through the branch position 83 to the second return pipe 81 and returns to the second sulfuric acid-containing liquid circulation pipe 71B. This circulates through 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 flow pipe 71B is supplied from the third circulation pipe 73 to the second sulfuric acid-containing liquid supply pipe 77. And 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.

By referring to the output of the liquid meter 65, the liquid amount of the sulfuric acid-containing liquid stored in the second circulation tank 51 is constantly monitored by the control device 4. Then, when the liquid amount of the sulfuric acid-containing liquid stored in the second circulation tank 51 becomes smaller than the lower limit liquid amount, the opening/closing valve 38 is opened and the liquid is passed from the first liquid storage section 11 through the liquid introducing pipe 31. A sulfuric acid-containing liquid is supplied.
The first sulfuric acid-containing liquid flow pipe 51B and/or the second sulfuric acid-containing liquid flow pipe 71B 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 is provided. When 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 lower limit concentration, the sulfuric acid replenishment unit 25 causes the sulfuric acid replenishment pipe. The sulfuric acid replenishment valve 45 that opens and closes 44 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 becomes high, and accordingly, after a lapse of a while, 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 high.

FIG. 3 is a schematic sectional view for explaining a configuration example of the processing unit 6.
The processing unit 6 holds a box-shaped chamber 107 having an internal space and one substrate W in a horizontal posture in the chamber 107, and holds the substrate W around a vertical rotation axis A1 passing through the center of the substrate W. A spin chuck (substrate holding unit) 108 to be rotated, an SPM nozzle 13 for supplying SPM to the upper surface of the substrate W held by the spin chuck 108 (the front surface Wa of the substrate W (see FIG. 4B)), and the spin chuck. A rinse liquid supply unit 110 for supplying a rinse liquid to the upper surface of the substrate W held on the wafer 108 (the front surface Wa of the substrate W (see FIG. 4B)), and the lower surface of the substrate W held on the spin chuck 108 ( It includes a lower surface nozzle 91 that discharges the processing liquid toward the central portion of the back surface Wb (see FIG. 7A) of the substrate W, and a cylindrical processing cup 111 that surrounds the spin chuck 108.

The chamber 107 has a box-shaped partition 112, an FFU (fan filter unit) 114 as a blower unit for sending clean air from the upper part of the partition 112 into the partition 112 (corresponding to the inside of the chamber 107), and the lower part of the partition 112. An exhaust device (not shown) for exhausting the gas in the chamber 107 from. The FFU 114 is arranged above the partition wall 112 and is attached to the ceiling of the partition wall 112. The FFU 114 sends 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. A downflow (downflow) is formed in the chamber 107 by the FFU 114 and the exhaust device (not shown).

As the spin chuck 108, a sandwich type chuck that horizontally holds the substrate W and horizontally holds the substrate W is adopted. Specifically, the spin chuck 108 includes a spin motor (rotating unit) M, a spin shaft 115 integrated with a drive shaft of the spin motor M, and a disc mounted substantially horizontally on the upper end of the spin shaft 115. A spin base 116.
The spin base 116 includes a horizontal circular upper surface 116 a having an outer diameter larger than the outer diameter of the substrate W. A plurality of (three or more, for example, six) holding members 117 are arranged on the peripheral portion of the upper surface 116a. The plurality of holding members 117 are arranged at appropriate intervals on the circumference corresponding to the outer peripheral shape of the substrate W at the peripheral portion of the upper surface of the spin base 116.

The SPM nozzle 13 is, for example, a straight nozzle that discharges SPM in a continuous flow state. The SPM nozzle 13 is attached to the tip of the nozzle arm 119. The SPM nozzle 13 is attached to the nozzle arm 119, for example, in a vertical posture that discharges the processing liquid (SPM) in a direction perpendicular to the upper surface (front surface Wa) of the substrate W. The nozzle arm 119 extends in the horizontal direction. Further, a nozzle moving unit 120 that moves the SPM nozzle 13 by moving the nozzle arm 119 is coupled to the nozzle arm 119. The nozzle moving unit 120 is configured to include an electric motor.

The nozzle moving unit 120 horizontally moves the SPM nozzle 13 by horizontally moving the nozzle arm 119 around a vertical swing axis set around the processing cup 111. The nozzle moving unit 120 has a processing position at which the SPM discharged from the SPM nozzle 13 lands on the upper surface (front surface Wa) of the substrate W and a retracted position at which the SPM nozzle 13 is located around the spin chuck 108 in plan view. In between, the SPM nozzle 13 is moved horizontally. In this embodiment, the processing position is, for example, the central position where the SPM ejected from the SPM nozzle 13 reaches the central portion of the upper surface (front surface Wa) of the substrate W.

The treatment liquid supply apparatus further includes a hydrogen peroxide solution supply unit 122 that supplies hydrogen peroxide solution (H ₂ O ₂ ) to the SPM nozzle 13. The hydrogen peroxide solution supply unit 122 includes a hydrogen peroxide solution pipe 135 connected to the SPM nozzle 13, a hydrogen peroxide solution valve 136 for opening and closing the hydrogen peroxide solution pipe 135, and a hydrogen peroxide solution valve 136. And a hydrogen peroxide solution flow rate adjusting valve (mixing ratio changing unit) 137 for adjusting the opening degree to adjust the flow rate of the hydrogen peroxide solution flowing through the hydrogen peroxide solution valve 136. The hydrogen peroxide solution flow rate adjusting valve 137 includes a valve body having a valve seat provided therein, 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. It may be configured. Hydrogen peroxide solution at a room temperature (about 23° C. to about 25° C.) whose temperature is not adjusted is supplied to the hydrogen peroxide solution pipe 135 from a hydrogen peroxide solution supply source (not shown).

When the first sulfuric acid-containing liquid valve 60 and the hydrogen peroxide water valve 136 are opened, the high-temperature (about 165° C.) sulfuric acid-containing liquid from the second sulfuric acid-containing liquid supply pipe 77 and the hydrogen peroxide water pipe 135 are opened. Hydrogen peroxide solution is supplied into the casing (not shown) of the SPM nozzle 13, and is sufficiently mixed (stirred) in the casing. By this mixing, the sulfuric acid-containing liquid and the hydrogen peroxide solution are uniformly mixed, and the sulfuric acid-containing liquid and the hydrogen peroxide solution are mixed by the reaction of the sulfuric acid-containing liquid and the hydrogen peroxide solution contained in the sulfuric acid-containing liquid (SPM). ) Is generated. SPM contains peroxymonosulfuric acid (H ₂ SO ₅ ) having a strong oxidizing power, and has a temperature higher than the temperature of the sulfuric acid-containing liquid (for example, about 165° C.) and the hydrogen peroxide solution (for example, about 190° C.) before mixing. Up to about 220°C). The generated high temperature SPM is discharged from a discharge port opened at the tip (for example, the lower end) of the casing 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 adjusting valve 79. The flow rate of the hydrogen peroxide solution supplied to the SPM nozzle 13 is changed by the hydrogen peroxide solution flow rate adjusting valve 137. Therefore, the mixing ratio of the sulfuric acid-containing solution and the hydrogen peroxide solution is changed by the second sulfuric acid-containing solution flow rate adjusting valve 79 and the hydrogen peroxide solution flow rate adjusting valve 137.

The rinse liquid supply unit 110 includes a rinse liquid nozzle 147 that discharges the rinse liquid toward the upper surface (front surface Wa) of the substrate W. The rinse liquid nozzle 147 is, for example, a straight nozzle that discharges liquid in a continuous flow state. The rinse liquid nozzle 147 is a fixed nozzle fixed to the partition wall 112 of the chamber 107. The discharge port of the rinse liquid nozzle 147 is directed to the central portion of the upper surface (front surface Wa) of the substrate W. The rinse liquid nozzle 147 may be a scan nozzle movable in the chamber 107. That is, the rinsing liquid supply unit 110 moves the rinsing liquid nozzle 147 to move the rinsing liquid deposition position on the upper surface (front surface Wa) of the substrate W within the upper surface (front surface Wa) of the substrate W. May be provided.

The rinse liquid nozzle 147 is connected to the rinse liquid pipe 148 that guides the rinse liquid from the rinse liquid supply source. A rinse liquid valve 149 for switching supply/stop of supply of the rinse liquid from the rinse liquid nozzle 147 is provided in the middle of the rinse liquid pipe 148. When the rinse liquid valve 149 is opened, the rinse liquid is supplied from the rinse liquid pipe 148 to the rinse liquid nozzle 147 and is discharged from the discharge port provided at the lower end of the rinse liquid nozzle 147.

When the rinse liquid valve 149 is closed, the supply of the rinse liquid from the rinse liquid pipe 148 to the rinse liquid nozzle 147 is stopped. The rinse liquid is, for example, deionized water (DIW), but not limited to DIW, carbonated water, electrolytic ionized water, hydrogen water, ozone water, ammonia water, and dilution concentration (for example, about 10 ppm to 100 ppm). It may be any of the above hydrochloric acid water. The rinse liquid may be at room temperature (20 to 40° C.) or may be heated before being supplied to the substrate W.

