CN116805595A - Substrate processing apparatus and substrate processing method - Google Patents

Abstract

The invention provides a substrate processing apparatus and a substrate processing method. A substrate processing apparatus (100) is provided with a tank (50), a path (70) including a 1 st path (C1), a heater (61), a hydrogen peroxide solution supply path (C3), and a control unit (102). The 1 st path (C1) supplies sulfuric acid from the tank (50) to the nozzle (36). The heater (61) heats the heating region (R1) of the 1 st path (C1). A control unit (102) mixes the sulfuric acid heated by the heater (61) with the hydrogen peroxide solution and then ejects the mixture from the nozzle (36) to the substrate (W), and then mixes the sulfuric acid having a temperature lower than that of the heated sulfuric acid with the hydrogen peroxide solution and then ejects the mixture from the nozzle (36) to the substrate (W).

Description

Substrate processing apparatus and substrate processing method

Technical Field

The present invention relates to a substrate processing apparatus and a substrate processing method.

Background

Conventionally, in a process for manufacturing a device including a substrate such as a semiconductor device and a liquid crystal display device, a substrate processing device for processing a substrate is used. The substrate is, for example, a semiconductor wafer or a glass substrate for a liquid crystal display device.

Patent document 1 describes a substrate processing apparatus that supplies a sulfuric acid/hydrogen peroxide solution mixture, which is produced by mixing a hydrogen peroxide solution at a flow rate of 0.1 to 0.35 with respect to a sulfuric acid mixture at 170 ℃ or higher, the flow rate of which is 1, to a substrate surface.

[ background art document ]

[ patent literature ]

Patent document 1 japanese patent laid-open publication No. 2009-16497

Disclosure of Invention

[ problem to be solved by the invention ]

In the substrate processing apparatus described in patent document 1, when the sulfuric acid-hydrogen peroxide solution mixture is supplied to the substrate surface, the sulfuric acid reacts with the hydrogen peroxide solution when the sulfuric acid is mixed with the hydrogen peroxide solution, and the sulfuric acid-hydrogen peroxide solution mixture becomes high temperature. The high-temperature sulfuric acid/hydrogen peroxide solution mixture is supplied to a substrate to process the substrate, and then the sulfuric acid/hydrogen peroxide solution mixture on the substrate is rinsed with a hydrogen peroxide solution.

In addition, when the supply of sulfuric acid is stopped for flushing the high-temperature sulfuric acid/hydrogen peroxide solution mixture on the substrate and only the hydrogen peroxide solution is supplied, the high-temperature sulfuric acid/hydrogen peroxide solution mixture remaining on the substrate reacts vigorously with the supplied hydrogen peroxide solution to become higher temperature, and the substrate also becomes higher temperature. Then, the high-temperature sulfuric acid hydrogen peroxide solution mixture is removed from the substrate by continuing to supply the hydrogen peroxide solution, and the supplied hydrogen peroxide solution abruptly drops the temperature of the substrate.

However, in this method, the sulfuric acid hydrogen peroxide solution mixed solution at a high temperature becomes higher due to the hydrogen peroxide solution, and the temperature of the substrate changes sharply. Therefore, there is a problem that damage such as peeling of a pattern on the substrate may be caused to the substrate. As a method for improving this problem, it is considered to change the mixing ratio (sulfuric acid concentration) of sulfuric acid to hydrogen peroxide solution, but it takes time to adjust the mixing ratio to a desired ratio.

The present invention has been made in view of the above-described problems, and an object of the present invention is to provide a substrate processing apparatus and a substrate processing method capable of suppressing damage to a substrate.

[ means of solving the problems ]

A substrate processing apparatus according to an aspect of the present invention is configured to process a substrate by supplying a processing liquid from a nozzle to the substrate. The substrate processing apparatus includes a 1 st tank, a path including a 1 st path, a 1 st valve, a 1 st heater, a hydrogen peroxide solution supply path, a water passing valve, and a control unit. The 1 st tank stores sulfuric acid. The 1 st path is to supply the sulfuric acid from the 1 st tank to the nozzle. The 1 st valve is interposed in the 1 st path. The 1 st heater heats the heating region of the 1 st path. The hydrogen peroxide solution supply path is for supplying the hydrogen peroxide solution to the nozzle. The water passing valve is interposed in the hydrogen peroxide solution supply path. The control unit controls the supply of the sulfuric acid and the hydrogen peroxide solution to the nozzle by controlling the opening and closing of the 1 st valve and the water passing valve. The control unit mixes the sulfuric acid heated by the 1 st heater with the hydrogen peroxide solution and then ejects the mixture from the nozzle to the substrate, and then mixes the sulfuric acid having a temperature lower than that of the heated sulfuric acid with the hydrogen peroxide solution and then ejects the mixture from the nozzle to the substrate.

In one aspect of the present invention, the path may further include a 2 nd path for supplying the sulfuric acid from the 1 st tank to the nozzle without passing through the heating region. The substrate processing apparatus may further include a 2 nd valve interposed in the 2 nd path. The control unit may control the supply of the sulfuric acid and the hydrogen peroxide solution to the nozzle by controlling the opening and closing of the 1 st valve, the 2 nd valve, and the water passing valve. The sulfuric acid passing through the 2 nd path may be merged into the hydrogen peroxide solution at a lower temperature than the sulfuric acid passing through the 1 st path. The control unit may control the 1 st valve, the 2 nd valve, and the water passing valve such that the sulfuric acid heated by the 1 st heater through the 1 st path is mixed with the hydrogen peroxide solution and then ejected from the nozzle to the substrate, and the sulfuric acid through the 2 nd path is mixed with the hydrogen peroxide solution and then ejected from the nozzle to the substrate.

In one aspect of the present invention, the substrate processing apparatus may further include a 1 st joining portion and a 2 nd joining portion. The 1 st merging portion may be disposed between the heating region and the discharge port of the nozzle, and merge the 1 st path with the hydrogen peroxide solution supply path. The 2 nd junction may be disposed between the heating region and the 1 st junction, and join the 1 st path and the 2 nd path.

In one aspect of the present invention, the 1 st path and the 2 nd path may branch off from the heating region on an upstream side in the flow direction of the sulfuric acid, and merge from the heating region on a downstream side in the flow direction of the sulfuric acid.

In one aspect of the present invention, the control unit may set the 1 st heater to 1 st output, and may set the sulfuric acid passing through the 1 st path to have a 1 st temperature. The control unit may set the 1 st heater to a 2 nd output lower than the 1 st output, so that the sulfuric acid passing through the 1 st path has a 2 nd temperature lower than the 1 st temperature.

In one aspect of the present invention, the path may further include a circulation pipe branched from the 1 st path and through which the sulfuric acid returns to the 1 st tank. The 1 st heater may be disposed upstream of a branching portion of the 1 st path and the circulation pipe in the flow direction of the sulfuric acid.

In one aspect of the present invention, the path may further include a circulation pipe branched from the 1 st path and through which the sulfuric acid returns to the 1 st tank. The 1 st heater may be disposed downstream of a branching portion of the 1 st path and the circulation pipe in the flow direction of the sulfuric acid.

In one aspect of the present invention, the substrate processing apparatus may further include a 2 nd heater for maintaining the sulfuric acid in the 1 st tank at a predetermined temperature.

In one aspect of the present invention, the substrate processing apparatus may further include a 2 nd tank and a 3 rd heater. The 2 nd tank may be disposed downstream of the 1 st tank in the sulfuric acid flow direction. The 3 rd heater may maintain the sulfuric acid in the 2 nd tank at a temperature higher than the temperature of the sulfuric acid in the 1 st tank.

In one aspect of the present invention, a substrate processing method is provided for processing a substrate by supplying a processing liquid to the substrate. The substrate processing method includes: a 1 st discharge step of discharging the sulfuric acid supplied from the 1 st tank and heated in the heating region through the 1 st path having the heating region and the hydrogen peroxide solution passing through the hydrogen peroxide solution supply path to the substrate; and a 2 nd discharge step of discharging the sulfuric acid, which is supplied from the 1 st tank and has a temperature lower than the heated sulfuric acid, and the hydrogen peroxide solution, which passes through the hydrogen peroxide solution supply path, to the substrate after the 1 st discharge step.

In one aspect of the present invention, in the 2 nd discharge step, the sulfuric acid passing through the 2 nd route without passing through the heating region and the hydrogen peroxide solution may be discharged to the substrate.

In one aspect of the present invention, the 1 st path and the 2 nd path may branch on an upstream side in a flow direction of the sulfuric acid with respect to the heating region, and merge on a downstream side in the flow direction of the sulfuric acid with respect to the heating region.

In one aspect of the present invention, the method may further include: a 1 st circulation step of heating the sulfuric acid passing through the 1 st path to a sulfuric acid having a 1 st temperature before the 1 st ejection step; and a 2 nd circulation step of changing the sulfuric acid passing through the 1 st path to sulfuric acid having a 2 nd temperature lower than the 1 st temperature before the 2 nd ejection step.

In one aspect of the present invention, the sulfuric acid in the 1 st tank may be maintained at a predetermined temperature.

In one aspect of the present invention, the sulfuric acid in the 2 nd tank disposed downstream of the 1 st tank in the sulfuric acid flow direction may be maintained at a temperature higher than the temperature of the sulfuric acid in the 1 st tank.

[ Effect of the invention ]

According to the present invention, a substrate processing apparatus and a substrate processing method capable of suppressing damage to a substrate can be provided.

Drawings

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

Fig. 2 is a schematic view of a substrate processing unit in the substrate processing apparatus of embodiment 1.

Fig. 3 is a schematic view of a processing liquid supply section of the substrate processing apparatus according to embodiment 1.

Fig. 4 is a block diagram of a substrate processing apparatus according to embodiment 1.

Fig. 5 is a flowchart of a substrate processing method of the substrate processing apparatus according to embodiment 1.

Fig. 6 is a schematic view of a processing liquid supply section of the substrate processing apparatus according to variation 1.

Fig. 7 is a schematic view of a processing liquid supply section of a substrate processing apparatus according to variation 2.

Fig. 8 is a schematic view of a processing liquid supply section of a substrate processing apparatus according to variation 3.

Fig. 9 is a schematic view of a processing liquid supply section of a substrate processing apparatus according to a modification 4.

Fig. 10 is a schematic view of a processing liquid supply unit of a substrate processing apparatus according to embodiment 2 of the present invention.

Fig. 11 is a flowchart of a substrate processing method of the substrate processing apparatus according to embodiment 2.

Fig. 12 is a schematic view of a processing liquid supply section of the substrate processing apparatus according to variation 5.

Fig. 13 is a schematic view of a processing liquid supply section of a substrate processing apparatus according to variation 6.

Fig. 14 is a schematic view of a substrate processing unit in the substrate processing apparatus of embodiment 3.

Fig. 15 is a schematic view of a processing liquid supply section of the substrate processing apparatus according to embodiment 3.

Fig. 16 is a flowchart of a substrate processing method of the substrate processing apparatus according to embodiment 3.

Fig. 17 is a schematic view of a processing liquid supply section of a substrate processing apparatus according to variation 7.

Fig. 18 is a schematic view of a processing liquid supply section of the substrate processing apparatus according to variation 8.

Fig. 19 is a schematic view of a processing liquid supply unit of a substrate processing apparatus according to embodiment 4 of the present invention.

Fig. 20 is a flowchart of a substrate processing method of the substrate processing apparatus according to embodiment 4.

Fig. 21 is a schematic view of a processing liquid supply section of a substrate processing apparatus according to variation 9.

Fig. 22 is a schematic view of a processing liquid supply section of the substrate processing apparatus according to the 10 th modification.

