Substrate processing apparatus and substrate processing method

Abstract

To provide a substrate processing apparatus and a substrate processing method, capable of improving a processing efficiency of a substrate.SOLUTION: A substrate processing apparatus 100 comprises a first liquid supply system 10, a second liquid supply system 20, and a nozzle 30. The first liquid supply system 10 includes a first pipe 12 connected to the nozzle 30, and supplies a first liquid to the nozzle 30 via the first pipe 12. The second liquid supply system 20 includes a plurality of second sub-pipes 23, 24, and 25 that are respectively connected to a plurality of parts that are different from each other of a liquid channel formed by the nozzle 30 and the first pipe 12. A period of a removing processing for removing an unnecessary film formed on a substrate W includes a first period and a second period. In the first period, a second liquid is supplied to the liquid channel from the second sub-pipes 23 and 24 that are partially connected to other than the most downstream of the liquid channel. In the second period, the second liquid is supplied to the liquid channel from the second sub-pipe 25 connected to the part of the most downstream of the liquid channel.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a substrate processing apparatus and a substrate processing method for removing an unnecessary film formed on one surface of a substrate.

Background Art

[0002] A substrate processing apparatus is used to perform various processes on substrates such as semiconductor substrates, substrates for flat panel displays (FPDs) such as liquid crystal display devices or organic EL (Electro Luminescence) display devices, substrates for optical disks, substrates for magnetic disks, substrates for magneto-optical disks, substrates for photomasks, ceramic substrates, or substrates for solar cells.

[0003] In the substrate processing apparatus described in Patent Document 1, an unnecessary resist film formed on one surface of a substrate (wafer) is removed using SPM (Sulfuric acid hydrogen peroxide mixture). More specifically, a substrate having a resist film is held in a horizontal posture by a spin chuck and rotated around a vertical axis. In this state, an SPM nozzle is disposed at a position above the rotating substrate, and SPM is supplied from the SPM nozzle toward the center of rotation of the substrate. SPM is a mixed solution of sulfuric acid (H2SO4) and hydrogen peroxide solution (H2O2) and has a strong oxidizing power. Thereby, the resist film on the substrate is peeled off from one surface of the substrate by the oxidizing power of SPM and removed.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] When SPM is supplied onto a substrate having a resist film, plural portions of the resist film are not necessarily removed uniformly. If the supply time of SPM to the substrate is increased to surely remove portions of the resist film that are difficult to remove from one surface of the substrate, the processing efficiency of the substrate decreases.

[0006] An object of the present invention is to provide a substrate processing apparatus and a substrate processing method that enable improvement of the processing efficiency of a substrate.

Means for Solving the Problems

[0007] A substrate processing apparatus according to an aspect of the present invention is a substrate processing apparatus that performs a removal process for removing an unnecessary film formed on one surface of a substrate with a processing liquid containing a peracid. The peracid is generated by mixing one of sulfuric acid and hydrogen peroxide solution as a first liquid and the other of sulfuric acid and hydrogen peroxide solution as a second liquid. The substrate processing apparatus includes a nozzle that discharges the processing liquid onto the one surface of the substrate, and a first pipe connected to the nozzle. The substrate processing apparatus includes a first liquid supply system that supplies the first liquid to the nozzle through the first pipe, and a plurality of second pipes respectively connected to three or more different portions of a liquid flow path formed by the nozzle and the first pipe. The substrate processing apparatus includes a second liquid supply system that supplies the second liquid to the liquid flow path through any one of the plurality of second pipes, and a control unit that controls the second liquid supply system. The plurality of second pipes include a downstream pipe connected to the most downstream portion of the plurality of portions of the liquid flow path, and a plurality of upstream pipes excluding the downstream pipe. The control unit performs a first control of not flowing the second liquid through the downstream pipe and flowing the second liquid through at least two of the plurality of upstream pipes during a first period during the removal process for one substrate, and performs a second control of flowing the second liquid through the downstream pipe and not flowing the second liquid through the plurality of upstream pipes during a second period during the removal process for the one substrate.