The lower surface nozzle 91 has a single ejection port 91 a facing the central portion of the lower surface (back surface Wb) of the substrate W held by the spin chuck 108. The ejection port 91a ejects the liquid vertically upward. The ejected liquid enters the central portion of the back surface Wb of the substrate W held by the spin chuck 108 substantially vertically. A lower surface supply pipe 92 is connected to the lower surface nozzle 91. The lower surface supply pipe 92 is inserted inside the spin shaft 115 which is a vertically arranged hollow shaft. A second sulfuric acid-containing liquid supply pipe 77 and a rinse liquid pipe 93 are connected to the lower surface supply pipe 92, respectively.

A rinse liquid valve 94 for opening and closing the rinse liquid pipe 93 is interposed in the rinse liquid pipe 93. The rinse liquid supplied to the rinse liquid pipe 93 is, for example, water at room temperature (about 23° C. to about 25° C.). In this embodiment, the water is any one of pure water (deionized water), carbonated water, electrolytic ion water, hydrogen water, ozone water, and ammonia water having a dilution concentration (for example, about 10 to 100 ppm).

When the second sulfuric acid-containing liquid valve 80 is opened while the rinse liquid valve 94 is closed, 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 supply pipe. It is supplied into the casing (not shown) of the lower surface nozzle 91 via 92. The high temperature sulfuric acid-containing liquid supplied to the lower surface nozzle 91 is discharged from the discharge port 91a in a substantially vertically upward direction. The high temperature sulfuric acid-containing liquid (second sulfuric acid-containing liquid) discharged from the lower surface nozzle 91 is incident substantially vertically on the central portion of the back surface Wb of the substrate W held by the spin chuck 108.

When the rinse liquid valve 94 is opened while the second sulfuric acid-containing liquid valve 80 is closed, the rinse liquid from the rinse liquid supply source reaches the lower surface nozzle 91 via the rinse liquid pipe 93 and the lower surface supply pipe 92. Supplied. The rinse 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 is incident on the central portion of the back surface Wb of the substrate W held by the spin chuck 108 substantially vertically.

The processing cup 111 is arranged outside (in a direction away from the rotation axis A1) the substrate W held by the spin chuck 108. The processing cup 111 surrounds the side of the spin base 116. When the processing liquid is supplied to the substrate W while the spin chuck 108 is rotating the substrate W, the processing liquid supplied to the substrate W is shaken off around the substrate W. When the processing liquid is supplied to the substrate W, the upper end portion 111 a of the processing cup 111 opened upward is arranged above the spin base 116. Therefore, the processing liquid such as the chemical liquid or water discharged around the substrate W is received by the processing cup 111. Then, the processing liquid received in the processing cup 111 is sent to the first circulation tank 22 of the first liquid storage section 11 or sent to a waste liquid device (not shown) via a cooling unit (not shown). Be done.

The processing cup 111 includes a plurality of cylindrical guards 143 to 145 (first, second and third guards 143, 144, 145) for receiving the processing liquid (chemical solution or rinse) scattered around the substrate W, and a plurality of A plurality of annular cups 141, 142 for receiving the processing liquid guided by the guards 143-145, and a cylindrical member 140 surrounding the guards 143-145 and the cups 141, 142.

The processing cup 111 further includes a guard elevating unit (switching unit) 146 for elevating and lowering the individual guards 143-145 independently. The guard lifting unit 146 includes, for example, an electric motor that generates power and a ball screw mechanism that transmits the power of the electric motor to any of the guards 143 to 145. When the guard elevating unit 146 elevates and lowers at least one of the three guards 143 to 145, the state of the processing cup 111 is switched.

As will be described later, the processing cup 111 is in the retracted state in which the upper ends of all the guards 143 to 145 are arranged below the substrate W (the state shown in FIG. 5) and the first guard 143 is set to the substrate W. A first facing state in which the second guard 144 faces the circumferential end surface of the substrate W, a third facing state in which the second guard 144 faces the circumferential end surface of the substrate W, and a third facing state in which the third guard 145 faces the circumferential end surface of the substrate W. It can be switched to either of the facing state.

The first cup 141 surrounds the spin chuck 108 inside the cylindrical member 140. The first cup 141 defines an annular first groove 150 into which the processing liquid used for processing the substrate W flows. A drainage port 151 is opened at the lowest point of the bottom of the first groove 150, and a drainage pipe 152 is connected to the drainage port 151. The processing liquid introduced into the drainage pipe 152 is sent to a waste liquid device (not shown) via a cooling unit (not shown) and processed in the waste liquid device.

The second cup 142 surrounds the first cup 141 inside the cylindrical member 140. The second cup 142 defines an annular second groove 153 into which the processing liquid used for processing the substrate W flows. A recovery port 154 is opened at the lowest point of the bottom of the second groove 153, and the recovery port 154 is connected to the upstream end of a recovery pipe 156. The recovery pipe 156 is connected to the first circulation tank 22 of the first liquid storage unit 11 via the recovery outlet pipe 26.

The innermost first guard 143 surrounds the spin chuck 108 inside the cylindrical member 140. The first guard 143 includes a cylindrical lower end portion 163 surrounding the spin chuck 108, a cylindrical portion 164 extending outward from the upper end of the lower end portion 163 (a direction away from the rotation axis A1 of the substrate W), and a cylinder. A cylindrical middle step portion 165 extending vertically upward from the upper end of the stepped portion 164, and an annular upper end portion 166 extending obliquely upward from the upper end of the intermediate step portion 165 inward (direction approaching the rotation axis A1 of the substrate W). And, including.

The lower end portion 163 of the first guard 143 is located on the first groove 150 of the first cup 141. The inner peripheral edge of the upper end portion 166 of the first guard 143 has a circular shape having a larger diameter than the substrate W held by the spin chuck 108 in a plan view. As shown in FIG. 5, the cross-sectional shape of the upper end portion 166 of the first guard 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 guard 144 that is second from the inner side surrounds the first guard 143 inside the cylindrical member 140. The second guard 144 includes a cylindrical portion 167 that surrounds the first guard 143, and an annular upper end portion 168 that extends obliquely upward from the upper end of the cylindrical portion 167 toward the center side (direction toward the rotation axis A1 of the substrate W). have. The cylindrical portion 167 of the second guard 144 is located on the second groove 153 of the second cup 142.

The inner peripheral edge of the upper end portion 168 of the second guard 144 has a circular shape having a larger diameter than the substrate W held by the spin chuck 108 in a plan view. The cross-sectional shape of the upper end portion 168 of the second guard 144 is linear. The cross-sectional shape of the upper end portion 168 may be a shape other than a linear shape such as an arc. The upper end 168 of the second guard 144 vertically overlaps the upper end 166 of the first guard 143. The upper end portion 168 of the second guard 144 is arranged so as to be close to the upper end portion 166 of the first guard 143 with a minute gap in the state where the first guard 143 and the second guard 144 are closest to each other. Is formed in.

The third guard 145 third from the inside surrounds the second guard 144 inside the cylindrical member 140. The third guard 145 includes a cylindrical portion 170 that surrounds the second guard 144, and an annular upper end portion 171 that extends obliquely upward from the upper end of the cylindrical portion 170 toward the center side (direction toward the rotation axis A1 of the substrate W). have. The inner peripheral edge of the upper end portion 171 has a circular shape having a larger diameter than the substrate W held by the spin chuck 108 in a plan view. The cross-sectional shape of the upper end portion 171 is linear. The cross-sectional shape of the upper end portion 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 guard 143, and the outer periphery of the casing of the spin chuck 108 are provided in a first distribution space (in other words, a chemical solution used for processing the substrate W). , Drainage space) SP1 is partitioned. The second groove 153 of the second cup 142, the outer wall 143b of the first guard 143, and the inner wall 144a of the second guard 144 have a second distribution space (in other words, a second distribution space into which the chemical solution used for processing the substrate W is introduced. Then, the collection space) SP2 is partitioned. The first distribution space SP1 and the second distribution space SP2 are isolated from each other by the first guard 143.

The guard lifting unit 146 is provided between the upper position where the upper ends of the guards 143 to 145 are located above the substrate W and the lower position where the upper ends of the guards 143 to 145 are located below the substrate W. Raise and lower ~145. The guard lifting unit 146 can hold the guards 143 to 145 at an arbitrary position between the upper position and the lower position. The supply of the processing liquid to the substrate W is performed in a state where any of the guards 143 to 145 faces the peripheral end surface of the substrate W.

In the first facing state of the processing cup 111 in which the innermost first guard 143 is opposed to the peripheral end surface of the substrate W, all of the first to third guards 143 to 145 are in the upper position (processing height position). Is located in. In the second facing state of the processing cup 111 in which the second guard 144 that is second from the inner side faces the peripheral end surface of the substrate W, the second and third guards 144 and 145 are arranged at the upper position and The one guard 143 is arranged at the lower position. In the third facing state of the processing cup 111 in which the outermost third guard 145 is opposed to the peripheral end surface of the substrate W, the third guard 145 is arranged at the upper position, and the first and second guards 143 are arranged. , 144 are arranged in the lower position. In the retracted state in which all the guards 143 to 145 are retracted from the peripheral end surface of the substrate W (see FIG. 5 ), all of the first to third guards 143 to 145 are 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 an arithmetic unit such as a CPU, a storage unit such as a fixed memory device and a hard disk drive, and an input/output unit for inputting and outputting information. The storage unit includes a computer-readable recording medium recording a computer program executed by the arithmetic unit. A step group is incorporated in the recording medium so as to cause the control device 4 to execute a resist removing process described later.