Detailed Description

Embodiments of a substrate processing method and a substrate processing apparatus according to the present invention are described below with reference to the drawings. In the drawings, the same or corresponding portions are denoted by the same reference numerals, and description thereof will not be repeated. In the present specification, in order to facilitate understanding of the invention, the X axis, the Y axis, and the Z axis orthogonal to each other are sometimes described. Typically, the X-axis and Y-axis are parallel to the horizontal direction and the Z-axis is parallel to the vertical direction.

(embodiment 1)

First, a substrate processing apparatus 100 according to embodiment 1 of the present invention will be described with reference to fig. 1. Fig. 1 is a schematic plan view of a substrate processing apparatus 100 according to the present embodiment.

The substrate processing apparatus 100 processes a substrate W. The substrate processing apparatus 100 processes the substrate W to perform at least one of etching, surface treatment, property imparting, processing film formation, film at least partial removal, and cleaning of the substrate W.

The substrate W is used as a semiconductor substrate. The substrate W comprises a semiconductor wafer. For example, the substrate W has a substantially disk shape. Here, the substrate processing apparatus 100 processes the substrates W piece by piece.

As shown in fig. 1, the substrate processing apparatus 100 includes a plurality of substrate processing units 10, a processing liquid tank 110, a processing liquid tank 120, a plurality of load ports LP, a transfer robot IR, a center robot CR, and a control device 101. The control device 101 controls the load port LP, the transfer robot IR, and the center robot CR. The control device 101 includes a control unit 102 and a storage unit 104.

The load port LP accommodates a plurality of substrates W stacked on each other. The transfer robot IR transfers the substrate W between the load port LP and the center robot CR. The center robot CR conveys the substrate W between the transfer robot IR and the substrate processing unit 10. The substrate processing unit 10 ejects processing liquids onto the substrates W, respectively, to process the substrates W. The processing liquid tank 120 accommodates processing liquid.

Specifically, the plurality of substrate processing units 10 are formed with a plurality of towers TW (4 towers TW in fig. 1) arranged to surround the center robot CR in a plan view. Each tower TW includes a plurality of substrate processing units 10 (3 substrate processing units 10 in fig. 1) stacked one above the other. The treatment liquid tanks 110 correspond to the plurality of towers TW, respectively. The processing liquid in the processing liquid tank 120 is supplied to the tower TW corresponding to the processing liquid tank 110 via any one of the processing liquid tanks 110. In addition, not only the processing liquid but also the gas may be supplied to the substrate processing unit 10 and the processing liquid tank 120.

The treatment liquid may contain a so-called chemical solution. The liquid medicine contains hydrofluoric acid. For example, the hydrofluoric acid may be heated to 40 ℃ or higher and 70 ℃ or lower, or may be heated to 50 ℃ or higher and 60 ℃ or lower. However, the hydrofluoric acid may not be heated. In addition, the liquid medicine may contain water or phosphoric acid.

Furthermore, the chemical solution may contain a hydrogen peroxide solution. The chemical solution may contain sulfuric acid or a sulfuric acid-hydrogen peroxide solution mixture. The chemical solution may contain SC1 (ammonia hydrogen peroxide solution mixture), SC2 (hydrochloric acid hydrogen peroxide solution mixture), or aqua regia (a mixture of concentrated hydrochloric acid and concentrated nitric acid).

Alternatively, the treatment liquid may contain a so-called rinse liquid. For example, the rinse liquid may contain Deionized Water (DIW), carbonated Water, electrolytic ion Water, ozone Water, ammonia Water, hydrochloric acid Water having a diluted concentration (for example, about 10ppm to 100 ppm), or reduced Water (hydrogen-rich Water).

A specific space within the substrate processing apparatus 100 is partitioned by the processing liquid tank 120. In the substrate processing apparatus 100, a boundary wall BW is arranged between a region where the center robot CR and the substrate processing unit 10 are disposed and a region where the processing liquid tank 120 is disposed. The processing liquid tank 120 divides a part of the space of the region of the outer portion of the boundary wall BW in the substrate processing apparatus 100.

The processing liquid tank 120 defines a specific space in the substrate processing apparatus 100 by a housing. The processing liquid tank 120 includes processing liquid piping for circulating processing liquid in the housing. In addition, the treatment liquid tank 120 typically has a preparation tank (tank) for preparing the treatment liquid. The treatment liquid tank 120 may have a preparation tank for 1 treatment liquid or may have a preparation tank for a plurality of treatment liquids. The treatment liquid tank 120 may have a pump, a nozzle, and/or a filter for circulating the treatment liquid.

Here, the treatment liquid tank 120 has a 1 st treatment liquid housing 122a and a 2 nd treatment liquid housing 122b. In fig. 1, in order to avoid excessive complexity of the drawing, the flow of the treatment liquid in the 1 st treatment liquid housing 122a is shown, in which the treatment liquid is supplied to the column TW corresponding to the treatment liquid tank 110 via any one of the treatment liquid tanks 110, and the flow of the treatment liquid in the 2 nd treatment liquid housing 122b is omitted.

The control device 101 controls various operations of the substrate processing apparatus 100. The control device 101 includes a control unit 102 and a storage unit 104. The control unit 102 has a processor. The control unit 102 has, for example, a central processing unit (Central Processing Unit: CPU). Alternatively, the control unit 102 may have a general-purpose arithmetic unit.

The storage unit 104 stores data and computer programs. The data includes recipe data (recipe data). The process recipe data includes information indicative of a plurality of process recipes. The process recipes define the processing contents and the processing sequence of the substrate W.

The storage unit 104 includes a main storage device and an auxiliary storage device. The main memory device is, for example, a semiconductor memory. The auxiliary storage device is, for example, a semiconductor memory and/or a hard disk. The storage 104 may also include removable media. The control unit 102 executes a computer program stored in the storage unit 104 to perform a substrate processing operation.

Next, a substrate processing unit 10 in the substrate processing apparatus 100 according to the present embodiment will be described with reference to fig. 2. Fig. 2 is a schematic view of the substrate processing unit 10 in the substrate processing apparatus 100.

The substrate processing unit 10 includes a chamber 12 and a substrate holding portion 20. The chamber 12 accommodates a substrate W. The substrate holding portion 20 holds a substrate W.

The chamber 12 is substantially box-shaped having an inner space. The chamber 12 accommodates a substrate W. Here, the substrate processing apparatus 100 is a single-wafer type processing apparatus for processing substrates W one by one, and 1 substrate W is stored in the chamber 12 at a time. The substrate W is accommodated in the chamber 12, and is processed in the chamber 12. At least a part of each of the substrate holding portion 20 and the processing liquid supply portion 30 described below is housed in the chamber 12.

The substrate holding portion 20 holds a substrate W. The substrate holding section 20 horizontally holds the substrate W such that the upper surface (front surface) Wa of the substrate W is directed upward and the rear surface (lower surface) Wb of the substrate W is directed vertically downward. The substrate holding portion 20 rotates the substrate W while holding the substrate W. The substrate holding portion 20 holds the substrate W and rotates the substrate W.

For example, the substrate holding portion 20 may be a clamp type for clamping an end portion of the substrate W. Alternatively, the substrate holding portion 20 may have any mechanism for holding the substrate W from the back surface Wb. For example, the substrate holding portion 20 may be a vacuum type. In this case, the substrate holding portion 20 holds the substrate W horizontally by sucking the center portion of the back surface Wb of the substrate W, which is a non-device-forming surface, onto the upper surface. Alternatively, the substrate holding portion 20 may be a combination of a chucking type and a vacuum type in which a plurality of chuck pins are brought into contact with the peripheral end surface of the substrate W.

For example, the substrate holding section 20 includes a spin base 21, a chuck member 22, a shaft 23, an electric motor 24, and a housing 25. The chuck member 22 is arranged on the rotating base 21. The chuck member 22 grips the substrate W. Typically, a plurality of chuck members 22 are provided on the rotating base 21.

The shaft 23 is a hollow shaft. The shaft 23 extends in the vertical direction along the rotation axis Ax. A rotation base 21 is coupled to an upper end of the shaft 23. The substrate W is placed above the spin base 21.

The spin base 21 has a disk shape and horizontally supports the substrate W. The shaft 23 extends downward from the center of the rotation base 21. The electric motor 24 imparts a rotational force to the shaft 23. The electric motor 24 rotates the shaft 23 in the rotation direction, thereby rotating the substrate W and the spin base 21 about the rotation axis Ax. The housing 25 encloses the shaft 23 and the electric motor 24.

The substrate processing apparatus 100 further includes a processing liquid supply unit 30. The processing liquid supply unit 30 supplies a processing liquid to the substrate W. Typically, the processing liquid supply section 30 supplies the processing liquid to the upper surface Wa of the substrate W.

The treatment liquid supply unit 30 includes a pipe 40, a valve 34, a nozzle 36, and a heater 60 (see fig. 3) described later. The nozzle 36 ejects the processing liquid onto the upper surface Wa of the substrate W. The nozzle 36 may discharge the processing liquid to the central portion of the substrate W, or may discharge the processing liquid to an area between the central portion and the peripheral portion of the substrate W, for example. The nozzle 36 has a discharge port 36a (see fig. 3), and the treatment liquid is discharged from the discharge port 36 a. The nozzle 36 is connected to a pipe 40. The processing liquid is supplied from a supply source to the piping 40. The valve 34 opens and closes the flow path in the pipe 40. The nozzle 36 is preferably configured to be movable with respect to the substrate W. The nozzle 36 can move in the horizontal direction and/or the vertical direction along with a movement mechanism controlled by the control unit 102. Note that in this specification, the moving mechanism is omitted to avoid overcomplicating the drawings.

The valve 34 adjusts the opening degree of the pipe 40 to adjust the flow rate of the treatment liquid supplied to the pipe 40. Specifically, the valve 34 includes a valve body (not shown) having a valve seat provided therein, a valve body for opening and closing the valve seat, and an actuator (not shown) for moving the valve body between an open position and a closed position.

The substrate processing apparatus 100 further includes a cup 80. The cup 80 collects the processing liquid scattered from the substrate W. The cup 80 can be lifted and lowered. For example, the cup holder 80 is raised vertically upward to the side of the substrate W while the processing liquid is supplied to the substrate W by the processing liquid supply unit 30. In this case, the cup 80 collects the processing liquid scattered from the substrate W by the rotation of the substrate W. After the process liquid supply unit 30 has completed the process liquid supply period to the substrate W, the cup 80 is lowered vertically downward from the side of the substrate W.

As described above, the control device 101 includes the control unit 102 and the storage unit 104. The control unit 102 controls the substrate holding unit 20, the processing liquid supply unit 30, and/or the cup 80. As an example, the control unit 102 controls the electric motor 24 and the valve 34.

The substrate processing apparatus 100 of the present embodiment can be suitably used for manufacturing a semiconductor element provided with a semiconductor. Typically, in a semiconductor device, a conductive layer and an insulating layer are laminated on a substrate. The substrate processing apparatus 100 can be suitably used for cleaning and/or processing (e.g., etching, characteristic change, etc.) of a conductive layer and/or an insulating layer in manufacturing a semiconductor device. In addition, the substrate processing apparatus 100 can be suitably used for removal of an insulating layer (e.g., a resist layer).

In the substrate processing unit 10 shown in fig. 2, the processing liquid supply unit 30 can supply 1 kind of processing liquid to the substrate W, but the processing liquid supply unit 30 may be capable of supplying a plurality of kinds of processing liquids to the substrate W. For example, the treatment liquid supply unit 30 may include a plurality of pipes 40, valves 34, and nozzles 36.