[0008] A substrate processing method according to another aspect of the present invention is a substrate processing method using a substrate processing apparatus that performs a removal process of removing an unnecessary film formed on one surface of a substrate with a processing liquid containing caro acid, wherein the caro acid is generated by mixing one of sulfuric acid and hydrogen peroxide water as a first liquid and the other of sulfuric acid and hydrogen peroxide water as a second liquid, the substrate processing apparatus includes a nozzle that discharges the processing liquid onto the one surface of the substrate and a first pipe connected to the nozzle, and includes a first liquid supply system that supplies the first liquid to the nozzle through the first pipe, and a plurality of second pipes respectively connected to three or more different portions of a liquid flow path formed by the nozzle and the first pipe, and includes a second liquid supply system that supplies the second liquid to the liquid flow path through any one of the plurality of second pipes, the plurality of second pipes include a downstream pipe connected to the most downstream portion of the plurality of portions of the liquid flow path and a plurality of upstream pipes excluding the downstream pipe, and the substrate processing method includes a first control step of, during a first period of the removal process for one substrate, not flowing the second liquid through the downstream pipe and flowing the second liquid through at least two of the plurality of upstream pipes, and a second control step of, during a second period of the removal process for the one substrate, flowing the second liquid through the downstream pipe and not flowing the second liquid through the plurality of upstream pipes.

Effect of the Invention

[0009] According to the present invention, it becomes possible to improve the processing efficiency of a substrate.

Brief Description of the Drawings

[0010]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Figure 6

Figure 7

Embodiments for Carrying Out the Invention

[0011] Hereinafter, a substrate processing apparatus and a substrate processing method according to an embodiment of the present invention will be described with reference to the drawings. In the following description, the substrate refers to a substrate for FPD (Flat Panel Display) used in a liquid crystal display device, an organic EL (Electro Luminescence) display device, etc., a semiconductor substrate, a substrate for an optical disk, a substrate for a magnetic disk, a substrate for a magneto-optical disk, a substrate for a photomask, a ceramic substrate, a substrate for a solar cell, or the like.

[0012] Further, the substrate processing apparatus described below is a single-wafer type substrate processing apparatus and is used for a removal process of removing an unnecessary film (in this example, a resist film) formed on one surface (main surface) of the substrate. In the removal process according to the present embodiment, a substrate having an unnecessary film formed on one surface is rotated in a horizontal posture. SPM (Sulfuric acid hydrogen peroxide mixture) is supplied as a processing liquid to one surface of the substrate. SPM is a mixed liquid of sulfuric acid (H2SO4) and hydrogen peroxide water (H2O2) and contains peroxymonosulfuric acid (H2SO5). Peroxymonosulfuric acid is generated by a chemical reaction between sulfuric acid and hydrogen peroxide water, has a strong oxidizing power, and reacts with the unnecessary film to dissolve the film. Thereby, the unnecessary film is peeled off and removed from one surface of the substrate.

[0013] <1>Configuration of the Substrate Processing Apparatus FIG. 1 is a schematic diagram showing the configuration of a substrate processing apparatus according to an embodiment of the present invention. As shown in FIG. 1, the substrate processing apparatus 100 mainly includes a spin chuck 1, a cup 2, a cup lifting device 2D, a processing liquid supply device 3, a nozzle support portion 4, a nozzle moving device 5, a control unit 6, and an operation unit 9.

[0014] The substrate processing apparatus 100 is provided at least partially in a chamber (not shown). The spin chuck 1 has a spin motor 1a, a spin base 1b, and chuck pins 1c. The spin motor 1a is provided at the bottom of the chamber such that the rotation axis protrudes upward. The spin base 1b has a disk shape and is attached in a horizontal posture to the upper end of the rotation axis of the spin motor 1a. A plurality of chuck pins 1c are provided on the upper surface of the spin base 1b and hold the peripheral portion of the substrate W. The spin motor 1a operates with the plurality of chuck pins 1c holding the substrate W. Thereby, the substrate W rotates around the vertical axis.