The control device 4 follows the predetermined program, the spin motor M, the nozzle moving unit 120, the guard elevating unit 146, the first liquid feeding device 32, the second liquid feeding device 56, the third liquid feeding device 76, The operations of the first circulation heater 24, the second circulation heater 52, the first heater 54, the third circulation heater 72, the second heater 74, etc. are controlled. In addition, the control device 4 according to a predetermined program, the opening/closing valve 38, the return valve 41, the sulfuric acid replenishment valve 45, the first sulfuric acid-containing liquid valve 60, the second sulfuric acid-containing liquid valve 80, the rinse liquid valve 94, The opening/closing operations of the hydrogen peroxide solution valve 136, the rinse liquid valve 149, etc. are controlled. Further, the control device 4 adjusts the opening degrees of the first sulfuric acid-containing liquid flow rate adjusting valve 59, the second sulfuric acid-containing liquid flow rate adjusting valve 79, and the hydrogen peroxide solution flow rate adjusting valve 137 according to a predetermined program. .. The measured values of the sulfuric acid concentration meter 64 and the liquid meter 65 are input to the control device 4, respectively.

FIG. 4B is an enlarged cross-sectional view showing the front surface Wa of the substrate W to be processed by the substrate processing apparatus 1. The substrate W to be processed is, for example, a silicon wafer, and the pattern 100 is formed on the surface Wa which is a pattern forming surface. The pattern 100 is, for example, a fine pattern. As shown in FIG. 4B, the pattern 100 may be one in which the structures 101 having a convex shape (columnar shape) are arranged in a matrix. 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. The pattern 100 may have an aspect ratio (ratio of the film thickness T to the line width W1) of, for example, about 5 to 500 (typically, about 5 to 50).

Further, the pattern 100 may be one in which line-shaped patterns formed by fine trenches are repeatedly arranged. The pattern 100 may be formed by providing a plurality of fine holes (voids or pores) in the thin film.
The pattern 100 includes, for example, an insulating film. Further, the pattern 100 may include a conductor film. More specifically, the pattern 100 is formed of a laminated film in which a plurality of films are laminated, and may further include an insulating film and a conductor film. The pattern 100 may be a pattern composed of a single layer film. The insulating film may be a silicon oxide film (SiO ₂ film) or a silicon nitride film (SiN film). Further, the conductor film may be an amorphous silicon film into which impurities for reducing the resistance have been introduced, or a metal film (for example, a metal wiring film).

Moreover, the pattern 100 may be a hydrophilic film. An example of the hydrophilic film is a TEOS film (a kind of silicon oxide film).
FIG. 5 is a flowchart of the first substrate processing example executed by the processing unit 6.
Hereinafter, a first substrate processing example, which is an example of processing of the substrate W, will be described with reference to FIGS. 1 to 5. An example of the processing of the substrate W is a resist removal processing 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. It is assumed that the substrate W has not undergone the process for ashing the resist.

When the substrate W is processed by the substrate processing apparatus 1, all the nozzles are retracted from above the spin chuck 108, and all the guards 143 to 145 are positioned at the lower position. The hands of the substrate transfer robots CR1 and CR2 (see FIG. 1) holding the substrate W in which at least a part of the surface (device formation surface) of the substrate W is covered with the resist are moved into the chamber 107. As a result, the substrate W is passed to the spin chuck 108 with the surface thereof facing upward, and is held by the spin chuck 108.

After the substrate W is held by the spin chuck 108, the control device 4 causes the spin motor M to start rotating. As a result, 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 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 supplies the sulfuric acid-containing liquid at high temperature (about 165° C.) to the back surface Wb of the substrate W on the back surface of the sulfuric acid-containing liquid (S3 in FIG. 5). I do. The sulfuric acid-containing liquid back surface supply step S3 is executed prior to the start of the SPM front surface supply step S4 described below.
Specifically, the control device 4 opens the second sulfuric acid-containing liquid valve 80. As a result, 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 via the lower surface supply pipe 92, and is almost discharged from the discharge port 91 a of the lower surface nozzle 91. It is discharged vertically upward. As a result, the high temperature sulfuric acid-containing liquid (second sulfuric acid-containing liquid) is incident substantially vertically on the central portion of the back surface Wb of the substrate W. The sulfuric acid-containing liquid supplied to the central portion of the back surface Wb of the substrate W receives the centrifugal force due to the rotation of the substrate W and spreads over the entire back surface Wb of the substrate W. As a result, the sulfuric acid-containing liquid is supplied to the entire back surface Wb of the substrate W. The sulfuric acid-containing liquid that moves on the back surface Wb of the substrate W is scattered from the peripheral portion of the substrate W toward the side of the substrate W.

Next, the control device 4 executes the SPM surface supply process (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. Further, the control device 4 simultaneously opens the first sulfuric acid-containing liquid valve 60 and the hydrogen peroxide solution valve 136. As a result, 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 solution is supplied to the SPM nozzle 13 through the hydrogen peroxide water pipe 135. The sulfuric acid-containing liquid and the hydrogen peroxide solution are mixed inside the SPM nozzle 13 to generate high-temperature (for example, 190 to 220° C.) SPM. The SPM is discharged from the discharge port of the SPM nozzle 13 and reaches the center of the upper surface (front surface Wa) of the substrate W.

The SPM ejected from the SPM nozzle 13 reaches the front surface Wa of the substrate W and then flows outward along the front surface Wa of the substrate W by centrifugal force. Therefore, SPM is supplied to the entire surface Wa of the substrate W, and a liquid film of SPM covering the entire surface Wa of the substrate W is formed on the substrate W. As a result, the resist and SPM chemically react, and the resist on the substrate W is removed from the substrate W by SPM. The SPM scatters from the peripheral portion of the substrate W toward the sides of the substrate W.

In the SPM front surface supply step S4, the control device 4 controls the nozzle moving unit 120 to move the SPM nozzle 13 to the peripheral position facing the peripheral portion of the front surface Wa of the substrate W and the center of the front surface Wa of the substrate W. It may be moved to and from a central position facing the section. In this case, since the SPM liquid deposition position on the upper surface of the substrate W passes through the entire front surface Wa of the substrate W, the entire front surface Wa of the substrate W is scanned at the SPM liquid deposition position. As a result, the entire surface Wa of the substrate W is uniformly processed.

When a predetermined period (for example, about 27 seconds) has elapsed from the start of SPM discharge, the control device 4 closes the first sulfuric acid-containing liquid valve 60 and the hydrogen peroxide solution valve 136 to discharge SPM from the SPM nozzle 13. To stop. As a result, the SPM surface supply step S4 ends. After that, the control device 4 controls the nozzle moving unit 120 (see FIG. 4) to return the SPM nozzle 13 to the retracted position. As will be described later, the SPM surface supply step S4 includes a first surface supply step S41 and a second surface supply step S42 that is executed subsequent to the end of the first surface supply step S41.

Then, a rinse step of supplying the rinse liquid to the substrate W (S5 in FIG. 5) is performed. Specifically, the control device 4 opens the rinse liquid valve 149 and causes the rinse liquid nozzle 147 to discharge the rinse liquid toward the central portion of the front surface Wa of the substrate W. The rinse liquid ejected from the rinse liquid nozzle 147 reaches the central portion of the front surface Wa of the substrate W covered with the SPM. The rinse liquid that has landed on the central portion of the front surface Wa of the substrate W receives the centrifugal force due to the rotation of the substrate W and flows on the upper surface of the substrate W toward the peripheral portion of the substrate W. As a result, the SPM on the substrate W is pushed outward by the rinse liquid and is discharged to the periphery of the substrate W. As a result, the SPM and the resist are washed away from the entire surface Wa of the substrate W. When a predetermined period has elapsed from the start of the rinse step S5, the control device 4 closes the rinse liquid valve 149 to stop the rinse liquid nozzle 147 from discharging the rinse liquid.

Next, a drying step (S6 in FIG. 5) of drying the substrate W is performed. Specifically, the control device 4 controls the spin motor M so that the drying rotation speed is higher than the rotation speed up to the sulfuric acid-containing liquid back surface supply step S3, the SPM front surface supply step S4, and the rinse step S5 (for example, several thousands). The substrate W is accelerated to (rpm) and the substrate W is rotated at the drying rotation speed. Thereby, a large centrifugal force is applied to the liquid on the substrate W, and the liquid adhering to the substrate W is shaken off around the substrate W. In this way, the liquid is removed from the substrate W and the substrate W is dried. Then, when a predetermined period elapses after the high speed rotation of the substrate W is started, the control device 4 stops the spin motor M and stops the rotation of the substrate W by the spin chuck 108 (S7 in FIG. 5).