Next, the processing liquid supply unit 30 of the substrate processing apparatus 100 according to the present embodiment will be described in detail with reference to fig. 1 to 3. Fig. 3 is a schematic view of the processing liquid supply unit 30 of the substrate processing apparatus 100 according to the present embodiment.

As shown in fig. 3, the treatment liquid supply unit 30 includes a tank 50, a path 70, a hydrogen peroxide solution supply path C3, and a heater 61 as the heater 60. Tank 50 stores sulfuric acid. The path 70 is a path for supplying sulfuric acid from the tank 50 to the nozzle 36. In the present embodiment, the path 70 includes a 1 st path C1 and a 2 nd path C2. The tank 50 is an example of "tank 1" of the present invention. The heater 61 is an example of the "1 st heater" of the present invention.

The 1 st path C1 is a path for supplying sulfuric acid from the tank 50 to the nozzle 36. The heater 61 heats the heating region R1 of the 1 st path C1. Therefore, the temperature of sulfuric acid passing through the heating region R1 rises. For example, the sulfuric acid passing through the heating region R1 reaches 170 to 190 ℃. It should be noted that a heater other than the heater 61 may be disposed in the 1 st path C1, but the heater 61 is the most downstream heater in the flow direction of sulfuric acid disposed in the 1 st path C1.

The 2 nd path C2 is a path for supplying sulfuric acid from the tank 50 to the nozzle 36 without passing through the heating region R1. In the present embodiment, no heater is disposed in the 2 nd path C2. The sulfuric acid passing through the 2 nd path C2 is lower in temperature than the sulfuric acid heated through the 1 st path C1.

The hydrogen peroxide solution supply path C3 is a path for supplying the hydrogen peroxide solution to the nozzle 36. The hydrogen peroxide solution supply path C3 is, for example, a path for supplying the hydrogen peroxide solution from a hydrogen peroxide solution tank, not shown, to the nozzle 36. In addition, a heater is not disposed in the hydrogen peroxide solution supply path C3, and the hydrogen peroxide solution passing through the hydrogen peroxide solution supply path C3 is at room temperature (for example, 25 ℃).

The treatment liquid supply section 30 includes the 1 st pipe 41, the 2 nd pipe 42, and the 3 rd pipe 43 as the pipes 40. In the present embodiment, the 1 st path C1 includes the 1 st pipe 41, the 2 nd path C2 includes the 2 nd pipe 42, and the hydrogen peroxide solution supply path C3 includes the 3 rd pipe 43.

The treatment liquid supply unit 30 includes a 1 st valve 34a, a 2 nd valve 34b, and a water passing valve 34c as the valves 34. The 1 st valve 34a is interposed in the 1 st path C1, and opens and closes the flow path of the 1 st path C1. The 2 nd valve 34b is interposed in the 2 nd path C2, and opens and closes the flow path of the 2 nd path C2. The water passing valve 34C is interposed in the hydrogen peroxide solution supply path C3, and opens and closes the flow path of the hydrogen peroxide solution supply path C3.

In the present embodiment, the sulfuric acid passing through the 1 st path C1 and the hydrogen peroxide solution passing through the hydrogen peroxide solution supply path C3 are joined at the 1 st joining portion P1. The 1 st merging portion P1 is disposed between the heating region R1 and the discharge port 36a of the nozzle 36, and is a portion where the 1 st path C1 merges with the hydrogen peroxide solution supply path C3. In the present embodiment, the 1 st merging portion P1 is disposed in the nozzle 36, for example.

For example, the mixing ratio of sulfuric acid to hydrogen peroxide solution passing through the 1 st path C1 is set to sulfuric acid in terms of volume ratio: hydrogen peroxide solution versus 8:2 increases the concentration of sulfuric acid. In addition, the mixing ratio of sulfuric acid to hydrogen peroxide solution passing through the 1 st path C1 is set to sulfuric acid in terms of volume ratio: the hydrogen peroxide solution is, for example, 8.5 to 9.5:1.5 to 0.5. The merged sulfuric acid and the hydrogen peroxide solution react with each other to form a hydrogen peroxide solution mixture at a high temperature (for example, 200 ℃ or higher).

The sulfuric acid passing through the 2 nd channel C2 and the hydrogen peroxide solution passing through the hydrogen peroxide solution supply channel C3 are joined, for example, in the nozzle 36. The sulfuric acid passing through the 2 nd path C2 merges into the hydrogen peroxide solution at a lower temperature than the sulfuric acid passing through the 1 st path C1. Therefore, the merged sulfuric acid and the hydrogen peroxide solution react with each other, but become a relatively low-temperature hydrogen peroxide solution mixed solution. The flow rate (amount of sulfuric acid flowing per unit time) of the sulfuric acid passing through the 2 nd path C2 is not particularly limited, but in the present embodiment, the flow rate is substantially the same as the flow rate of the sulfuric acid passing through the 1 st path C1.

The control unit 102 controls the 1 st valve 34a, the 2 nd valve 34b, and the water passing valve 34C in such a manner that sulfuric acid passing through the 1 st path C1 is mixed with the hydrogen peroxide solution and then discharged from the nozzle 36 to the substrate W, and then sulfuric acid passing through the 2 nd path C2 is mixed with the hydrogen peroxide solution and then discharged from the nozzle 36 to the substrate W. Therefore, when the supply of sulfuric acid is stopped for flushing the sulfuric acid-hydrogen peroxide solution mixture on the substrate W with the hydrogen peroxide solution, the sulfuric acid-hydrogen peroxide solution mixture at a high temperature can be suppressed from becoming higher, and the temperature of the substrate W can be suppressed from rapidly changing. Therefore, damage such as pattern peeling on the substrate W caused to the substrate W can be suppressed.

Specifically, the sulfuric acid and the hydrogen peroxide solution passing through the 1 st path C1 are mixed, and then the merged sulfuric acid and the hydrogen peroxide solution react with each other to obtain a sulfuric acid/hydrogen peroxide solution mixed solution having a high temperature (for example, 200 ℃ or higher). After the high-temperature sulfuric acid/hydrogen peroxide solution mixture is discharged onto the substrate W, if the supply of sulfuric acid is stopped, the high-temperature sulfuric acid/hydrogen peroxide solution mixture and the hydrogen peroxide solution are joined together on the substrate W. At this time, the mixed solution of the sulfuric acid and the hydrogen peroxide solution remaining on the substrate W is at a high temperature, and thus reacts vigorously with the hydrogen peroxide solution to become a higher temperature, and the substrate W also becomes a high temperature. Then, the sulfuric acid hydrogen peroxide solution mixture is removed from the substrate W by further supplying the hydrogen peroxide solution onto the substrate W, and the supplied hydrogen peroxide solution abruptly drops the temperature of the substrate W.

On the other hand, in the present embodiment, sulfuric acid passing through the 1 st path C1 is mixed with a hydrogen peroxide solution and then ejected from the nozzle 36 to the substrate W, and sulfuric acid passing through the 2 nd path C2 is mixed with a hydrogen peroxide solution and then ejected from the nozzle 36 to the substrate W. The sulfuric acid passing through the 2 nd path C2 merges into the hydrogen peroxide solution at a lower temperature than the sulfuric acid passing through the 1 st path C1. Therefore, the merged sulfuric acid and the hydrogen peroxide solution react with each other, but become a relatively low-temperature hydrogen peroxide solution mixed solution. After the relatively low-temperature sulfuric acid/hydrogen peroxide solution mixture is discharged onto the substrate W, if the supply of sulfuric acid is stopped, the relatively low-temperature sulfuric acid/hydrogen peroxide solution mixture and the hydrogen peroxide solution are joined together on the substrate W. At this time, the mixed solution of the sulfuric acid and the hydrogen peroxide solution remaining on the substrate W is at a relatively low temperature, and thus can suppress a severe reaction with the hydrogen peroxide solution. Therefore, the sulfuric acid hydrogen peroxide solution mixture can be suppressed from becoming high temperature, and the temperature rise of the substrate W can also be suppressed. Then, the sulfuric acid hydrogen peroxide solution mixture is removed from the substrate W by further supplying the hydrogen peroxide solution onto the substrate W, and the supplied hydrogen peroxide solution relatively slowly decreases the temperature of the substrate W.

In addition, in the present embodiment, since it is not necessary to adjust the mixing ratio of sulfuric acid and hydrogen peroxide solution to a desired ratio to suppress damage to the substrate W, the time can be shortened as compared with a method of adjusting the mixing ratio to a desired ratio.

In the present embodiment, by providing the 2 nd path C2 in which sulfuric acid is supplied from the tank 50 to the nozzle 36 without passing through the heating region R1, sulfuric acid having a lower temperature than sulfuric acid heated through the 1 st path C1 can be easily mixed with the hydrogen peroxide solution.

Next, a substrate processing apparatus 100 according to the present embodiment will be described with reference to fig. 1 to 4. Fig. 4 is a block diagram of a substrate processing apparatus 100.

As shown in fig. 4, the control device 101 controls various operations of the substrate processing apparatus 100. The control device 101 controls the transfer robot IR, the center robot CR, the substrate holding unit 20, and the processing liquid supply unit 30. Specifically, the control device 101 transmits control signals to the transfer robot IR, the center robot CR, the substrate holding unit 20, and the processing liquid supply unit 30, thereby controlling the transfer robot IR, the center robot CR, the substrate holding unit 20, and the processing liquid supply unit 30.

Specifically, the control unit 102 controls the transfer robot IR, and transfers the substrates W by the transfer robot IR.

The control unit 102 controls the center robot CR, and transfers the substrate W through the center robot CR. For example, the center robot CR receives an unprocessed substrate W and carries the substrate W into any one of the substrate processing units 10. In addition, the center robot CR receives the processed substrate W from the substrate processing unit 10 and carries out the substrate W.

The control unit 102 controls the substrate holding unit 20 to start rotation of the substrate W, change the rotation speed, and stop rotation of the substrate W. For example, the control unit 102 can control the substrate holding unit 20 to change the rotation speed of the substrate holding unit 20. Specifically, the control unit 102 can change the rotation speed of the substrate W by changing the rotation speed of the electric motor 24 of the substrate holding unit 20.

The control unit 102 can control the valve 34 of the treatment liquid supply unit 30 to switch the state of the valve 34 from the open state to the closed state. Specifically, the control unit 102 can control the valve 34 of the treatment liquid supply unit 30 to open the valve 34, thereby allowing the treatment liquid or the like flowing through the pipe 40 toward the nozzle 36 to pass through. The control unit 102 can stop the supply of the processing liquid or the like flowing through the pipe 40 toward the nozzle 36 by controlling the valve 34 of the processing liquid supply unit 30 to close the valve 34. That is, the control unit 102 controls the supply of the sulfuric acid and the hydrogen peroxide solution to the nozzle 36 by controlling the opening and closing of the 1 st valve 34a, the 2 nd valve 34b, and the water passing valve 34c, for example.

The control unit 102 controls the heater 60 to heat the tank 50 and the pipe 40 to a predetermined temperature. Specifically, the control unit 102 controls the on/off of the heater 60 to maintain the temperature of at least one of the sulfuric acid in the tank 50 and the sulfuric acid passing through the pipe 40 at a predetermined temperature. In the present embodiment, the control unit 102 controls the heater 60 to heat the sulfuric acid passing through the heating region R1 of the 1 st path C1 to a predetermined temperature.

Next, a substrate processing method of the substrate processing apparatus 100 according to the present embodiment will be described with reference to fig. 1 to 5. Fig. 5 is a flowchart of a substrate processing method of the substrate processing apparatus 100 according to the present embodiment. Step S103 is an example of the "1 st ejection step" of the present invention. Step S107 is an example of the "2 nd ejection step" of the present invention.