[0015] As described above, in this example, a mechanical spin chuck 1 that holds the peripheral portion of the substrate W is used. However, the present invention is not limited to this, and instead of the mechanical spin chuck, a suction type spin chuck that sucks and holds the lower surface of the substrate W may be used.

[0016] The cup 2 is provided so as to surround the spin chuck 1. The cup 2 is supported by the cup lifting device 2D so as to be movable up and down. The cup lifting device 2D includes an air cylinder or the like and moves the cup 2 between two predetermined height positions (an upper position and a lower position described later).

[0017] The processing liquid supply device 3 mainly consists of a first liquid supply system 10, a second liquid supply system 20, and a nozzle 30. The first liquid supply system 10 includes a first liquid supply source 11, a first pipe 12, a valve 12a, an adjustment unit 12b, and a stirring unit 12c. The first liquid supply source 11 is a supply source of sulfuric acid and is composed of a liquid delivery device including a factory's power equipment or a liquid storage unit. The upstream end of the first pipe 12 is connected to the first liquid supply source 11. The downstream end of the first pipe 12 is connected to the nozzle 30. The valve 12a, the adjustment unit 12b, and the stirring unit 12c are provided on the first liquid supply source 11 so as to be arranged in this order from the upstream end to the downstream end of the first liquid supply source 11.

[0018] The valve 12a is, for example, a ball valve, which allows the flow of the liquid in the first pipe 12 when it is in the open state and blocks the flow of the liquid in the first pipe 12 when it is in the closed state. The adjustment unit 12b includes a flow regulator such as a motor needle valve or a regulator, and adjusts the flow rate of the liquid flowing through the first pipe 12. In this example, the adjustment unit 12b is a motor needle valve. The stirring unit 12c is, for example, an in-line mixer, and mixes a plurality of types of liquids (in this example, sulfuric acid and hydrogen peroxide solution) flowing through the first pipe 12 by generating a vortex or the like in the first pipe 12.

[0019] In the present embodiment, among the liquid flow paths formed by the first pipe 12 and the nozzle 30, the portion located between the adjustment unit 12b and the stirring unit 12c is called the first portion MP1. The portion located between the stirring unit 12c and the nozzle 30 is called the second portion MP2, and the portion located at the nozzle 30 is called the third portion MP3.

[0020] The second liquid supply system 20 includes a second liquid supply source 21, a second main pipe 22, a plurality (three in this example) of second sub-pipes 23, 24, 25, a plurality (three in this example) of valves 23a, 24a, 25a, and a plurality (three in this example) of adjustment units 23b, 24b, 25b. The second liquid supply source 21 is a supply source of hydrogen peroxide solution, and is composed of a liquid delivery device including a factory's power equipment or a liquid storage unit, similar to the example of the first liquid supply source 11.

[0021] The upstream end of the second main pipe 22 is connected to the second liquid supply source 21. The second main pipe 22 has a plurality (two in this example) of branch portions arranged from upstream to downstream. The upstream ends of the second sub-pipes 23, 24, 25 are connected to the upstream-side branch portion of the second main pipe 22, the downstream-side branch portion of the second main pipe 22, and the downstream end of the second main pipe 22, respectively. On the other hand, the downstream ends of the second sub-pipes 23, 24, 25 are connected to the first portion MP1, the second portion MP2, and the third portion MP3 of the liquid flow path described above, respectively.

[0022] A valve 23a and an adjustment unit 23b are provided in the second sub-pipe 23 so as to be arranged from upstream to downstream in this order. A valve 24a and an adjustment unit 24b are provided in the second sub-pipe 24 so as to be arranged from upstream to downstream in this order. A valve 25a and an adjustment unit 25b are provided in the second sub-pipe 25 so as to be arranged from upstream to downstream in this order.

[0023] The valves 23a, 24a, 25a have the same configuration as the valve 12a. Also, the adjustment units 23b, 24b, 25b have the same configuration as the adjustment unit 12b. Note that some of the valves among the valves 12a, 23a, 24a, 25a may have a configuration different from that of the other valves. Also, some of the adjustment units among the adjustment units 12b, 23b, 24b, 25b may have a configuration different from that of the other adjustment units.