Next, the substrate W is unloaded from the chamber 107 (S8 in FIG. 5). Specifically, the control device 4 causes the hands of the substrate transfer robots CR1 and CR2 to enter the inside of the chamber 107 in a state where all the guards 143 to 145 are located at the lower position. Then, the control device 4 causes the hands of the substrate transport robots CR1 and CR2 to hold the substrate W on the spin chuck 108. After that, the control device 4 retracts the hands of the substrate transfer robots CR1 and CR2 from the chamber 107. As a result, the substrate W from which the resist has been removed from the front surface Wa (for example, the device formation surface) is carried out from the chamber 107.

Next, in the SPM surface supply step (S4 in FIG. 5), changes in the supply flow rate of the sulfuric acid-containing liquid to the upper and lower surfaces of the substrate W and the supply flow rate of hydrogen peroxide solution to the upper surface of the substrate W, and the first guard. Operations and the like of 143 and the second guard 144 will be described.
FIG. 6 is a timing chart showing the operation and the like of the first guard 143 and the second guard 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 guard 144, and the recovery OFF indicates the recovery from the substrate W. This indicates that the discharged liquid (sulfuric acid-containing liquid or SPM) has stopped flowing into the recovery pipe 156. In FIG. 6, ON of the drainage means that the liquid (sulfuric acid-containing liquid or SPM) discharged from the substrate W flows into the drainage pipe 152 via the first guard 143, and OFF of the drainage is This indicates that the liquid (sulfuric acid-containing liquid or SPM) discharged from the substrate W is stopped from flowing into the drain pipe 152.

FIG. 7A is a schematic diagram for explaining the sulfuric acid-containing liquid back surface supply step S3. 7B and 7C are schematic diagrams for explaining the SPM surface supply step S4.
In the following, reference is made to FIGS. 7A to 7C are referred to 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 execute the following operations and the like.

As shown in FIG. 6, the processing cup 111 has the middle of the three guards 143 to 145 before the lower surface nozzle 91 starts discharging the sulfuric acid-containing liquid (before time T1 shown in FIG. 6 ). The second guard 144 is set in a second facing state where it faces the peripheral end surface of the substrate W.
When the second sulfuric acid-containing liquid valve 80 is opened at time T1 shown in FIG. 6, as shown in FIG. 7A, the high-temperature (for example, about 165° C.) sulfuric acid-containing liquid is supplied to the lower surface nozzle 91, and the lower surface nozzle 91 outputs it. The high-temperature sulfuric acid-containing solution is discharged toward the back surface Wb of the substrate W (sulfuric acid-containing solution back surface supply step S3 in FIG. 5). As a result, as shown in FIG. 7A, the entire back surface Wb of the substrate W is covered with the liquid film of the sulfuric acid-containing liquid. The substrate W is warmed by the liquid film of the high temperature sulfuric acid-containing liquid.

The sulfuric acid-containing liquid discharged from the substrate W is received by the inner wall 144a of the second guard 144 and guided to the second cup 142, as shown in FIG. 7A. Then, the sulfuric acid-containing liquid in the second cup 142 is sent to the first circulation tank 22 of the first liquid storage section 11 via the recovery pipe 156. As a result, the sulfuric acid-containing liquid supplied to the substrate W is recovered (collection step; recovery ON shown in FIG. 6). When a predetermined period (a period sufficient to warm the entire substrate W to the same temperature as the liquid temperature of the sulfuric acid-containing liquid, for example, about 5 seconds) has elapsed since the second sulfuric acid-containing liquid valve 80 was opened, At time T2 shown in FIG. 6, the second sulfuric acid-containing liquid valve 80 is closed.

The guard elevating unit 146 raises the first guard 143 to the upper position after the second sulfuric acid-containing liquid valve 80 is closed. Therefore, the processing cup 111 switches from the second facing state to the first facing state in which the first guard 143 faces the peripheral end surface of the substrate W.
Thereafter, when the first sulfuric acid-containing liquid valve 60 and the hydrogen peroxide solution valve 136 are opened at time T3 shown in FIG. 6, the sulfuric acid-containing solution and the hydrogen peroxide solution are supplied to the SPM nozzle 13 (see FIG. 5). 1 surface supply step S41). The sulfuric acid-containing liquid and the hydrogen peroxide solution are mixed in the SPM nozzle 13, and the SPM is created in the SPM nozzle 13. The created 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 surface Wa of the substrate W is formed. Then, the resist is removed from the front surface Wa of the substrate W by the liquid film of SPM. Since the SPM surface supply step S4 is started to be performed on the substrate W that has been sufficiently heated, the resist removal efficiency by SPM is high. 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 not set to be long, It is possible to remove SPM almost completely. Therefore, the processing period of the SPM surface supply step S4 (more specifically, the processing period of the first surface supply step S41) is as short as possible within the range in which the resist can be roughly removed from the surface Wa of the substrate W. It is set to a period (for example, about 12 seconds).

The SPM discharged from the substrate W is received by the inner wall 143 a of the first guard 143 and guided to the first cup 141. Then, the SPM in the first cup 141 is discharged to the drainage pipe 152 (ON of drainage shown in FIG. 6; drainage step).
A large amount of resist is contained in the SPM discharged from the substrate W during a predetermined period after the start of the SPM surface supply step S4. If a sulfuric acid-containing solution is prepared based on SPM containing a large amount of such resist, it is difficult to prepare a clean sulfuric acid-containing solution. Therefore, the SPM discharged from the substrate W during this period is drained (discarded) without being reused (not collected), so that the SPM containing a large amount of resist is supplied to the sulfuric acid-containing liquid producing apparatus 8. Can be prevented. As a result, a clean sulfuric acid-containing liquid can be created in the sulfuric acid-containing liquid creating device 8.

On the other hand, it is preferable to minimize the drainage (disposal) of SPM from the viewpoint of environmental consideration. Therefore, if the SPM discharged from the substrate W does not contain the resist, it is preferable to collect and reuse the SPM.
After the first sulfuric acid-containing liquid valve 60 and the hydrogen peroxide solution valve 136 are opened, a predetermined period (a period in which SPM discharged from the substrate W contains almost no resist, for example, about 12 seconds) elapses. The guard lifting unit 146 lowers the first guard 143 to the lower position at time T5 shown in FIG. Therefore, the processing cup 111 is switched to the second facing state in which the second guard 144 faces the peripheral end surface of the substrate W. The SPM discharged from the substrate W is received by the inner wall 144a of the second guard 144 and guided by the second cup 142 (second surface supply step S42 in FIG. 5). Then, the SPM in the second cup 142 is sent to the first circulation tank 22 of the first liquid storage section 11 via the recovery pipe 156. As a result, the SPM supplied to the substrate W is collected (collection step). Note that, of the SPM surface supply step S4, the SPM surface supply step in which the processing cup 11 is executed in the first facing state is referred to as a first surface supply step.

After the processing cup 111 is switched to the second facing state or when a predetermined period (for example, about 15 seconds) elapses, the first sulfuric acid-containing liquid valve 60 and the hydrogen peroxide solution valve 136 are turned on at time T6 shown in FIG. It is closed, and the discharge of SPM from the SPM nozzle 13 is stopped.
After the discharge of the SPM from the SPM nozzle 13 is stopped at time T6 shown in FIG. 6, the guard elevating unit 146 starts raising the first guard 143 from the lower position, and at time T7 shown in FIG. Raise to position. As a result, in the processing cup 111, the SPM nozzle 13 has stopped discharging the SPM, and the first guard 143 covers the periphery of the substrate W while the entire upper surface of the substrate W is covered with the SPM liquid film. It switches to a first facing state that faces the end face. In this state, the rinse step of supplying the rinse liquid to the substrate W (S5 in FIG. 5) is performed. The drying step of drying the substrate W (S6 in FIG. 5) is performed in a state where the processing cup 111 is set in a third facing state in which the third guard 145 faces the peripheral end surface of the substrate W.

As described above, according to this embodiment, the high-temperature sulfuric acid-containing liquid serving as a base for creating the SPM supplied to the front 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). .. By supplying the high temperature sulfuric acid-containing liquid to the back surface Wb of the substrate W prior to the SPM front surface supply step S4, the substrate W is warmed prior to the start of the SPM front surface supply step S4. Therefore, it is possible to execute the SPM surface supply step S4 on the substrate W that has been sufficiently heated. Thereby, the resist removal efficiency by 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 relatively short, The resist can be roughly removed. This makes it possible to reduce the consumption of SPM, and thus the consumption of the sulfuric acid-containing liquid.

Further, the collecting step is performed in parallel with the sulfuric acid-containing liquid back surface supplying 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 then, in the sulfuric acid-containing liquid producing device 8, based on the recovered sulfuric acid-containing liquid. A sulfuric acid-containing liquid is created (sulfuric acid-containing liquid creating step). 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 producing the SPM used in the SPM front surface supply step S4. Thereby, the heating of the substrate W using the sulfuric acid-containing liquid can be performed without increasing the consumption amount of the sulfuric acid-containing liquid.