As shown in fig. 5, in step S101, the control unit 102 merges the sulfuric acid passing through the heating region R1 into the hydrogen peroxide solution. At this time, the 2 nd valve 34b is closed. In addition, the heater 61 is turned on. Hereinafter, sulfuric acid passing through the heating region R1 is sometimes described as relatively high-temperature sulfuric acid.

Specifically, the control unit 102 switches the 1 st valve 34a from the closed state to the open state. The control unit 102 also switches the water valve 34c from the closed state to the open state. Thereby, sulfuric acid is supplied from the tank 50 toward the nozzle 36. The sulfuric acid is heated to a predetermined temperature (for example, 170 to 190 ℃ C. Or higher) by the heater 61 in the heating region R1 of the 1 st pipe 41. In addition, the hydrogen peroxide solution is supplied toward the nozzle 36.

The relatively high temperature sulfuric acid heated in the heating region R1 merges with the hydrogen peroxide solution. The relatively high-temperature sulfuric acid merges with the hydrogen peroxide solution between the heating region R1 and the ejection port 36a of the nozzle 36. In this embodiment, relatively high temperature sulfuric acid is combined with the hydrogen peroxide solution in the nozzle 36. In addition, the water valve 34c may be opened before the 1 st valve 34a is opened.

Next, in step S103, a relatively high-temperature sulfuric acid and hydrogen peroxide solution is ejected onto the substrate W. Specifically, a sulfuric acid/hydrogen peroxide solution mixture containing sulfuric acid at a relatively high temperature and a hydrogen peroxide solution at a high temperature (for example, 200 ℃ or higher) is ejected from the ejection port 36a of the nozzle 36 to the substrate W for a predetermined period of time. Thereby, for example, a predetermined region of a resist layer (not shown) of the substrate W is etched.

Next, in step S105, the control unit 102 merges the relatively low-temperature sulfuric acid into the hydrogen peroxide solution. Specifically, the control unit 102 switches the 2 nd valve 34b from the closed state to the open state. The control unit 102 also switches the 1 st valve 34a from the open state to the closed state. Thereby, relatively low temperature sulfuric acid is supplied from the tank 50 toward the nozzle 36. In addition, the supply of sulfuric acid at a relatively high temperature is stopped.

Further, it is preferable that the switching of the 2 nd valve 34b from the closed state to the open state is performed before the switching of the 1 st valve 34a from the open state to the closed state. Specifically, in the 1 st merging point P1 in the nozzle 36, the 2 nd valve 34b is preferably switched from the closed state to the open state so that the sulfuric acid having a relatively low temperature reaches the 1 st merging point P1 in a state where the sulfuric acid having a relatively high temperature is already present. This can suppress the high-temperature sulfuric acid/hydrogen peroxide solution mixture in which only the hydrogen peroxide solution is supplied from the nozzle 36 onto the substrate W.

Next, in step S107, a relatively low-temperature sulfuric acid and hydrogen peroxide solution is ejected onto the substrate W. Specifically, a mixture of sulfuric acid and hydrogen peroxide solution at a relatively low temperature, which contains sulfuric acid at a relatively low temperature, is ejected from the ejection port 36a of the nozzle 36 to the substrate W for a prescribed time.

Next, in step S109, the control unit 102 stops the supply of sulfuric acid. Specifically, the control unit 102 switches the 2 nd valve 34b from the open state to the closed state. Thereby, only the hydrogen peroxide solution is supplied onto the substrate W. At this time, the hydrogen peroxide solution merges into the relatively low-temperature sulfuric acid hydrogen peroxide solution mixture remaining on the substrate W, and thus the sulfuric acid hydrogen peroxide solution mixture can be inhibited from reacting vigorously with the hydrogen peroxide solution. Therefore, the sulfuric acid hydrogen peroxide solution mixture can be suppressed from becoming high temperature, and the temperature rise of the substrate W can also be suppressed. Then, the sulfuric acid hydrogen peroxide solution mixture is removed from the substrate W by further supplying the hydrogen peroxide solution onto the substrate W, and the temperature of the substrate W is lowered relatively slowly.

Next, in step S111, the control unit 102 stops the supply of the hydrogen peroxide solution. Specifically, the control unit 102 switches the water valve 34c from the open state to the closed state. Thereby, the supply of the processing liquid to the substrate W is stopped.

As described above, the substrate processing method of the present embodiment ends.

(variation 1)

Next, a substrate processing apparatus 100 according to a modification 1 of the present invention will be described with reference to fig. 6. In the 1 st modification, an example will be described in which the 1 st path C1 and the 2 nd path C2 merge at the upstream side of the 1 st merging portion P1 in the sulfuric acid flow direction, unlike the 1 st embodiment described with reference to fig. 1 to 5. Fig. 6 is a schematic view of a processing liquid supply unit 30 of a substrate processing apparatus 100 according to variation 1.

As shown in fig. 6, in the 1 st modification example, the treatment liquid supply portion 30 has a 2 nd merging portion P2. The 2 nd merging portion P2 merges the 1 st path C1 and the 2 nd path C2. The 2 nd merging portion P2 is disposed between the 1 st merging portion P1 and the heating region R1, and merges the 1 st path C1 and the 2 nd path C2.

Specifically, the portion of the 1 st pipe 41 on the upstream side (the tank 50 side) of the heating region R1 is referred to as a pipe 41a, and the portion on the downstream side (the nozzle 36 side) of the heating region R1 is referred to as a pipe 41b. In this case, the 2 nd pipe 42 is connected to the pipe 41b. The portion of the pipe 41b downstream of the 2 nd junction P2 (on the side of the nozzle 36) is a common path between the 1 st path C1 and the 2 nd path C2. In variation 1, the 2 nd channel C2 is formed by the 2 nd pipe 42 and a part of the pipe 41b. The relatively low-temperature sulfuric acid is supplied to the nozzle 36 through the 2 nd pipe 42 and a part of the pipe 41b.

In the 1 st modification, the 1 st path C1 and the 2 nd path C2 join between the 1 st joining portion P1 and the heating region R1. Thus, both the relatively high temperature sulfuric acid and the relatively low temperature sulfuric acid merge into the hydrogen peroxide solution at the same location. Thus, sulfuric acid can be stably mixed with the hydrogen peroxide solution.

Further, since a part of the pipe 41b can be a common pipe for the 1 st path C1 and the 2 nd path C2, the size of the treatment liquid supply unit 30 can be reduced.

Other structures, other effects, and substrate processing methods of modification 1 are the same as those of embodiment 1.

(variation 2)

Next, a substrate processing apparatus 100 according to a modification 2 of the present invention will be described with reference to fig. 7. In the modification 2, an example will be described in which the 1 st path C1 and the 2 nd path C2 branch upstream of the heating region R1 in the sulfuric acid flow direction, unlike the 1 st modification described with reference to fig. 6. Fig. 7 is a schematic view of a processing liquid supply unit 30 of a substrate processing apparatus 100 according to variation 2.

As shown in fig. 7, in variation 2, the treatment liquid supply portion 30 has a branching portion P3. The branching portion P3 is a portion where the 1 st path C1 and the 2 nd path C2 branch. The branching portion P3 is disposed upstream (on the tank 50 side) of the heating region R1 in the sulfuric acid flow direction. That is, the 1 st path C1 and the 2 nd path C2 branch upstream of the heating region R1 in the sulfuric acid flow direction.

In the modification 2, the 1 st path C1 and the 2 nd path C2 merge with each other on the downstream side (the nozzle 36 side) of the heating region R1 in the sulfuric acid flow direction. Specifically, the treatment liquid supply unit 30 has a 2 nd merging portion P2 merging the 1 st path C1 and the 2 nd path C2, as in the 1 st modification. The 2 nd merging portion P2 is arranged downstream of the heating region R1 in the sulfuric acid flow direction.

Specifically, the 2 nd pipe 42 is connected to the pipe 41a and the pipe 41b of the 1 st pipe 41. The portion of the pipe 41a on the upstream side (the tank 50 side) of the branching portion P3 is a common path between the 1 st path C1 and the 2 nd path C2. In variation 2, the 2 nd path C2 is constituted by a part of the pipe 41a, the 2 nd pipe 42, and a part of the pipe 41b. The relatively low-temperature sulfuric acid is supplied to the nozzle 36 through a part of the pipe 41a, the 2 nd pipe 42, and a part of the pipe 41b.

In variation 2, the 1 st valve 34a for opening and closing the flow path of the 1 st path C1 is disposed between the branching portion P3 and the 2 nd merging portion P2. The 2 nd valve 34b for opening and closing the flow path of the 2 nd path C2 is disposed in the 2 nd pipe 42.

In the modification 2, the 1 st path C1 and the 2 nd path C2 branch on the upstream side with respect to the heating region R1, and join on the downstream side with respect to the heating region R1. Therefore, since a part of the pipe 41a and a part of the pipe 41b can be made to be a common pipe for the 1 st path C1 and the 2 nd path C2, the size of the treatment liquid supply section 30 can be further reduced.

Other structures, other effects, and substrate processing methods of variation 2 are the same as those of variation 1.

(variation 3)

Next, a substrate processing apparatus 100 according to a modification 3 of the present invention will be described with reference to fig. 8. In the modification 3, an example will be described in which the treatment liquid supply unit 30 includes the heater 62, unlike the embodiment 1 described with reference to fig. 1 to 5. Fig. 8 is a schematic view of a processing liquid supply unit 30 of a substrate processing apparatus 100 according to variation 3.

As shown in fig. 8, in variation 3, the treatment liquid supply unit 30 further includes a heater 62 as the heater 60. The heater 62 is an example of the "2 nd heater" of the present invention. The heater 62 is a heater for maintaining sulfuric acid in the tank 50 at a specified temperature. In variation 3, the heater 62 maintains the sulfuric acid in the tank 50 at a specified temperature by heating the tank 50. For example, sulfuric acid in tank 50 is maintained above 150 ℃. The heater 62 may not heat the tank 50. For example, a circulation pipe for circulating sulfuric acid may be connected to the tank 50, and the circulation pipe may be heated by the heater 62.

In modification 3, by providing the heater 62 for maintaining the sulfuric acid in the tank 50 at a predetermined temperature, the temperature of the sulfuric acid passing through the heating region R1 can be easily raised to a desired temperature (for example, 170 to 190 ℃ or higher).

Other structures, other effects, and substrate processing methods of variation 3 are the same as those of embodiment 1.

(modification 4)

Next, a substrate processing apparatus 100 according to a modification 4 of the present invention will be described with reference to fig. 9. In the 4 th modification, an example will be described in which the 3 rd pipe 43 is connected to the 1 st pipe 41, unlike the 1 st modification described with reference to fig. 6. Fig. 9 is a schematic view of a processing liquid supply unit 30 of a substrate processing apparatus 100 according to a modification example 4.

As shown in fig. 9, in modification 4, the 1 st path C1 and the hydrogen peroxide solution supply path C3 merge between the nozzle 36 and the heating region R1.

Specifically, the 3 rd pipe 43 is connected to the pipe 41b of the 1 st pipe 41. The hydrogen peroxide solution supply path C3 is formed by the 3 rd piping 43 and a part of the piping 41b.

In modification 4, the 3 rd pipe 43 is connected to the pipe 41b between the 2 nd junction P2 and the nozzle 36. Further, the portion of the pipe 41b downstream of the 1 st joining portion P1 (on the side of the nozzle 36) is a common pipe for the 1 st path C1, the 2 nd path C2, and the hydrogen peroxide solution supply path C3.