[0024] In the above-described processing liquid supply device 3, a part of the configuration of the first liquid supply system 10 and a part of the configuration of the second liquid supply system 20 are supported at a position above the spin chuck 1 by, for example, an arm member 7 (FIG. 2) made of a hard resin.

[0025] FIG. 2 is a plan view of a substrate processing apparatus 100 for explaining the functions of the nozzle support portion 4 and the nozzle moving device 5 in FIG. 1. As shown in the upper part of FIG. 2, rails 5r are provided at the bottom of the chamber on the sides of the spin chuck 1 and the cup 2 in a plan view. The rails 5r are provided so as to extend in one direction at positions close to the spin chuck 1 and the cup 2. In the following description, the direction in which the rails 5r extend in a plan view is referred to as the rail direction. Also, in a plan view, a straight line passing through the rotation center of the spin chuck 1 and extending in the rail direction is referred to as a virtual line VL.

[0026] An arm member 7 that supports a part of the processing liquid supply device 3 has, for example, a rod shape and supports the nozzle 30 at its tip portion. The nozzle support portion 4 supports the arm member 7 so that the nozzle 30 is located on the virtual line VL and is provided on the rail 5r so as to be movable in the rail direction. A motor that constitutes a part of the nozzle moving device 5 is attached to the nozzle support portion 4. Thereby, the nozzle support portion 4 moves on the rail 5r when the nozzle moving device 5 operates.

[0027] In the substrate processing apparatus 100, a standby position WP is set at a position on the virtual line VL that is deviated from the spin chuck 1 and the cup 2 in a plan view. Also, a processing position PP is set at a position on the virtual line VL that overlaps the rotation center of the spin chuck 1 in a plan view. When the substrate processing apparatus 100 is in a standby state where no removal processing is performed, the nozzle 30 of the processing liquid supply device 3 is held at the standby position WP in a plan view as shown in the upper part of FIG. 2. On the other hand, when the substrate processing apparatus 100 performs removal processing, the nozzle 30 of the processing liquid supply device 3 is held at the processing position PP in a plan view as shown in the lower part of FIG. 2.

[0028] In this embodiment, when the nozzle 30 of the processing liquid supply device 3 is held at the processing position PP during the removal process, the nozzle 30 is positioned such that the discharge port of the nozzle 30 faces the rotation center of the spin chuck 1. In this embodiment, the center of the substrate W held by the spin chuck 1 is located on the vertical axis passing through the rotation center of the spin chuck 1. Thereby, in this embodiment, when the nozzle 30 is held at the processing position PP, the discharge port of the nozzle 30 faces the center of the substrate W.

[0029] During the removal process, the processing liquid is discharged from the discharge port of the nozzle 30 of the processing liquid supply device 3 toward one surface of the substrate W. The discharged processing liquid collides with one surface of the substrate W (accurately, one surface of the substrate W or the resist film covering one surface of the substrate W), and then spreads radially from the center of the substrate W toward the outer peripheral end by centrifugal force.

[0030] Note that the substrate processing apparatus 100 according to this embodiment includes a rinse nozzle (not shown) and a rinse liquid supply system (not shown) that supplies the rinse liquid to the rinse nozzle. The rinse nozzle discharges the rinse liquid toward one surface of the substrate W on which the processing liquid remains after the resist film is removed by the processing liquid. Thereby, the processing liquid on the substrate W is removed (rinse process). Details of the control unit 6 and the operation unit 9 will be described later.

[0031] <2>Control System of Substrate Processing Apparatus The control system of the substrate processing apparatus 100 will be described together with the configurations of the control unit 6 and the operation unit 9 in FIG. 1. FIG. 3 is a block diagram showing the configuration of the control system of the substrate processing apparatus 100 in FIG. 1. As shown in FIG. 3, the control unit 6 includes a CPU (Central Processing Unit) 61, a RAM (Random Access Memory) 62, a ROM (Read Only Memory) 63, and a storage device 64.