The temperature of the substrate W immediately after being held by the spin chuck 108 is room temperature. When the high temperature (for example, about 190° C. to about 220° C.) SPM is supplied to the substrate W at room temperature without performing the sulfuric acid-containing liquid back surface supply process S3 before the SPM front surface supply process S4, the surface temperature of the substrate W suddenly increases. There is a risk that the pattern 100 formed on the front surface Wa of the substrate W will be given a heat shock. This heat shock is considered to be one of the causes of the collapse of the pattern 100.

However, in this first substrate processing example, the temperature of the substrate W is raised before the SPM front surface supply step S4 is started by executing the sulfuric acid-containing liquid back surface supply step S3 before the SPM front surface supply step S4. Therefore, the SPM surface supply step S4 can be started in a state where the temperature of the substrate W is raised more than immediately after being held by the spin chuck 108. Therefore, it is possible to suppress the occurrence of heat shock due to the supply of SPM, and thus it is possible to suppress or prevent damage to the pattern 100 formed on the front surface Wa of the substrate W.

Further, 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 during the SPM surface supply step S4.
When the sulfuric acid-containing solution valve 60 and the hydrogen peroxide solution valve 136 are opened at time T3 shown in FIG. 6, the sulfuric acid-containing solution is supplied to the SPM nozzle 13 at the first sulfuric acid-containing solution flow rate, and the hydrogen peroxide solution is firstly supplied. Is supplied to the SPM nozzle 13 at a flow rate of H ₂ O ₂ . Therefore, the sulfuric acid-containing liquid and the hydrogen peroxide solution 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). As a result, the first SPM is created in the SPM nozzle 13 and ejected from the SPM nozzle 13 toward the upper surface of the substrate W (first surface supply step S41 in FIG. 5). As a result, a first SPM liquid film covering the entire upper surface of the substrate W is formed.

Then, when a predetermined period has elapsed since the first sulfuric acid-containing liquid valve 60 and the hydrogen peroxide solution valve 136 were opened, the second sulfuric acid-containing liquid flow rate adjusting valve 79 and the hydrogen peroxide at time T4 shown in FIG. At least one opening of the water flow rate adjusting valve 137 is changed so that the sulfuric acid-containing liquid and the hydrogen peroxide solution have a second mixture ratio (second sulfuric acid-containing liquid flow rate/second mixture ratio) larger than the first mixture ratio. H ₂ O ₂ flow rate) in the SPM nozzle 13. FIG. 6 shows an example in which the openings of both the sulfuric acid-containing liquid flow rate adjusting valve 59 and the hydrogen peroxide solution flow rate adjusting valve 137 are changed. As a result, the second SPM is created in the SPM nozzle 13 and discharged from the SPM nozzle 13 toward the upper surface of the substrate W (second surface supply step S42 in FIG. 5). As a result, the liquid film of the first SPM covering the entire upper surface of the substrate W is replaced with the liquid film of the second SPM covering the entire 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 second sulfuric acid-containing liquid flow rate that is higher than the first sulfuric acid-containing liquid flow rate, and the hydrogen peroxide solution is supplied from the first H ₂ O ₂ flow rate. Is also supplied to the SPM nozzle 13 at a _second H ₂ O ₂ flow rate that is small. The second flow rate of the sulfuric acid-containing liquid and the second flow rate of the H ₂ O ₂ have a constant flow rate of the SPM discharged from the SPM nozzle 13 even if the mixing ratio (ratio of the sulfuric acid-containing solution to the hydrogen peroxide solution) is changed. The flow rate of the SPM discharged from the SPM nozzle 13 may be set to be maintained or increased or decreased. The mixing ratio is 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 the state where the concentration of hydrogen peroxide is high to the state where the concentration of the sulfuric acid-containing liquid is high.

Such a density change is not limited to the first substrate processing example, and may be performed in a second substrate processing example or a third substrate processing example described later.
FIG. 8 is a flowchart of the second substrate processing example 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 performed in parallel with the SPM front surface supply step S4 instead of before the SPM front surface supply step S4. That's the point I decided to do. In the second substrate processing example, the sulfuric acid-containing liquid back surface supply step S13 is performed in parallel with the second front surface supply step S42.

After the substrate W is held by the spin chuck 108, the control device 4 causes the spin motor M to start rotating. As a result, 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). With the SPM nozzle 13 arranged at the processing position, the control device 4 simultaneously opens the first sulfuric acid-containing liquid valve 60 and the hydrogen peroxide solution valve 136. As a result, the sulfuric acid-containing liquid and the hydrogen peroxide solution 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 (front surface Wa) of the substrate W.

Further, in the first surface supply step S41, the processing cup 111 is set in the first facing state. Therefore, the SPM discharged from the substrate W is received by the inner wall 143a of the first guard 143 and guided to the first cup 141. Then, the SPM in the first cup 141 is discharged to the drainage pipe 152 (drainage step).
When a predetermined period (for example, about 12 seconds) has passed since the first sulfuric acid-containing liquid valve 60 and the hydrogen peroxide solution valve 136 were opened (when the SPM discharged from the substrate W contains almost no resist), The second surface supply step S42 is started. That is, the guard elevating unit 146 lowers the first guard 143 to the lower position. As a result, the processing cup 111 is switched to the second facing state in which the second guard 144 faces the peripheral end surface of the substrate W, as shown in FIG. 9. As a result, the SPM discharged from the substrate W is received by the inner wall 144a of the second guard 144 and guided to the second cup 142.

The sulfuric acid-containing liquid discharged from the substrate W is received by the inner wall 144a of the second guard 144 and guided to the second cup 142, as shown in FIG.
Further, in parallel with the second front surface supply step S42, the sulfuric acid-containing liquid back surface supply step S13 (see FIG. 8) is executed. After the processing cup 111 is switched to the second facing state, the controller 4 opens the second sulfuric acid-containing liquid valve 80. As a result, as shown in FIG. 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 (second The sulfuric acid-containing liquid is discharged (sulfuric acid-containing liquid back surface supply step S13). As a result, as shown in FIG. 9, the entire back surface Wb of the substrate W is covered with the liquid film of the sulfuric acid-containing liquid. The substrate W is warmed by the liquid film of the high temperature sulfuric acid-containing liquid.

12A to 12D are schematic diagrams for explaining removal (peeling) of the resist 181 formed on the front 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 so as to selectively cover the pattern 100. On the surface of the resist 181, there is a hardened layer 182 which has been altered by the ion implantation process which is a pretreatment. That is, the resist 181 formed on the front surface Wa of the substrate W includes the hardened layer 182 and the non-hardened layer 183 that has not deteriorated.

In the second front surface supplying step S42, high temperature SPM of, for example, about 190° C. to about 220° C. is supplied to the front surface Wa of the substrate W, and at the same time, a high temperature sulfuric acid-containing liquid of, for example, about 165° C. is applied to the back surface Wb of the substrate W. Is supplied to. The temperature of the substrate W is raised by supplying the sulfuric acid-containing liquid to the back surface Wb of the substrate W, and accordingly, the resist 181 is heated from the entire area including the bottom surface. The heating from the bottom surface of the resist 181 effectively raises the temperature of the resist 181. As a result, as shown in FIG. 12B, the gas 184 is generated in the non-cured layer 183, and the generated gas 184 fills the non-cured layer 183. Then, the pressure in the non-cured layer 183 increases, which causes the crack 185 in the cured layer 182 as shown in FIG. 12C.

Then, the SPM enters the inside of the hardened layer 182 through the crack 185 formed in the hardened layer 182. The entered SPM acts on the non-cured layer 183 and removes the non-cured layer 183 from the front surface Wa of the substrate W, as shown in FIG. 12D.
In the second surface supply step S42, the SPM and the sulfuric acid-containing liquid are supplied to the second cup 142. Then, the SPM and sulfuric acid-containing liquid in the second cup 142 is sent to the first circulation tank 22 of the first liquid storage unit 11 via the recovery pipe 156. As a result, the SPM and the sulfuric acid-containing liquid supplied to the substrate W are recovered (collection step).

When a predetermined period (a period sufficient to warm the entire substrate W to the same temperature as the liquid temperature of the sulfuric acid-containing liquid, for example, about 5 seconds) has elapsed since the second sulfuric acid-containing liquid valve 80 was opened, control is performed. The device 4 closes the second sulfuric acid-containing liquid valve 80 to stop the discharge of the sulfuric acid-containing liquid from the lower surface nozzle 91. After that, when a predetermined period (for example, about 15 seconds) elapses from the lowering of the first guard 143, the control device 4 closes the first sulfuric acid-containing liquid valve 60 and the hydrogen peroxide solution valve 136, and the SPM nozzle 13 The discharge of SPM from is stopped.