In modification 4, by connecting the 3 rd pipe 43 to the 1 st pipe 41, a part of the 1 st pipe 41 can be made common, and thus, the size of the treatment liquid supply section 30 can be further reduced. In addition, since the time from the merging to the ejection is longer than in the case where the sulfuric acid and the hydrogen peroxide solution are merged in the nozzle 36, the sulfuric acid and the hydrogen peroxide solution can be mixed more uniformly.

Other structures, other effects, and substrate processing methods of variation 4 are the same as those of variation 1.

(embodiment 2)

Next, a substrate processing apparatus 100 according to embodiment 2 of the present invention will be described with reference to fig. 10. In embodiment 2, an example will be described in which the treatment liquid supply unit 30 includes a tank 50 and a tank 51, unlike embodiment 1 described with reference to fig. 1 to 5. Fig. 10 is a schematic view of the processing liquid supply unit 30 of the substrate processing apparatus 100 according to the present embodiment. Hereinafter, the differences from embodiment 1 will be mainly described.

As shown in fig. 10, in embodiment 2, the treatment liquid supply unit 30 includes a tank 50, a tank 51, a path 70 (1 st path C1, 2 nd path C2), a hydrogen peroxide solution supply path C3, a heater 61, a heater 62, and a heater 63. Tank 50 and tank 51 store sulfuric acid. The path 70 is a path for supplying sulfuric acid from the tank 51 to the nozzle 36.

In the present embodiment, the tank 51 is an example of "tank 1" of the present invention. The tank 50 is an example of "tank 2" of the present invention. The heater 63 is an example of the "2 nd heater" of the present invention. The heater 62 is an example of the "3 rd heater" of the present invention.

In the present embodiment, a 1 st path C1 is a path for supplying sulfuric acid from the tank 51 to the nozzle 36. The 2 nd path C2 is a path for supplying sulfuric acid from the tank 51 to the nozzle 36.

Specifically, the treatment liquid supply section 30 includes a 1 st pipe 41, a 2 nd pipe 42, a 3 rd pipe 43, and a 4 th pipe 44 as the pipes 40. The 4 th pipe 44 connects the tank 50 and the tank 51. In the present embodiment, the 1 st path C1 includes the 4 th pipe 44, the tank 50, and the 1 st pipe 41. In the present embodiment, the 2 nd pipe 42 connects the tank 51 and the nozzle 36. The 2 nd path C2 includes a 2 nd pipe 42.

The treatment liquid supply section 30 further includes a 4 th valve 34d as a valve 34. The 4 th valve 34d is disposed in the 4 th pipe 44. The 4 th valve 34d opens and closes the flow path of the 4 th pipe 44. When the amount of sulfuric acid in the tank 50 is smaller than the predetermined amount, the control unit 102 switches the 4 th valve 34d from the closed state to the open state. Thereby, sulfuric acid is supplied from the tank 51 to the tank 50.

The treatment liquid supply unit 30 includes a heater 61, a heater 62, and a heater 63 as the heater 60. The heater 62 is a heater for maintaining the sulfuric acid in the tank 50 at a predetermined temperature, as in the modification 3. The heater 62 is the same as in variation 3, and therefore, the description thereof is omitted.

The heater 63 is a heater for maintaining the sulfuric acid in the tank 51 at a specified temperature. In embodiment 2, the heater 63 heats the tank 51 to maintain the sulfuric acid in the tank 51 at a predetermined temperature. The sulfuric acid in tank 51 is maintained at a lower temperature than the sulfuric acid in tank 50. For example, sulfuric acid in the tank 51 is maintained at, for example, 120 ℃ or higher and less than 150 ℃. The heater 62 may not heat the tank 51. For example, a circulation pipe for circulating sulfuric acid may be connected to the tank 51, and the circulation pipe may be heated by the heater 63.

Further, in the present embodiment, the treatment liquid supply unit 30 includes a return pipe 45 and a return pipe 46, and a valve 34e and a valve 34f. The return pipe 45 is connected to the pipe 41b of the 1 st pipe 41. The valve 34e is disposed in the return pipe 45. The valve 34e opens and closes the flow path of the return pipe 45.

The return pipe 46 is connected to a portion of the 2 nd pipe 42 downstream of the 2 nd valve 34b (on the side of the nozzle 36). The valve 34f is disposed in the return pipe 46. The valve 34f opens and closes the flow path of the return pipe 46.

Other configurations of embodiment 2 are the same as those of embodiment 1.

Next, a substrate processing method of the substrate processing apparatus 100 according to the present embodiment will be described with reference to fig. 10 and 11. Fig. 11 is a flowchart of a substrate processing method of the substrate processing apparatus 100 according to the present embodiment. Steps S201 to S211 of the present embodiment correspond to steps S101 to S111 of embodiment 1. Step S203 is an example of the "1 st ejection step" of the present invention. Step S207 is an example of the "2 nd ejection step" of the present invention. In this embodiment, a description will be mainly given of a difference from embodiment 1.

As shown in fig. 11, in step S201, the control unit 102 merges the relatively high-temperature sulfuric acid passing through the heating region R1 into the hydrogen peroxide solution. At this time, the 2 nd valve 34b, the valve 34e, and the valve 34f are closed. In addition, the heater 61, the heater 62, and the heater 63 are turned on.

Next, in step S203, a relatively high-temperature sulfuric acid and hydrogen peroxide solution is ejected onto the substrate W.

Next, in step S205, the control unit 102 merges the relatively low-temperature sulfuric acid into the hydrogen peroxide solution. Specifically, the control unit 102 switches the 2 nd valve 34b from the closed state to the open state. The control unit 102 also switches the 1 st valve 34a from the open state to the closed state. Thereby, relatively low temperature sulfuric acid is supplied from the tank 51 toward the nozzle 36.

Next, in step S207, a relatively low-temperature sulfuric acid and hydrogen peroxide solution is ejected onto the substrate W.

Next, in step S209, the control unit 102 stops the supply of sulfuric acid.

Next, in step S211, the control unit 102 stops the supply of the hydrogen peroxide solution.

Next, in step S213, the control unit 102 opens the valves 34e and 34f to suppress the processing liquid from falling from the nozzles 36. Specifically, the control unit 102 switches the valve 34e from the closed state to the open state. Thereby, the treatment liquid remaining between the return pipe 45 and the discharge port 36a of the nozzle 36 is introduced into the return pipe 45 by the siphon principle. The control unit 102 also switches the valve 34f from the closed state to the open state. Thus, the treatment liquid remaining between the return pipe 46 and the discharge port 36a of the nozzle 36 is introduced into the return pipe 46 by the siphon principle. Therefore, the treatment liquid can be suppressed from falling from the discharge port 36a of the nozzle 36. Then, the control unit 102 closes the valves 34e and 34 f.

As described above, the substrate processing method of the present embodiment ends.

Other effects of embodiment 2 and other substrate processing methods are the same as those of embodiment 1.

(variation 5)

Next, a substrate processing apparatus 100 according to a modification 5 of the present invention will be described with reference to fig. 12. In the modification 5, an example will be described in which the 1 st path C1 and the 2 nd path C2 branch upstream of the heating region R1 in the sulfuric acid flow direction, unlike the embodiment 2 described with reference to fig. 10 and 11. Fig. 12 is a schematic view of a processing liquid supply unit 30 of the substrate processing apparatus 100 according to the modification example 5.

As shown in fig. 12, in the 5 th modification example, the treatment liquid supply portion 30 has a branching portion P3 as in the 2 nd modification example. The branching portion P3 is a portion where the 1 st path C1 and the 2 nd path C2 branch. The branching portion P3 is disposed upstream of the heating region R1 in the sulfuric acid flow direction. That is, the 1 st path C1 and the 2 nd path C2 branch upstream of the heating region R1 in the sulfuric acid flow direction.

In the 5 th modification, the 1 st path C1 and the 2 nd path C2 merge on the downstream side of the heating region R1 in the sulfuric acid flow direction, as in the 2 nd modification shown in fig. 7. Specifically, the treatment liquid supply unit 30 includes a 2 nd merging portion P2 where the 1 st path C1 merges with the 2 nd path C2, as in the 2 nd modification. The 2 nd merging portion P2 is arranged downstream of the heating region R1 in the sulfuric acid flow direction.

Specifically, the 2 nd pipe 42 is connected to the pipe 41a and the pipe 41b of the 1 st pipe 41. Further, the portion of the pipe 41a on the upstream side (the tank 50 side) of the branching portion P3 and the 4 th pipe 44 are a common path between the 1 st path C1 and the 2 nd path C2. In the 5 th modification, the 4 th pipe 44 and the 1 st pipe 41 form the 1 st path C1. The 4 th pipe 44, a part of the pipe 41a, the 2 nd pipe 42, and a part of the pipe 41b constitute a 2 nd path C2.

In the 5 th modification, as in the 2 nd modification, the 1 st valve 34a for opening and closing the flow path of the 1 st path C1 is disposed between the branching portion P3 and the 2 nd merging portion P2. The 2 nd valve 34b for opening and closing the flow path of the 2 nd path C2 is disposed in the 2 nd pipe 42.

In the 5 th modification, the 1 st path C1 and the 2 nd path C2 branch on the upstream side with respect to the heating region R1, and join on the downstream side with respect to the heating region R1. Therefore, the 4 th pipe 44, a part of the pipe 41a, and a part of the pipe 41b can be made common to the 1 st path C1 and the 2 nd path C2, and thus the size of the treatment liquid supply section 30 can be further suppressed from increasing.

Other structures, other effects, and substrate processing methods of variation 5 are the same as those of embodiment 2.

(variation 6)

Next, a substrate processing apparatus 100 according to a modification 6 of the present invention will be described with reference to fig. 13. In the modification 6, an example will be described in which a circulation pipe 47 for circulating sulfuric acid is provided, unlike the modification 5 described with reference to fig. 12. Fig. 13 is a schematic view of a processing liquid supply unit 30 of a substrate processing apparatus 100 according to a modification 6.

As shown in fig. 13, in modification 6, the treatment liquid supply unit 30 includes a circulation pipe 47. In modification 6, the circulation pipe 47 is connected to the pipe 41b. The circulation pipe 47 is connected to a portion of the pipe 41b downstream of the 2 nd junction P2, for example. The circulation pipe 47 connects the pipe 41b and the tank 51, for example. The circulation pipe 47 returns the sulfuric acid passing through the pipe 41b to the tank 51. The circulation pipe 47 may connect the pipe 41a or the 2 nd pipe 42 to the tank 51. The circulation pipe 47 may connect the pipe 41a, the 2 nd pipe 42, or the pipe 41b to the tank 50 to return the sulfuric acid to the tank 50.

The treatment liquid supply unit 30 includes a valve 34g and a valve 34h. The valve 34g is disposed in the circulation pipe 47. The valve 34g opens and closes the flow path of the circulation pipe 47. The valve 34h is disposed downstream of the portion of the pipe 41b to which the circulation pipe 47 is connected. The valve 34h opens and closes the flow path of the pipe 41b.

When sulfuric acid is supplied to the nozzle 36, the valve 34g is closed and the valve 34h is opened. On the other hand, when sulfuric acid is returned to tank 51 (or tank 50), valve 34g is opened and valve 34h is closed.

In the modification 6, when sulfuric acid is not supplied to the nozzle 36, the sulfuric acid in the tank 50 is returned to the tank 50 through, for example, the pipe 41a, the 2 nd pipe 42 (or the heating region R1), the pipe 41b, the circulation pipe 47, the tank 51, and the 4 th pipe 44. That is, the piping 41a, the 2 nd piping 42 (or the heating region R1), the piping 41b, the circulation piping 47, the tank 51, and the 4 th piping 44 constitute a circulation path for circulating the sulfuric acid in the tank 50. This can maintain the temperature of the sulfuric acid in the pipes 41a, 2 nd pipe 42, 41b, etc. at a predetermined temperature.