[0032] The RAM 62 is used as the working area of the CPU 61. The system program is stored in the ROM 63. The storage device 64 includes a storage medium such as a hard disk or a semiconductor memory, and stores a film removal program for performing the removal process. Further, the storage device 64 stores the operating conditions of the substrate processing apparatus 100 regarding the removal process. Details of the operating conditions will be described later.

[0033] Note that the film removal program may be provided in a state stored in a recording medium such as a CD-ROM 65 and installed in the ROM 63 or the storage device 64. Alternatively, the film removal program may be distributed from a server outside the substrate processing apparatus 100 via a communication network and installed in the ROM 63 or the storage device 64.

[0034] When the CPU 61 executes the film removal program, the operations of each part of the substrate processing apparatus 100 during the removal process are controlled. Specifically, the control unit 6 rotates the substrate W by controlling the spin motor 1a while the substrate W is placed on the spin base 1b and held by a plurality of chuck pins 1c.

[0035] Also, the control unit 6 controls the cup lifting device 2D so that the cup 2 is held at the lower position when the substrate W is placed on the spin chuck 1, when the substrate W is taken out from the spin chuck 1, and when the removal process is not performed. Here, the lower position is the position of the cup 2 when the upper end of the cup 2 is below the substrate W held by the spin chuck 1.

[0036] Also, the control unit 6 controls the cup lifting device 2D so that the cup 2 is held at the upper position during the removal process. Here, the upper position is the position of the cup 2 when the upper end of the cup 2 is above the substrate W held by the spin chuck 1 and the inner peripheral surface of the cup 2 faces the outer peripheral end of the substrate W in the horizontal plane. In this case, the processing liquid scattered from the substrate W during the removal process is received by the inner peripheral surface of the cup 2. The processing liquid received by the cup 2 is discarded through the drain pipe.

[0037] Further, while the removal process is being performed, the control unit 6 controls the nozzle moving device 5 so that the nozzle 30 of the processing liquid supply device 3 is held at the processing position PP. Further, while the removal process is not being performed, the control unit 6 controls the nozzle moving device 5 so that the nozzle 30 of the processing liquid supply device 3 is held at the standby position WP.

[0038] As described above, the operation conditions of the substrate processing apparatus 100 regarding the removal process are stored in the storage device 64 of the control unit 6. During the removal process, the control unit 6 controls the plurality of valves 12a, 23a, 24a, 25a and the plurality of adjustment units 12b, 23b, 24b, 25b of the processing liquid supply device 3 based on the operation conditions stored in the storage device 64. In this case, in the processing liquid supply device 3, hydrogen peroxide water is supplied from the second liquid supply system 20 to any one of the first portion MP1, the second portion MP2, and the third portion MP3 of the liquid flow path in a state where sulfuric acid flows through the first pipe 12. Thereby, sulfuric acid and hydrogen peroxide water are mixed in the liquid flow path, and a processing liquid (SPM) is generated.

[0039] The operation unit 9 in FIG. 1 includes a keyboard and a pointing device and is configured to be operable by a user. The user can input the above operation conditions by operating the operation unit 9. When there is an input of operation conditions in the operation unit 9, the control unit 6 stores the input operation conditions in the storage device 64.

[0040] <3> Changes in the state when the film on the substrate W is removed As described in the problems to be solved by the invention, in the resist film removal process, even when a processing liquid containing chromic acid is supplied onto one surface of the substrate W, the plurality of portions of the resist film on one surface of the substrate W are not necessarily removed uniformly. The present inventor focused on this point and assumed that the method of generating the processing liquid might contribute to the non-uniformity of the resist film removal. Therefore, the present inventor conducted the following film removal experiment using the processing liquid supply device 3 having the configuration of FIG. 1 above.

[0041] First, the inventor prepared two sample substrates on which a resist film was formed by a common method. In the following description, the two sample substrates are referred to as the first sample substrate and the second sample substrate, respectively. The inventor supplied treatment liquids generated by different methods to the first sample substrate and the second sample substrate, and observed the changes in the resist film on each substrate during the supply of the treatment liquid.