According to the second substrate processing example, the high-temperature sulfuric acid-containing liquid serving as a base for creating the SPM supplied to the front 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). ). By supplying the high temperature sulfuric acid-containing liquid 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, the substrate W is warmed while executing the SPM surface supply step S4. Be done. Therefore, the SPM surface supply step S4 can be performed on the substrate W while sufficiently raising the temperature. Thereby, the resist removal efficiency by 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 relatively short, The resist can be roughly removed. This makes it possible to reduce the consumption of SPM, and thus the consumption of the sulfuric acid-containing liquid.

Further, in the second front surface supply step S42, the high temperature SPM is supplied to the front surface Wa of the substrate W, and at the same time, the high temperature sulfuric acid-containing liquid is supplied to the rear surface Wb of the substrate W. The SPM can enter the non-cured layer 183 through the crack 185 of the cured layer 182 generated by heating the resist 181, and thus the resist removal efficiency can be improved. Therefore, the processing period of the SPM surface supply step S4 (more specifically, the processing period of the first surface supply step S41) can be shortened.

Further, the collecting step is executed in parallel with the sulfuric acid-containing liquid back surface supplying 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 then, in the sulfuric acid-containing liquid producing device 8, based on the recovered sulfuric acid-containing liquid. A sulfuric acid-containing liquid is created (sulfuric acid-containing liquid creating step). 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 producing the SPM used in the SPM front surface supply step S4. Thereby, the heating of the substrate W using the sulfuric acid-containing liquid can be performed without increasing the consumption amount of the sulfuric acid-containing liquid.

Further, since the sulfuric acid-containing liquid back surface supply step S13 in which the recovery step is performed in parallel is executed in parallel with the second front surface supply step S42 instead of in parallel with the first front surface supply step S41, a large amount of resist is contained. The sulfuric acid-containing liquid can be recovered without recovering SPM. This makes it possible to heat the substrate W using the sulfuric acid-containing liquid while preventing an increase in the consumption amount of the sulfuric acid-containing liquid without recovering the SPM containing a large amount of resist.

FIG. 10 is a flowchart of the third substrate processing example executed by the processing unit 6.
The third substrate processing example is different from the first substrate processing example in that the sulfuric acid-containing liquid back surface supply step S23 is performed in parallel with the SPM front surface supply step S4 instead of before the SPM front surface supply step S4. That's the point I decided to do. In the third substrate processing example, the sulfuric acid-containing liquid back surface supply step S3 is performed in parallel with the first front surface supply step S41.

After the substrate W is held by the spin chuck 108, the control device 4 causes the spin motor M to start rotating. As a result, 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). With the SPM nozzle 13 arranged at the processing position, the control device 4 simultaneously opens the first sulfuric acid-containing liquid valve 60 and the hydrogen peroxide solution valve 136. As a result, the sulfuric acid-containing liquid and the hydrogen peroxide solution 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 (front surface Wa) of the substrate W.

Further, in the first surface supply step S41, the processing cup 111 is set in the first facing state. Therefore, the SPM discharged from the substrate W is received by the inner wall 143a of the first guard 143 and guided to the first cup 141.
Further, in parallel with the first front surface supply step S41, the sulfuric acid-containing liquid back surface supply step S23 (see FIG. 10) is performed. With the processing cup 111 in the first facing state, the controller 4 opens the second sulfuric acid-containing liquid valve 80. As a result, as shown in FIG. 11, the 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 lower surface nozzle 91 is heated toward the rear surface Wb of the substrate W. The sulfuric acid-containing liquid is discharged (sulfuric acid-containing liquid back surface supply step S23). As a result, as shown in FIG. 11, the entire back surface Wb of the substrate W is covered with the liquid film of the sulfuric acid-containing liquid. The substrate W is warmed by the liquid film of the high temperature sulfuric acid-containing liquid. The sulfuric acid-containing liquid discharged from the substrate W is received by the inner wall 143a of the first guard 143 and guided to the first cup 141, as shown in FIG.

The sulfuric acid-containing liquid discharged from the substrate W is received by the inner wall 144a of the second guard 144 and guided to the second cup 142, as shown in FIG.
Further, in parallel with the second front surface supply step S42, the sulfuric acid-containing liquid back surface supply step S13 (see FIG. 8) is executed. After the processing cup 111 is switched to the second facing state, the controller 4 opens the second sulfuric acid-containing liquid valve 80. As a result, as shown in FIG. 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 back surface Wb of the substrate W is covered with the liquid film of the sulfuric acid-containing liquid. The substrate W is warmed by the liquid film of the high temperature sulfuric acid-containing liquid.

In the first front surface supply step S41, a high temperature SPM of, for example, about 190° C. to about 220° C. is supplied to the front surface Wa of the substrate W, and at the same time, a high temperature sulfuric acid-containing liquid of, for example, about 165° C. is applied to the back surface Wb of the substrate W. Is supplied to. The temperature of the substrate W is raised by supplying the sulfuric acid-containing liquid to the back surface Wb of the substrate W, and accordingly, the resist 181 is heated from the entire area including the bottom surface. The heating from the bottom surface of the resist 181 effectively raises the temperature of the resist 181 and the gas 184 generated in the non-cured layer 183 fills the non-cured layer 183. Then, the pressure in the non-hardened layer 183 increases, and as a result, the crack 185 is generated in the hardened layer 182. Then, the SPM that has entered the inside of the hardened layer 182 from the crack 185 formed in the hardened layer 182 acts on the non-hardened layer 183 and removes the non-hardened layer 183 from the front surface Wa of the substrate W (see FIGS. 12A to 12D). ).

In the first surface supply step S41, the SPM and sulfuric acid-containing liquid is supplied to the first cup 141. Then, the SPM and the sulfuric acid-containing liquid in the first cup 142 are discharged to the drainage pipe 152 (drainage step).
When a predetermined period (a period sufficient to warm the entire substrate W to the same temperature as the liquid temperature of the sulfuric acid-containing liquid, for example, about 5 seconds) has elapsed since the second sulfuric acid-containing liquid valve 80 was opened, control is performed. The device 4 closes the second sulfuric acid-containing liquid valve 80 to stop the discharge of the sulfuric acid-containing liquid from the lower surface nozzle 91.

After that, a predetermined period (a period in which SPM discharged from the substrate W contains almost no resist, for example, about 12 seconds) has been set since the first sulfuric acid-containing liquid valve 60 and the hydrogen peroxide solution valve 136 were opened. After a lapse of time, execution of the second surface supply step S42 is started. That is, the guard elevating unit 146 lowers the first guard 143 to the lower position. As a result, the processing cup 111 is switched to the second facing state in which the second guard 144 faces the peripheral end surface of the substrate W. As a result, the SPM discharged from the substrate W is received by the inner wall 144a of the second guard 144 and guided to the second cup 142. Then, the SPM in the second cup 142 is sent to the first circulation tank 22 of the first liquid storage section 11 via the recovery pipe 156. As a result, the SPM supplied to the substrate W is collected (collection step).

Further, when a predetermined period (for example, about 15 seconds) elapses from the lowering of the first guard 143, the control device 4 closes the first sulfuric acid-containing liquid valve 60 and the hydrogen peroxide solution valve 136, and the SPM nozzle 13 The discharge of SPM from is stopped.
According to the third substrate processing example, the high temperature sulfuric acid-containing liquid serving as a base for creating the SPM supplied to the front 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. ). By supplying the high-temperature sulfuric acid-containing liquid 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, the substrate W is warmed while executing the SPM surface supply step S4. Be done. Therefore, the SPM surface supply step S4 can be performed on the substrate W while sufficiently raising the temperature. Thereby, the resist removal efficiency by 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 relatively short, The resist can be roughly removed. This makes it possible to reduce the consumption of SPM, and thus the consumption of the sulfuric acid-containing liquid.

Further, in the second front surface supply step S42, the high temperature SPM is supplied to the front surface Wa of the substrate W, and at the same time, the high temperature sulfuric acid-containing liquid is supplied to the rear surface Wb of the substrate W. The SPM can enter the non-cured layer 183 through the crack 185 of the cured layer 182 generated by heating the resist 181, and thus the resist removal efficiency can be improved. Therefore, the processing period of the SPM surface supply step S4 (more specifically, the processing period of the first surface supply step S41) can be shortened.

In particular, the high temperature sulfuric acid-containing liquid is supplied to the back surface Wb of the substrate W from the start of the SPM front surface supply step S4. This allows SPM to enter the non-cured layer 183 at an early stage after the start of the SPM surface supply step S4. Accordingly, the resist 181 can be removed from the front surface Wa of the substrate W at an early stage after the start of the SPM surface supply step S4, and thus, the processing period of the SPM surface supply step S4 (more specifically, the first Further, it is possible to further shorten the processing period of the surface supply step S41.

FIG. 13 is a schematic view of a substrate processing apparatus 201 according to another embodiment of the present invention as seen from above.
The substrate processing apparatus 201 according to this embodiment is different from the embodiment shown in FIGS. 1 to 12D in that the processing liquid supply device serves as a sulfuric acid-containing liquid producing device and uses the sulfuric acid-containing liquid used in the processing unit 6. This is a point in which two sulfuric acid producing devices, namely a first sulfuric acid-containing liquid producing device 208A for producing and a second sulfuric acid-containing liquid producing device 208B for producing the sulfuric acid-containing liquid used in the processing unit 6, are provided. In the example of FIG. 13, two pairs of the first sulfuric acid-containing liquid preparation device 208A and the second sulfuric acid-containing liquid preparation device 208B are provided.