In the modification 6, the tank 50 is heated by the heater 62 to circulate the sulfuric acid at a predetermined temperature. For example, the pipe 41a may be heated by the heater 62 to circulate sulfuric acid at a predetermined temperature.

Other configurations and other effects of the modification 6 are the same as those of embodiment 2. The substrate processing method of variation 6 is the same as that of variation 2.

(embodiment 3)

Next, a substrate processing apparatus 100 according to embodiment 3 of the present invention will be described with reference to fig. 14, 15, and 16. In embodiment 3, an example will be described in which a relatively low-temperature hydrogen peroxide solution mixture is obtained using sulfuric acid passing through the 1 st path C1, unlike embodiments 1 and 2 and the like. Fig. 14 is a schematic view of a substrate processing unit 10 in the substrate processing apparatus 100 of embodiment 3. Hereinafter, the differences from embodiment 1 will be mainly described.

As shown in fig. 14, the substrate processing apparatus 100 includes a shielding member 90. The shielding member 90 is housed in the chamber 12. The shielding member 90 shields the substrate W held in the substrate holding portion 20 from the vertically upper side.

The shielding member 90 is disposed above the substrate holding portion 20. The shielding member 90 faces the substrate W. The outer diameter of the shielding member 90 is substantially equal to or slightly larger than the outer diameter of the substrate W. The shielding member 90 is moved between the approach position and the retreat position with respect to the substrate W. The substrate processing apparatus 100 further includes a moving mechanism (not shown) for moving the shielding member 90 between the approaching position and the retracted position. When the shielding member 90 is located at the approaching position, the shielding member 90 descends and approaches the upper surface Wa of the substrate W at a specified interval. In the approach position, the shielding member 90 covers the upper surface Wa of the substrate W to shield the upper side of the substrate W. When the shielding member 90 is located at the retracted position, the shielding member 90 is located at a position vertically upward away from the approach position. When the shielding member 90 is changed from the approaching position to the retracted position, the shielding member 90 is lifted away from the substrate W.

The shielding member 90 receives the liquid splashed from the substrate W when the processing liquid is discharged from the nozzle 36 to the substrate W. This suppresses scattering of the processing liquid around the substrate holding portion 20 and the like.

The substrate processing apparatus 100 further includes a fluid supply unit 130. The fluid supply unit 130 includes a pipe 140, a valve 134, and a nozzle 136. The nozzle 136 is disposed on the shielding member 90. The nozzles 136 eject fluid onto the upper surface Wa of the substrate W. The fluid comprises a treatment liquid or gas. The treatment liquid is not particularly limited, and may contain, for example, a rinse liquid or isopropyl alcohol (IPA). The gas is not particularly limited, and may be, for example, nitrogen or clean air.

The nozzle 136 may discharge the fluid to the central portion of the substrate W, or may discharge the fluid to an area between the central portion and the peripheral portion of the substrate W, for example. The nozzle 136 has an ejection port (not shown) from which a fluid is ejected. The number of the ejection ports is not particularly limited, and may be 1 or 2 or more. In the present embodiment, a plurality of ejection ports are arranged. The nozzle 136 is connected to a pipe 140. Fluid is supplied from a supply source to the pipe 140. The valve 134 opens and closes the flow path in the pipe 140.

The valve 134 adjusts the opening degree of the pipe 140 to adjust the flow rate of the fluid supplied to the pipe 140. Specifically, the valve 134 includes a valve body (not shown) having a valve seat provided therein, a valve body that opens and closes the valve seat, and an actuator (not shown) that moves the valve body between an open position and a closed position.

Next, the processing liquid supply unit 30 of the substrate processing apparatus 100 according to the present embodiment will be described with reference to fig. 15. Fig. 15 is a schematic plan view of the substrate processing apparatus 100 of the present embodiment.

As shown in fig. 15, in embodiment 3, the treatment liquid supply unit 30 includes a tank 50, a path 70, a hydrogen peroxide solution supply path C3, and a heater 61, as in embodiment 1. Path 70 includes path 1, path C1. In the present embodiment, unlike embodiment 1, the path 70 does not include the 2 nd path C2. Tank 50 stores sulfuric acid. The tank 50 is an example of "tank 1" of the present invention. The heater 61 is an example of the "1 st heater" of the present invention.

The heater 61 can heat the heating region R1 of the 1 st path C1. In the present embodiment, the heater 61 is switched on and off by the control unit 102. That is, the heater 61 can be switched between a heating state in which the heating region R1 is heated and a non-heating state in which the heating region R1 is not heated.

The heating region R1 is heated by the heater 61, so that the temperature of sulfuric acid passing through the heating region R1 rises. For example, the temperature of the sulfuric acid heated in the heating region R1 through the heating region R1 becomes the 1 st temperature. The 1 st temperature is, for example, 170℃to 190℃or higher.

On the other hand, when the heater 61 does not heat the heating region R1, the temperature of sulfuric acid passing through the heating region R1 does not rise. When the heater 61 does not heat the heating region R1, the sulfuric acid passing through the heating region R1 has the 2 nd temperature. The 2 nd temperature is, for example, normal temperature to 150 ℃. That is, the sulfuric acid that is not heated in the heating region R1 when passing through the heating region R1 has a lower temperature than the sulfuric acid that is heated in the heating region R1. Hereinafter, sulfuric acid heated in the heating region R1 is sometimes described as relatively high-temperature sulfuric acid, and sulfuric acid not heated in the heating region R1 is sometimes described as relatively low-temperature sulfuric acid.

The treatment liquid supply section 30 includes a 1 st pipe 41 and a 3 rd pipe 43 as pipes 40. In this embodiment, unlike embodiment 1, the treatment liquid supply unit 30 does not include the 2 nd pipe 42.

The treatment liquid supply unit 30 includes a 1 st valve 34a and a water passing valve 34c as the valves 34. In this embodiment, unlike embodiment 1, the treatment liquid supply unit 30 does not include the 2 nd valve 34b.

In the present embodiment, the relatively high-temperature sulfuric acid heated in the heating region R1 reacts with the hydrogen peroxide solution to obtain a hydrogen peroxide solution mixture having a high temperature (for example, 200 ℃ or higher).

On the other hand, the sulfuric acid of a relatively low temperature that is not heated in the heating region R1 merges into the hydrogen peroxide solution at a temperature lower than that of the heated sulfuric acid of a relatively high temperature. Thus, the sulfuric acid at a relatively low temperature reacts with the hydrogen peroxide solution, but becomes a mixed solution of hydrogen peroxide solutions at a relatively low temperature. The flow rate (amount of sulfuric acid flowing per unit time) of the sulfuric acid at a relatively low temperature is not particularly limited, but is substantially the same as the flow rate of the sulfuric acid at a relatively high temperature in the present embodiment.

The control unit 102 sets the heater 61 to the 1 st output, thereby converting the sulfuric acid passing through the 1 st path C1 into relatively high-temperature sulfuric acid. The relatively high temperature sulfuric acid has a temperature of 1 st. The 1 st temperature is, for example, 170℃to 190℃or higher. The control unit 102 sets the heater 61 to the 2 nd output lower than the 1 st output, thereby converting the sulfuric acid passing through the 1 st path C1 into sulfuric acid having a relatively low temperature. The relatively low temperature sulfuric acid has a 2 nd temperature lower than the 1 st temperature. The 2 nd temperature is, for example, a temperature of normal temperature to 150 ℃.

In the present embodiment, the control unit 102 turns on the heater 61 to change the sulfuric acid passing through the 1 st path C1 to the sulfuric acid having the 1 st temperature. The control unit 102 turns off the heater 61 to convert the sulfuric acid passing through the 1 st path C1 into sulfuric acid having the 2 nd temperature.

In the present embodiment, the control unit 102 controls the heater 61 in such a manner that relatively high-temperature sulfuric acid is mixed with the hydrogen peroxide solution and then ejected from the nozzle 36 to the substrate W, and then relatively low-temperature sulfuric acid is mixed with the hydrogen peroxide solution and then ejected from the nozzle 36 to the substrate W. Therefore, when the supply of sulfuric acid is stopped for flushing the sulfuric acid-hydrogen peroxide solution mixture on the substrate W with the hydrogen peroxide solution, the sulfuric acid-hydrogen peroxide solution mixture at a high temperature can be suppressed from becoming higher, and the temperature of the substrate W can be suppressed from rapidly changing. Therefore, damage such as pattern peeling on the substrate W caused to the substrate W can be suppressed.

In addition, in this embodiment, as in embodiment 1, since there is no need to adjust the mixing ratio of sulfuric acid and hydrogen peroxide solution to a desired ratio to suppress damage to the substrate W, the time can be shortened as compared with the method of adjusting the mixing ratio to a desired ratio.

In addition, unlike embodiment 1, the present embodiment does not require the provision of the 2 nd path C2 and the 2 nd valve 34b, and therefore can simplify the structure of the substrate processing apparatus 100.

Other configurations of embodiment 3 are the same as those of embodiment 1.

Next, a substrate processing method of the substrate processing apparatus 100 according to the present embodiment will be described with reference to fig. 15 and 16. Fig. 16 is a flowchart of a substrate processing method of the substrate processing apparatus 100 according to the present embodiment. Steps S301 to S311 of the present embodiment correspond to steps S101 to S111 of embodiment 1. Step S301 is an example of the "1 st flow process" of the present invention. Step S303 is an example of the "1 st ejection step" of the present invention. Step S305 is an example of the "2 nd flow process" of the present invention. Step S307 is an example of the "2 nd ejection step" of the present invention. In this embodiment, a description will be mainly given of a difference from embodiment 1.

As shown in fig. 16, in step S301, the control unit 102 merges the relatively high-temperature sulfuric acid passing through the heating region R1 into the hydrogen peroxide solution. At this time, the heater 61 is turned on, and the sulfuric acid from the tank 50 is heated in the heating region R1 to be sulfuric acid of a relatively high temperature.

Next, in step S303, a relatively high-temperature sulfuric acid and hydrogen peroxide solution is ejected onto the substrate W.

Next, in step S305, the control unit 102 merges the relatively low-temperature sulfuric acid into the hydrogen peroxide solution. Specifically, the control unit 102 turns off the heater 61. Thereby, the heater 61 is switched from the on state to the off state. Thereby, the sulfuric acid passing through the 1 st path C1 is not heated in the heating region R1, so that the sulfuric acid of relatively low temperature is supplied toward the nozzle 36.

Next, in step S307, a relatively low-temperature sulfuric acid and hydrogen peroxide solution is ejected onto the substrate W.

Next, in step S309, the control unit 102 stops the supply of sulfuric acid.

Next, in step S311, the control unit 102 stops the supply of the hydrogen peroxide solution.

As described above, the substrate processing method of the present embodiment ends.

In embodiment 3, sulfuric acid at a relatively high temperature is mixed with a hydrogen peroxide solution and then ejected onto the substrate W, and then the output of the heater 61 is switched, whereby sulfuric acid at a relatively low temperature is mixed with a hydrogen peroxide solution and then ejected onto the substrate W. Therefore, damage such as pattern peeling on the substrate W can be suppressed from being caused to the substrate W by merely switching the output of the heater 61.

In the substrate processing, for example, a rinse liquid may be discharged from the nozzle 136 disposed in the shielding member 90. In this case, after step S311, the rinse liquid may be discharged from the nozzle 136 to the substrate W.

In the substrate processing, nitrogen gas, for example, may be ejected from the nozzle 136 disposed in the shielding member 90. For example, during the period from step S303 to step S309, nitrogen gas, for example, may be discharged from the nozzle 136. In this case, since a downward air flow is generated above the substrate W, the processing liquid ejected from the nozzle 36 onto the substrate W can be prevented from splashing around the substrate W.