[0042] Specifically, the inventor positioned the nozzle 30 so as to face the center of the substrate W while the first sample substrate was held horizontally and rotated by the spin chuck 1. In addition, the inventor opened the three valves 12a, 23a, and 24a of the treatment liquid supply device 3 shown in FIG. 1 and closed the valve 25a.

[0043] Here, in the treatment liquid supply device 3, it is assumed that each of the adjustment units 12b, 23b, 24b, and 25b is adjusted so that when a liquid flows through the pipe to which the adjustment unit is attached, the flow rate of the liquid becomes a predetermined flow rate.

[0044] In this case, in the treatment liquid supply device 3, sulfuric acid is supplied from the first liquid supply source 11 to the first pipe 12 at a predetermined flow rate. In addition, hydrogen peroxide water is supplied from the second liquid supply source 21 to the first part MP1 in the liquid flow path through the second main pipe 22 and the second sub-pipe 23. As a result, sulfuric acid and hydrogen peroxide water merge in the first part MP1, and the mixed liquid is sent to the stirring unit 12c. In the stirring unit 12c, the liquid flowing inside the stirring unit 12c (in this example, the mixed liquid of sulfuric acid and hydrogen peroxide water) is stirred. Further, hydrogen peroxide water is supplied from the second liquid supply source 21 to the second part MP2 in the liquid flow path through the second main pipe 22 and the second sub-pipe 24. As a result, the mixed liquid and the new hydrogen peroxide water merge in the second part MP2, and their mixed liquid is sent to the nozzle 30 as the treatment liquid.

[0045] The inventor captured an image of one side of the first sample substrate using a camera every 60 seconds starting from the time when the supply of the processing liquid to the first sample substrate began. Also, the inventor confirmed the temporal change of the resist film during the removal process of the first sample substrate based on the image obtained by imaging.

[0046] Figure 4 is a schematic diagram showing the results of the film removal experiment for the first sample substrate. In the upper part of Figure 4, a plan view of the first sample substrate at the time 60 seconds after the start of the supply of the processing liquid is shown. In the middle part of Figure 4, a plan view of the first sample substrate at the time 120 seconds after the start of the supply of the processing liquid is shown. In the lower part of Figure 4, a plan view of the first sample substrate at the time 180 seconds after the start of the supply of the processing liquid is shown.

[0047] Each of the plan views in Figure 4 schematically represents an image of the first sample substrate obtained by imaging the first sample substrate. In each of the upper, middle, and lower plan views of Figure 4, the resist film existing on one side of the first sample substrate is shown as a dot pattern.

[0048] In the following description, the ratio of the area of the portion where the resist film has been removed to the area of the entire one side of the substrate is called the removal rate of the resist film. Also, an inner portion R1 and an outer portion R2 are defined on one side of the substrate. The inner portion R1 has a circular shape and is located at the center of the substrate. The radius of the inner portion R1 is about 2 / 3 of the radius of the substrate. The outer portion R2 has an annular shape including the outer peripheral end of the substrate W and surrounds the inner portion R1.

[0049] As shown in the upper part of Figure 4, at the time 60 seconds after the start of the supply of the processing liquid, the resist film was hardly removed over the entire first sample substrate. The removal rate of the resist film in the first sample substrate at this time was about 4%.

[0050] As shown in the middle part of FIG. 4, at the time point 120 seconds after the start of the supply of the processing liquid, the resist film of the inner portion R1 of the first sample substrate is hardly removed. However, the resist film of the outer portion R2 of the first sample substrate has been removed. The removal rate of the resist film on the first sample substrate at this time was about 58%.

[0051] As shown in the lower part of FIG. 4, at the time point 180 seconds after the start of the supply of the processing liquid, the resist film of the inner portion R1 of the first sample substrate is removed in a wider range compared to the time point 120 seconds after the start. In addition, in the inner portion R1 of the first sample substrate, the portions where the resist film has been removed are relatively uniformly dispersed. The removal rate of the resist film on the first sample substrate at this time was about 76%.