Each first sulfuric acid-containing liquid preparation device 208A corresponds to three columns arranged on one side of the transfer chamber 5. The first sulfuric acid-containing liquid preparation device 208A has the same configuration as that of the sulfuric acid-containing liquid preparation device 8 described above. The SPM discharged from the processing units 6 included in the corresponding three columns is supplied to each of the first sulfuric acid-containing liquid producing devices 208A. Each first sulfuric acid-containing liquid preparation device 208A supplies the high temperature sulfuric acid-containing liquid to all surface supply units (SPM nozzles 13) included in the processing units 6 included in the corresponding three columns. However, each of the first sulfuric acid-containing solution producing devices 208A does not supply the sulfuric acid-containing solution to the back surface supply unit (bottom surface nozzle 91) included in the processing unit 6 included in the corresponding three columns. That is, the first sulfuric acid-containing liquid preparation device 208A is a sulfuric acid-containing liquid preparation device dedicated to surface supply. Each of the first sulfuric acid-containing liquid producing devices 208A includes a first liquid storage unit 11 and a second liquid storage unit 12.

Each second sulfuric acid-containing liquid producing apparatus 208B corresponds to three columns arranged on one side of the transfer chamber 5. The second sulfuric acid-containing liquid preparation device 208B has the same configuration as the sulfuric acid-containing liquid preparation device 8 described above. The SPM discharged from the processing units 6 included in the corresponding three columns is supplied to each of the second sulfuric acid-containing liquid preparation devices 208B. Each of the second sulfuric acid-containing solution producing devices 208B supplies the high temperature sulfuric acid-containing solution to all the back surface supply units (bottom surface nozzles 91) included in the processing units 6 included in the corresponding three columns. However, each of the second sulfuric acid-containing liquid producing devices 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 columns. That is, the second sulfuric acid-containing liquid preparation device 208B is a sulfuric acid-containing liquid preparation device dedicated to the back surface supply. Each of the second sulfuric acid-containing liquid preparation devices 208B includes a first liquid storage unit 11 and a second liquid storage unit 12.

Between the first sulfuric acid-containing liquid preparation device 208A and the second sulfuric acid-containing liquid preparation device 208B, the sulfuric acid-containing liquid is transferred from the first sulfuric acid-containing liquid preparation device 208A to the second sulfuric acid-containing liquid preparation device 208B. A sulfuric acid-containing liquid supply pipe 209 for supplying the liquid is connected. An opening/closing valve 210 for opening/closing the sulfuric acid-containing liquid supply pipe 209 is provided in the sulfuric acid-containing liquid supply pipe 209. The sulfuric acid-containing liquid supply pipe 209 includes a liquid storage part (first liquid storage part 11 and/or second liquid storage part 12) of the first sulfuric acid-containing liquid preparation device 208A and a second sulfuric acid-containing liquid preparation device. A connection is made between the liquid storage unit 208B (first liquid storage unit 11 and/or second liquid storage unit 12).

The sulfuric acid-containing liquid created by the first sulfuric acid-containing liquid creating apparatus 208A is supplied to the front surface Wa of the substrate W. That is, this sulfuric acid-containing liquid is sulfuric acid used exclusively for removing the resist, and high standards are set not only for temperature but also for sulfuric acid concentration. 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 apparatus 208A is set to, for example, the first lower limit concentration (for example, 92%). When the threshold value of the sulfuric acid concentration becomes lower than the first lower limit concentration, the control device 4 opens the open/close valve 210 to change the sulfuric acid-containing liquid stored in the first sulfuric acid-containing liquid producing device 208A to the second sulfuric acid. The sulfuric acid replenishment valve 45 is opened while supplying to the contained liquid preparation device 208B, and a new sulfuric acid containing liquid from the sulfuric acid replenishment unit 25 is replenished to the first sulfuric acid containing liquid preparation device 208A.

Then, when 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 replenishment pipe 44 is opened and closed. 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 becomes high, and accordingly, after a lapse of a while, 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 high.

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, this sulfuric acid-containing liquid is a sulfuric acid-containing liquid used exclusively for raising the temperature of the substrate W, and the standard of the sulfuric acid concentration is looser than that in the case of the first sulfuric acid-containing liquid producing apparatus 208A. In this embodiment, the lower limit concentration of the sulfuric acid concentration created by the second sulfuric acid-containing liquid producing device 208B is set to, for example, the second lower limit concentration (for example, 85%). When the threshold value of the sulfuric acid concentration falls below the second lower limit concentration, it is stored in the liquid storage section (first liquid storage section 11 and/or second liquid storage section 12) of the second sulfuric acid-containing solution producing apparatus 208B. The sulfuric acid-containing liquid present is drained. At this time, a new sulfuric acid-containing liquid from the sulfuric acid replenishing unit 25 may be replenished or not be replenished in the second sulfuric acid-containing liquid producing apparatus 208B.

According to this embodiment, in addition to the effects of the embodiment of FIGS. 1 to 12, the following effects are exhibited.
That is, the second sulfuric acid-containing liquid preparation device 208B is a sulfuric acid-containing liquid preparation device dedicated to the back surface supply. The sulfuric acid-containing liquid used exclusively for raising the temperature of the substrate has a loose standard for its sulfuric acid concentration. Therefore, it is possible to set the lower limit concentration of the sulfuric acid concentration of the second sulfuric acid-containing liquid producing apparatus 208B to be low. This makes it possible to reduce the amount of drainage of the sulfuric acid-containing liquid from the second sulfuric acid-containing liquid producing device 208B. Therefore, the consumption of the sulfuric acid-containing liquid can be further reduced.

Further, when the sulfuric acid concentration of the sulfuric acid-containing liquid prepared by the first sulfuric acid-containing liquid preparing device 208A is lower than a predetermined lower limit concentration, the first sulfuric acid-containing liquid preparing device 208A changes to the second sulfuric acid-containing liquid preparing device. A solution containing sulfuric acid is supplied to 208B. The sulfuric acid-containing liquid whose sulfuric acid concentration is lower than the lower limit concentration in the first sulfuric acid-containing liquid preparation device 208A should be originally drained. However, such a sulfuric acid-containing liquid is collected in the second sulfuric acid-containing liquid producing apparatus 208B and utilized as sulfuric acid dedicated to the back surface supply. Therefore, the consumption of the sulfuric acid-containing liquid can be further reduced.

Although two embodiments of the present invention and three substrate processing examples have been described above, the present invention can be implemented in other forms.
Further, in the first liquid storage unit 11, the SPM recovered from the recovery/delivery pipe 26 is temporarily collected in the reclaim tank 21 and then stored in the first circulation tank 22, but the reclaim tank 21 is described. Alternatively, the first circulation tank 22 may be directly stored without passing through. In this case, the reclaim tank 21 may be eliminated.

Further, the case where the in-nozzle mixing method in which the sulfuric acid-containing liquid and the hydrogen peroxide solution are mixed inside the SPM nozzle 13 is adopted has been described, but the sulfuric acid-containing liquid and the hydrogen peroxide solution are connected to the nozzle. An in-pipe mixing method of mixing in the liquid pipe or in a mixing pipe connected to the treatment liquid pipe may be adopted.
Further, one sulfuric acid-containing liquid preparation device 8 (or a pair of the first sulfuric acid-containing liquid preparation device 208A and the second sulfuric acid-containing liquid preparation device 208B) is provided in the processing unit 6 included in a plurality of (three) columns. Instead of supplying the sulfuric acid-containing liquid, only the processing unit 6 included in one column may be supported.

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, an SPM for heating the back surface Wb is created by mixing the sulfuric acid-containing solution created by the sulfuric acid-containing solution creating device 8; 208A, 208B with the hydrogen peroxide solution from the hydrogen peroxide solution supply unit. Alternatively, instead of the sulfuric acid-containing liquid producing apparatus 8; 208A, 208B, an SPM producing apparatus for producing SPM based on the collected SPM may be provided.

Further, in each of the above-described embodiments, the case where the substrate processing apparatus 1, 201 is an apparatus for processing the substrate W made of a semiconductor wafer has been described, but the substrate processing apparatus may be a substrate for a liquid crystal display device, an organic EL (electroluminescence). An apparatus for processing substrates such as FPD (Flat Panel Display) substrates, optical disc substrates, magnetic disc substrates, magneto-optical disc substrates, photomask substrates, ceramic substrates, and solar cell substrates for display devices. Good.

In addition, various design changes can be made within the scope of the matters described in the claims.