Other substrate processing methods and other effects of embodiment 3 are the same as those of embodiment 1.

(variation 7)

Next, a substrate processing apparatus 100 according to a modification 7 of the present invention will be described with reference to fig. 17. In the modification 7, an example will be described in which the treatment liquid supply unit 30 includes the heater 62, unlike in the embodiment 3 described with reference to fig. 15 and 16. Fig. 17 is a schematic view of a processing liquid supply unit 30 of a substrate processing apparatus 100 according to a modification 7.

As shown in fig. 17, in the 7 th modification example, the treatment liquid supply section 30 further includes a heater 62 as the heater 60. The heater 62 is an example of the "2 nd heater" of the present invention. The heater 62 is a heater for maintaining sulfuric acid in the tank 50 at a specified temperature. In variation 7, the heater 62 maintains the sulfuric acid in the tank 50 at a specified temperature by heating the tank 50. For example, sulfuric acid in tank 50 is maintained above 150 ℃. The heater 62 may not heat the tank 50. For example, a circulation pipe for circulating sulfuric acid may be connected to the tank 50, and the circulation pipe may be heated by the heater 62.

In modification 7, by providing the heater 62 for maintaining the sulfuric acid in the tank 50 at a predetermined temperature, the temperature of the sulfuric acid passing through the heating region R1 can be easily raised to a desired temperature (for example, 170 to 190 ℃ or higher).

Other structures, other effects, and substrate processing methods of variation 7 are the same as those of embodiment 3.

(variation 8)

Next, a substrate processing apparatus 100 according to a modification 8 of the present invention will be described with reference to fig. 18. In the 8 th modification, an example will be described in which the 3 rd pipe 43 is connected to the 1 st pipe 41, unlike the 3 rd embodiment described with reference to fig. 15. Fig. 18 is a schematic view of a processing liquid supply unit 30 of a substrate processing apparatus 100 according to a modification 8.

As shown in fig. 18, in the 8 th modification example, the 1 st path C1 and the hydrogen peroxide solution supply path C3 merge between the nozzle 36 and the heating region R1.

Specifically, the 3 rd pipe 43 is connected to the pipe 41b of the 1 st pipe 41. The hydrogen peroxide solution supply path C3 is formed by the 3 rd piping 43 and a part of the piping 41b. The portion of the pipe 41b downstream of the 1 st joining portion P1 (on the side of the nozzle 36) is a common pipe between the 1 st path C1 and the hydrogen peroxide solution supply path C3.

In the 8 th modification, by connecting the 3 rd pipe 43 to the 1 st pipe 41, a part of the 1 st pipe 41 can be made common, and thus, the size of the treatment liquid supply section 30 can be further suppressed from increasing. In addition, since the time from the merging to the ejection is longer than in the case where the sulfuric acid and the hydrogen peroxide solution are merged in the nozzle 36, the sulfuric acid and the hydrogen peroxide solution can be mixed more uniformly.

Other structures, other effects, and substrate processing methods of variation 8 are the same as those of embodiment 3.

(embodiment 4)

Next, a substrate processing apparatus 100 according to embodiment 4 of the present invention will be described with reference to fig. 19 and 20. In embodiment 4, an example will be described in which the treatment liquid supply unit 30 includes the tanks 50 and 51, unlike embodiment 3 described with reference to fig. 15 and 16. Fig. 19 is a schematic view of the processing liquid supply unit 30 of the substrate processing apparatus 100 according to the present embodiment. Hereinafter, a description will be mainly given of the differences from embodiment 3.

As shown in fig. 19, in embodiment 4, the treatment liquid supply unit 30 includes a tank 50, a tank 51, a path 70, a hydrogen peroxide solution supply path C3, a heater 61, a heater 62, and a heater 63. Tank 50 and tank 51 store sulfuric acid. Path 70 includes path 1, path C1. In embodiment 4, unlike embodiment 2, the path 70 does not include the 2 nd path C2.

In the present embodiment, the tank 51 is an example of "tank 1" of the present invention. The tank 50 is an example of "tank 2" of the present invention. The heater 63 is an example of the "2 nd heater" of the present invention. The heater 62 is an example of the "3 rd heater" of the present invention.

In the present embodiment, a 1 st path C1 is a path for supplying sulfuric acid from the tank 51 to the nozzle 36.

Specifically, the treatment liquid supply unit 30 includes a 1 st pipe 41, a 3 rd pipe 43, and a 4 th pipe 44 as the pipes 40. The 4 th pipe 44 connects the tank 50 and the tank 51. In the present embodiment, the 1 st path C1 is constituted by the 4 th pipe 44, the tank 50, and the 1 st pipe 41.

The treatment liquid supply section 30 further includes a 4 th valve 34d as a valve 34. The 4 th valve 34d is disposed in the 4 th pipe 44. The 4 th valve 34d opens and closes the flow path of the 4 th pipe 44. When the amount of sulfuric acid in the tank 50 is smaller than the predetermined amount, the control unit 102 switches the 4 th valve 34d from the closed state to the open state. Thereby, sulfuric acid is supplied from the tank 51 to the tank 50.

The treatment liquid supply unit 30 includes a heater 61, a heater 62, and a heater 63 as the heater 60. The heater 62 is a heater for maintaining the sulfuric acid in the tank 50 at a predetermined temperature, as in the modification 7. The heater 62 is the same as in the 7 th modification, and therefore, the description thereof is omitted.

The heater 63 is a heater for maintaining the sulfuric acid in the tank 51 at a specified temperature. In the present embodiment, the heater 63 heats the tank 51 to maintain the sulfuric acid in the tank 51 at a predetermined temperature. The sulfuric acid in tank 51 is maintained at a lower temperature than the sulfuric acid in tank 50. For example, sulfuric acid in the tank 51 is maintained at, for example, 120 ℃ or higher and less than 150 ℃. The heater 62 may not heat the tank 51. For example, a circulation pipe for circulating sulfuric acid may be connected to the tank 51, and the circulation pipe may be heated by the heater 63.

Further, in the present embodiment, the treatment liquid supply unit 30 includes a return pipe 45 and a valve 34e. The return pipe 45 is connected to the pipe 41b of the 1 st pipe 41. The valve 34e is disposed in the return pipe 45. The valve 34e opens and closes the flow path of the return pipe 45.

Other configurations of embodiment 4 are the same as those of embodiment 3.

Next, a substrate processing method of the substrate processing apparatus 100 according to the present embodiment will be described with reference to fig. 19 and 20. Fig. 20 is a flowchart of a substrate processing method of the substrate processing apparatus 100 according to the present embodiment. Steps S401 to S411 of the present embodiment correspond to steps S301 to S311 of embodiment 3. Step S401 is an example of the "1 st flow process" of the present invention. Step S403 is an example of the "1 st ejection step" of the present invention. Step S405 is an example of the "2 nd flow process" of the present invention. Step S407 is an example of the "2 nd ejection step" of the present invention. In this embodiment, a description will be mainly given of a difference from embodiment 3.

As shown in fig. 20, in step S401, the control unit 102 merges the relatively high-temperature sulfuric acid passing through the heating region R1 into the hydrogen peroxide solution. At this time, the heaters 61, 62, and 63 are turned on, and the sulfuric acid from the tank 50 is heated in the heating region R1 to be sulfuric acid of relatively high temperature.

Next, in step S403, a relatively high-temperature sulfuric acid and hydrogen peroxide solution is ejected onto the substrate W.

Next, in step S405, the control unit 102 merges the relatively low-temperature sulfuric acid into the hydrogen peroxide solution.

Next, in step S407, a relatively low-temperature sulfuric acid and hydrogen peroxide solution is ejected onto the substrate W.

Next, in step S409, the control unit 102 stops the supply of sulfuric acid.

Next, in step S411, the control unit 102 stops the supply of the hydrogen peroxide solution.

Next, in step S413, the control unit 102 opens the valve 34e to suppress the processing liquid from falling from the nozzle 36. Specifically, the control unit 102 switches the valve 34e from the closed state to the open state. Thereby, the treatment liquid remaining between the return pipe 45 and the discharge port 36a of the nozzle 36 is introduced into the return pipe 45 by the siphon principle. Therefore, the treatment liquid can be suppressed from falling from the discharge port 36a of the nozzle 36. Then, the control unit 102 closes the valve 34 e.

As described above, the substrate processing method of the present embodiment ends.

Other effects of embodiment 4 and other substrate processing methods are the same as those of embodiment 3.

(variation 9)

Next, a substrate processing apparatus 100 according to a modification 9 of the present invention will be described with reference to fig. 21. In the modification 9, an example will be described in which a circulation pipe 47 for circulating sulfuric acid is provided, unlike embodiments 3 and 4 and the like. Fig. 21 is a schematic view of a processing liquid supply unit 30 of a substrate processing apparatus 100 according to variation 9.

As shown in fig. 21, in the 9 th modification example, the treatment liquid supply portion 30 includes a branching portion P4 and a circulation pipe 47. The branching portion P4 is a portion where the 1 st path C1 branches off from the circulation pipe 47. In modification 9, the branching portion P4 is disposed in the pipe 41b. That is, in the 9 th modification, the circulation pipe 47 is connected to the pipe 41b. The circulation pipe 47 connects the pipe 41b and the tank 51, for example. The circulation pipe 47 returns the sulfuric acid passing through the pipe 41b to the tank 51. The circulation pipe 47 may connect the pipe 41b and the tank 50 to return the sulfuric acid to the tank 50.

In the modification 9, the heater 61 is disposed upstream of the branch portion P4 in the sulfuric acid flow direction in the 1 st path C1. Therefore, the sulfuric acid passing through the circulation path can be heated by the heater 61.

The treatment liquid supply unit 30 includes a valve 34g and a valve 34h. The valve 34g is disposed in the circulation pipe 47. The valve 34g opens and closes the flow path of the circulation pipe 47. The valve 34h is disposed downstream of the branch portion P4 in the pipe 41 b. The valve 34h opens and closes the flow path of the pipe 41 b.

When sulfuric acid is supplied to the nozzle 36, the valve 34g is closed and the valve 34h is opened. On the other hand, when sulfuric acid is returned to tank 51 (or tank 50), valve 34g is opened and valve 34h is closed.

In the 9 th modification, when sulfuric acid is not supplied to the nozzle 36, the sulfuric acid in the tank 50 is returned to the tank 50 through, for example, the pipe 41a, the heating region R1, the pipe 41b, the circulation pipe 47, the tank 51, and the 4 th pipe 44. That is, the piping 41a, the heating region R1, the piping 41b, the circulation piping 47, the tank 51, and the 4 th piping 44 constitute a circulation path for circulating the sulfuric acid in the tank 50. This can maintain the temperature of the sulfuric acid in the pipes 41a and 41b at a predetermined temperature.

In addition, in the modification 9, an example in which the tank 50 is heated by the heater 62 to circulate the sulfuric acid at a predetermined temperature is shown, but the present invention is not limited to this. For example, the pipe 41a may be heated by the heater 62 to circulate sulfuric acid at a predetermined temperature.

Other configurations and other effects of the 9 th modification are the same as those of the 4 th embodiment. The substrate processing method according to variation 9 is the same as that according to embodiment 3.

(variation 10)

Next, a substrate processing apparatus 100 according to a 10 th modification of the present invention will be described with reference to fig. 22. In the 10 th modification, an example will be described in which the heater 61 is disposed downstream of the branch portion P4, unlike in the 9 th modification. Fig. 22 is a schematic view of a processing liquid supply unit 30 of the substrate processing apparatus 100 according to the 10 th modification.

As shown in fig. 22, in the 10 th modification example, the treatment liquid supply portion 30 includes a branching portion P4 and a circulation pipe 47, as in the 9 th modification example. The branching portion P4 is a portion where the 1 st path C1 branches off from the circulation pipe 47. In the 10 th modification, the branching portion P4 is disposed in the pipe 41a. That is, the circulation pipe 47 is connected to the pipe 41a.

In the 10 th modification, the heater 61 is disposed downstream of the branch portion P4 in the sulfuric acid flow direction in the 1 st path C1. That is, the heater 61 is disposed between the circulation path and the nozzle 36.

In the 10 th modification, as described above, the heater 61 is disposed downstream of the branch portion P4 in the 1 st pipe 41. Therefore, the heater 61 can be disposed in the vicinity of the nozzle 36. Therefore, the temperature of the sulfuric acid heated by the heater 61 can be suppressed from decreasing until the sulfuric acid reaches the nozzle 36.

Other structures, other effects, and substrate processing methods of variation 10 are the same as those of variation 9.

The embodiments of the present invention have been described above with reference to the drawings. However, the present invention is not limited to the above-described embodiments, and can be implemented in various modes within a range not departing from the gist thereof. In addition, a plurality of components disclosed in the above embodiment can be appropriately changed. For example, some of all the components shown in a certain embodiment may be added to the components of another embodiment, or some of all the components shown in a certain embodiment may be deleted from the embodiment.

The drawings are schematically shown mainly for each component for the convenience of understanding the invention, and the thickness, length, number, interval, and the like of each component shown in the drawings may be different from those in practice for the convenience of manufacturing the drawings. The configuration of each component shown in the above embodiment is an example, and is not particularly limited, and various modifications can be made without departing from the scope of the present invention.

For example, in the 4 th modification example shown in fig. 9, an example is shown in which the 1 st path C1 and the hydrogen peroxide solution supply path C3 merge between the nozzle 36 and the heating region R1, but the present invention is not limited to this. In the same manner as in embodiment 1, 1 st to 3 rd variations, 2 nd embodiment, 5 th variation, 6 th variation, 3 rd embodiment, 7 th variation, 4 th embodiment, 9 th variation and 10 th variation, the 1 st path C1 and the hydrogen peroxide solution supply path C3 may be merged between the nozzle 36 and the heating region R1.

For example, in embodiment 2 shown in fig. 10 and 11, return pipes 45 and 46 are provided to prevent the treatment liquid from falling from the nozzle 36. In the same manner as in embodiment 1, 1 st to 4 th variations, 6 th variations, 3 rd embodiment, 7 th variations, 8 th variations, 9 th variations and 10 th variations, the return piping 45 may be provided. In embodiment 2, the return pipes 45 and 46 may not be provided.

For example, in the 6 th modification shown in fig. 13, an example in which the circulation pipe 47 is provided is shown, but the present invention is not limited to this. In the same manner as in embodiment 1, 1 to 4, 2, 5, 3, 7, 8 and 4, a circulation pipe 47 for circulating sulfuric acid may be provided.

In embodiment 2 shown in fig. 10 and 11, for example, the sulfuric acid is supplied directly to the nozzle 36 from the upstream tank (tank 51) when there are 2 tanks, but the present invention is not limited to this. The sulfuric acid may be directly supplied to the nozzle 36 from a downstream tank (tank 50) in the case of 2 tanks.

In addition, for example, in embodiment 2 shown in fig. 10 and 11, an example in which the heater 61 is provided is shown, but the present invention is not limited to this. For example, in embodiment 2, the heater 61 may not be provided. In this case, the heater 62 corresponds to the "1 st heater" of the present invention. Further, for example, the tank 50 corresponds to a "heating region" of the present invention.

In addition, for example, in embodiment 3 shown in fig. 14 to 16, an example in which the substrate processing apparatus 100 includes the shielding member 90 has been described, but the present invention is not limited thereto. In the same manner as in embodiment 1, 1 to 4, 2, 5, and 6, the substrate processing apparatus 100 may further include a shielding member 90 or a fluid supply unit 130.

In addition, for example, in embodiment 3 shown in fig. 14 to 16, an example in which the heater 61 is turned off when sulfuric acid at a relatively low temperature is mixed with the hydrogen peroxide solution in step S305 (the 2 nd flow-through step) has been described, but the present invention is not limited thereto. If the temperature of sulfuric acid is lower than that in step S301 (the 1 st flow-through step), the heater 61 may be turned on.

In the above embodiment, the relatively high-temperature sulfuric acid, the relatively low-temperature sulfuric acid, and the hydrogen peroxide solution were supplied from 1 nozzle 36 to the substrate W, but the present invention is not limited thereto. For example, relatively high temperature sulfuric acid, relatively low temperature sulfuric acid, and hydrogen peroxide solution may be supplied to the substrate W from 2 or 3 nozzles. That is, for example, sulfuric acid at a relatively high temperature and hydrogen peroxide solution may be joined to each other on the substrate W, or sulfuric acid at a relatively low temperature and hydrogen peroxide solution may be joined to each other on the substrate W.

[ Industrial availability ]

The present invention can be used in the field of a substrate processing apparatus and a substrate processing method.

[ description of symbols ]

34a 1 st valve

34b 2 nd valve

34c water passing valve

36 nozzle

36a discharge port

50 tank (tank 1, tank 2)

51 tank (tank 1)

61 heater (heater 1)

62 heater (heater 2, heater 3)

63 heater (No. 2 heater)

70 path

100 substrate processing apparatus

102 control part

C1:1st path

C2:2 nd path

C3 Hydrogen peroxide solution supply route

P1:1st junction

P2:2. Th junction

P4 branch part

R1 heating region

S301, S401 step (flow-through step 1)

S103, S203, S303, S403 step (1 st ejection step)

S305, S405 step (2 nd flow Process)

S107, S207, S307, S407, step (No. 2 ejection step)

W is the substrate.

Claims (15)

1. A substrate processing apparatus for processing a substrate by supplying a processing liquid from a nozzle to the substrate, the apparatus comprising:

tank 1, storing sulfuric acid;

a path including a 1 st path for supplying the sulfuric acid from the 1 st tank to the nozzle;

a 1 st valve interposed in the 1 st path;

a 1 st heater for heating the heating region of the 1 st path;

a hydrogen peroxide solution supply path for supplying a hydrogen peroxide solution to the nozzle;

A water passing valve interposed in the hydrogen peroxide solution supply path; and

a control unit configured to control the supply of the sulfuric acid and the hydrogen peroxide solution to the nozzle by controlling the opening and closing of the 1 st valve and the water passing valve; and is also provided with

The control part is

Mixing the sulfuric acid heated by the 1 st heater with the hydrogen peroxide solution, spraying the mixture to the substrate from the nozzle,

sulfuric acid having a lower temperature than the heated sulfuric acid is then mixed with the hydrogen peroxide solution and sprayed from the nozzle onto the substrate.

2. The substrate processing apparatus of claim 1 wherein the path further comprises a 2 nd path that supplies the sulfuric acid from the 1 st tank to the nozzle without via the heating zone,

the substrate processing apparatus further includes a 2 nd valve interposed in the 2 nd path,

the control unit controls the supply of the sulfuric acid and the hydrogen peroxide solution to the nozzle by controlling the opening and closing of the 1 st valve, the 2 nd valve, and the water passing valve,

the sulfuric acid passing through the 2 nd path merges into the hydrogen peroxide solution at a lower temperature than the sulfuric acid passing through the 1 st path,

the control part controls the 1 st valve, the 2 nd valve and the water passing valve in such a way that,

Mixing the sulfuric acid heated by the 1 st heater through the 1 st path with the hydrogen peroxide solution, and then spraying the mixture from the nozzle onto the substrate,

then, the sulfuric acid passing through the 2 nd path is mixed with the hydrogen peroxide solution and then ejected from the nozzle to the substrate.

3. The substrate processing apparatus according to claim 2, further comprising:

a 1 st merging portion disposed between the heating region and the discharge port of the nozzle, and merging the 1 st path with the hydrogen peroxide solution supply path; and

and a 2 nd junction portion disposed between the heating region and the 1 st junction portion, and joining the 1 st path and the 2 nd path.

4. The substrate processing apparatus according to claim 2, wherein the 1 st path and the 2 nd path branch on an upstream side of the flow direction of the sulfuric acid with respect to the heating region and join on a downstream side of the flow direction of the sulfuric acid with respect to the heating region.

5. The substrate processing apparatus according to claim 1, wherein the 1 st heater is set to 1 st output by the control section so that sulfuric acid passing through the 1 st path has a 1 st temperature,

The control unit sets the 1 st heater to a 2 nd output lower than the 1 st output, and causes the sulfuric acid passing through the 1 st path to have a 2 nd temperature lower than the 1 st temperature.

6. The substrate processing apparatus according to claim 5, wherein the path further comprises a circulation pipe branched from the 1 st path and for returning the sulfuric acid to the 1 st tank,

the 1 st heater is disposed upstream of a branching portion of the 1 st path and the circulation pipe in a flow direction of the sulfuric acid.

7. The substrate processing apparatus according to claim 5, wherein the path further comprises a circulation pipe branched from the 1 st path and for returning the sulfuric acid to the 1 st tank,

the 1 st heater is disposed downstream of a branching portion of the 1 st path and the circulation pipe in the flow direction of the sulfuric acid.

8. The substrate processing apparatus according to any one of claims 1 to 7, further comprising a 2 nd heater for maintaining sulfuric acid in the 1 st tank at a specified temperature.

9. The substrate processing apparatus according to claim 8, further comprising:

a 2 nd tank disposed downstream of the 1 st tank in the sulfuric acid flow direction; and

And a 3 rd heater for maintaining the sulfuric acid in the 2 nd tank at a temperature higher than the temperature of the sulfuric acid in the 1 st tank.

10. A substrate processing method for processing a substrate by supplying a processing liquid to the substrate, comprising:

a 1 st discharge step of discharging the sulfuric acid supplied from the 1 st tank and heated in the heating region through the 1 st path having the heating region and the hydrogen peroxide solution passing through the hydrogen peroxide solution supply path to the substrate; and

and a 2 nd discharge step of discharging the sulfuric acid, which is supplied from the 1 st tank and has a temperature lower than the heated sulfuric acid, and the hydrogen peroxide solution, which passes through the hydrogen peroxide solution supply path, to the substrate after the 1 st discharge step.

11. The substrate processing method according to claim 10, wherein in the 2 nd discharge step, sulfuric acid passing through a 2 nd path without passing through the heating region and the hydrogen peroxide solution are discharged to the substrate.

12. The substrate processing method according to claim 11, wherein the 1 st path and the 2 nd path branch on an upstream side of the flow direction of sulfuric acid with respect to the heating region and join on a downstream side of the flow direction of sulfuric acid with respect to the heating region.

13. The substrate processing method of claim 10, further comprising:

a 1 st circulation step of heating the sulfuric acid passing through the 1 st path to a sulfuric acid having a 1 st temperature before the 1 st ejection step; and

and a 2 nd circulation step of changing the sulfuric acid passing through the 1 st path to sulfuric acid having a 2 nd temperature lower than the 1 st temperature before the 2 nd ejection step.

14. The substrate processing method according to any one of claims 10 to 13, wherein sulfuric acid in the 1 st tank is maintained at a specified temperature.

15. The substrate processing method according to claim 14, wherein sulfuric acid in a 2 nd tank disposed downstream of the 1 st tank in a flow direction of the sulfuric acid is maintained at a temperature higher than a temperature of the sulfuric acid in the 1 st tank.