1: Substrate processing device 4: Control device 8: Sulfuric acid-containing liquid preparation device 13: SPM nozzle (surface supply unit)
91: Lower surface nozzle (rear surface supply unit)
108: Spin chuck (substrate holding unit)
146: Guard lifting unit (switching unit)
152: drainage pipe 156: recovery pipe 201: substrate processing device 208A: first sulfuric acid-containing liquid preparation device 208B: second sulfuric acid-containing liquid preparation device 209: sulfuric acid-containing liquid supply pipe W: substrate Wa: front surface Wb: back surface

Claims (21)

A substrate processing apparatus for processing a substrate using SPM, which is a mixed solution of sulfuric acid and hydrogen peroxide water,
A substrate holding unit for holding the substrate,
A recovery pipe into which the liquid supplied to the substrate held by the substrate holding unit and discharged from the substrate flows,
A sulfuric acid-containing liquid producing device for producing a high-temperature first sulfuric acid-containing liquid containing sulfuric acid based on the liquid fed into the recovery pipe,
A surface supply unit for supplying the SPM created based on the high temperature first sulfuric acid-containing liquid created in the sulfuric acid-containing liquid creating device to the surface of the substrate held by the substrate holding unit;
A back surface supply unit for supplying the second sulfuric acid-containing solution containing the high temperature first sulfuric acid-containing solution prepared in the sulfuric acid-containing solution preparing device to the back surface of the substrate held by the substrate holding unit; A substrate processing apparatus including: Further comprising a control device for controlling the sulfuric acid-containing liquid preparation device, the front surface supply unit and the back surface supply unit,
The control device is
A sulfuric acid-containing liquid producing step of producing a high temperature first sulfuric acid-containing liquid by the sulfuric acid-containing liquid producing device based on the liquid flowing into the recovery pipe;
An SPM surface supplying step of supplying SPM created based on the high-temperature first sulfuric acid-containing solution created by the sulfuric acid-containing solution creating device to the surface of the substrate held by the substrate holding unit;
Prior to the SPM surface supplying step or in parallel with the SPM surface supplying step, a high-temperature first solution prepared by the sulfuric acid-containing solution preparing apparatus for heating the substrate held in the substrate holding unit. The substrate processing apparatus according to claim 1, further comprising: a sulfuric acid-containing liquid back surface supplying step of supplying a second sulfuric acid-containing liquid containing a sulfuric acid-containing liquid to the back surface of the substrate held by the substrate holding unit. A drainage pipe into which a liquid supplied from the substrate and supplied to the substrate held by the substrate holding unit flows,
Further comprising a switching unit for switching a pipe into which the liquid discharged from the substrate held by the substrate holding unit flows, between the drainage pipe and the recovery pipe,
The control device controls the switching unit,
The control device further executes a recovery step of causing the liquid discharged from the substrate held by the substrate holding unit to flow into the recovery pipe by the switching unit, in parallel with the sulfuric acid-containing liquid back surface supply step. The substrate processing apparatus according to claim 2. The control device executes the sulfuric acid-containing liquid back surface supply step prior to the SPM front surface supply step,
In parallel with the SPM surface supply step, the control device further executes a draining step of causing the liquid discharged from the substrate held by the substrate holding unit to flow into the drainage pipe by the switching unit. The substrate processing apparatus according to claim 3. The substrate processing apparatus according to claim 3, wherein the control device executes the sulfuric acid-containing liquid back surface supply process in parallel with the SPM front surface supply process. In the SPM surface supply step, the control device supplies a first surface supply step of supplying SPM to the surface of the substrate held by the substrate holding unit, and the supply of SPM is stopped in the first surface supply step. And a second surface supplying step of supplying SPM to the surface of the substrate held by the substrate holding unit,
The control device performs the sulfuric acid-containing liquid back surface supply step in parallel with the second front surface supply step,
The substrate processing apparatus according to claim 5, wherein the control device executes the recovery step by the switching unit in parallel with the second front surface supply step and the sulfuric acid-containing liquid back surface supply step. And a draining step in which the controller causes the liquid discharged from the substrate held by the substrate holding unit to flow into the drain pipe by the switching unit, in parallel with the first surface supply step. The substrate processing apparatus according to claim 6, which is executed. A drainage pipe into which a liquid supplied from the substrate and supplied to the substrate held by the substrate holding unit flows,
Further comprising a switching unit for switching a pipe into which the liquid discharged from the substrate held by the substrate holding unit flows, between the drainage pipe and the recovery pipe,
The control device controls the switching unit,
In the SPM surface supply step, the control device supplies a first surface supply step of supplying SPM to the surface of the substrate held by the substrate holding unit, and the supply of SPM is stopped in the first surface supply step. And a second surface supplying step of supplying SPM to the surface of the substrate held by the substrate holding unit,
The control device performs the sulfuric acid-containing liquid back surface supply step in parallel with the first front surface supply step,
In parallel with the first front surface supplying step and the sulfuric acid-containing liquid rear surface supplying step, the control device causes the switching unit to discharge the liquid discharged from the substrate held by the substrate holding unit to the drain pipe. The substrate processing apparatus according to claim 2, further comprising a draining step of causing the liquid to flow into the substrate. The sulfuric acid-containing liquid producing device,
A first sulfuric acid-containing liquid producing apparatus that supplies the high-temperature first sulfuric acid-containing liquid to the front surface supply unit and does not supply the first sulfuric acid-containing liquid to the back surface supply unit;
9. A second sulfuric acid-containing liquid producing apparatus that supplies a 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 front surface supply unit. The substrate processing apparatus according to any one of claims. When the sulfuric acid concentration of the first sulfuric acid-containing liquid prepared by the first sulfuric acid-containing liquid producing device is below a predetermined lower limit concentration, the first sulfuric acid-containing liquid producing device produces the second sulfuric acid-containing liquid by the first sulfuric acid-containing liquid producing device. The substrate processing apparatus according to claim 9, further comprising a sulfuric acid supply pipe for supplying the first sulfuric acid-containing liquid to the preparation apparatus. The substrate processing apparatus according to claim 1, wherein 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. 11. The second sulfuric acid-containing liquid supplied to the back surface of the substrate held by the substrate holding unit is SPM, which is a mixed liquid of the first sulfuric acid-containing liquid and hydrogen peroxide water. The substrate processing apparatus according to any one of claims. Mixing sulfuric acid and hydrogen peroxide solution, which is executed in a substrate processing apparatus, including a substrate holding unit and a recovery pipe into which a liquid supplied to the substrate held by the substrate holding unit and discharged from the substrate flows. A substrate processing method for processing a substrate using SPM, which is a liquid,
A sulfuric acid-containing liquid producing step of producing a high-temperature first sulfuric acid-containing liquid containing sulfuric acid based on the liquid flowing into the recovery pipe;
An SPM surface supplying step of supplying the SPM prepared based on the prepared high temperature first sulfuric acid-containing liquid to the surface of the substrate held by the substrate holding unit;
A second high-temperature sulfuric acid-containing liquid prepared for heating the substrate held by the substrate holding unit prior to or in parallel with the SPM surface-feeding process. And a sulfuric acid-containing liquid back surface supplying step of supplying the sulfuric acid-containing liquid to the back surface of the substrate held by the substrate holding unit. 14. The substrate processing method according to claim 13, further comprising a recovery step of causing a liquid discharged from the substrate held by the substrate holding unit to flow into the recovery pipe in parallel with the sulfuric acid-containing liquid back surface supply step. .. The substrate processing apparatus further includes a drainage pipe into which the liquid supplied to the substrate held by the substrate holding unit and discharged from the substrate flows in.
The sulfuric acid-containing liquid back surface supply step is executed prior to the SPM front surface supply step,
The substrate processing method according to claim 14, further comprising a draining step of causing a liquid discharged from the substrate held by the substrate holding unit to flow into the drainage pipe, in parallel with the SPM surface supply step. .. The substrate processing method according to claim 14, wherein the sulfuric acid-containing liquid back surface supply step is performed in parallel with the SPM front surface supply 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 the step of supplying SPM in the first surface supplying step is stopped, A second surface supplying step of supplying SPM 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 front surface supply step,
The substrate processing method according to claim 16, wherein the recovery step is performed in parallel with the second front surface supply step and the sulfuric acid-containing liquid back surface supply step. The substrate processing apparatus further includes a drainage pipe into which the liquid supplied to the substrate held by the substrate holding unit and discharged from the substrate flows in.
18. The substrate according to claim 17, further comprising a draining step of causing a liquid drained from the substrate held by the substrate holding unit to flow into the drainage pipe in parallel with the first surface supply step. Processing method. The substrate processing apparatus further includes a drainage pipe into which the liquid supplied to the substrate held by the substrate holding unit and discharged from the substrate flows in.
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 the step of supplying SPM in the first surface supplying step is stopped, A second surface supplying step of supplying SPM 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 front surface supply step,
In parallel with the first front surface supply step and the sulfuric acid-containing liquid back surface supply step, a drainage step of causing a liquid discharged from the substrate held by the substrate holding unit to flow into the drainage pipe is further included. The substrate processing method according to claim 13. The substrate processing method according to claim 13, wherein 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. 20. The second sulfuric acid-containing liquid supplied to the back surface of the substrate held by the substrate holding unit is SPM, which is a mixed liquid of the first sulfuric acid-containing liquid and hydrogen peroxide water. The substrate processing method according to any one of claims.

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