[0052] Next, the inventor positioned the nozzle 30 so as to face the center of the substrate W while the second sample substrate was held horizontally and rotated by the spin chuck 1. In addition, the inventor opened the two valves 12a and 25a of the processing liquid supply device 3 shown in FIG. 1 and closed the valves 23a and 24a.

[0053] Here, in the processing liquid supply device 3, it is assumed that each of the adjustment parts 12b, 23b, 24b, and 25b is adjusted so that when liquid flows through the pipe to which the adjustment part is attached, the flow rate of the liquid becomes a predetermined flow rate.

[0054] In this case, in the processing liquid supply device 3, sulfuric acid is supplied from the first liquid supply source 11 to the first pipe 12 at a predetermined flow rate. In addition, hydrogen peroxide water is supplied from the second liquid supply source 21 to the third part MP3 in the liquid flow path through the second main pipe 22 and the second sub-pipe 25. As a result, sulfuric acid and hydrogen peroxide water merge in the third part MP3 (in this example, inside the nozzle 30), and the mixture of them is discharged from the nozzle 30.

[0055] The inventor captured an image of one side of the second sample substrate using a camera every 60 seconds starting from the time when the supply of the processing liquid to the second sample substrate began. Further, the inventor observed the temporal change of the resist film during the removal process of the second sample substrate based on the image obtained by the imaging.

[0056] FIG. 5 is a schematic diagram showing the results of the film removal experiment for the second sample substrate. In the upper part of FIG. 5, a plan view of the second sample substrate at the time 60 seconds after the start of the supply of the processing liquid is shown. In the middle part of FIG. 5, a plan view of the second sample substrate at the time 120 seconds after the start of the supply of the processing liquid is shown. In the lower part of FIG. 5, a plan view of the second sample substrate at the time 180 seconds after the start of the supply of the processing liquid is shown.

[0057] Each plan view in FIG. 5 schematically represents an image of the second sample substrate obtained by imaging the second sample substrate, similar to each plan view in FIG. 4. In each of the upper, middle, and lower plan views in FIG. 5, the resist film existing on one surface of the second sample substrate is shown by a dot pattern.

[0058] As shown in the upper part of FIG. 5, at the time 60 seconds after the start of the supply of the processing liquid, the resist film was hardly removed over the entire second sample substrate. The removal rate of the resist film in the second sample substrate at this time was about 4%.

[0059] As shown in the middle part of FIG. 5, at the time 120 seconds after the start of the supply of the processing liquid, the resist film was sparsely removed over the entire second sample substrate. The removal rate of the resist film in the second sample substrate at this time was about 19%.

[0060] As shown in the lower part of FIG. 5, at the time 180 seconds after the start of the supply of the processing liquid, most of the resist film in the inner part R1 of the second sample substrate was removed. However, a relatively large amount of the resist film in the outer part R2 of the second sample substrate remained. The removal rate of the resist film in the second sample substrate at this time was about 75%.

[0061] As described above, on the first sample substrate, a removal process was performed using a processing solution generated by supplying hydrogen peroxide water to two portions (the first portion MP1 and the second portion MP2) on the upstream side of the nozzle 30 in the liquid flow path. As a result, on the first sample substrate, it was confirmed that the resist film tended to be sequentially removed from the outer portion R2 toward the inner portion R1.

[0062] On the other hand, on the second sample substrate, a removal process was performed using a processing solution generated by supplying hydrogen peroxide water only to the portion of the nozzle 30 (the third portion MP3) in the liquid flow path. As a result, on the second sample substrate, it was confirmed that the resist film tended to be sequentially removed from the inner portion R1 toward the outer portion R2.

[0063] As a result of these, the inventor obtained the finding that the method for generating the processing solution contributes to the non-uniformity of the removal of the resist film. Based on this finding, the inventor considered that the resist film can be efficiently removed from the entire surface of one substrate W by switching the method for generating the processing solution among a plurality of methods during the removal process of one substrate W. More specifically, the inventor focused on the non-uniformity of the removal of the resist film that occurs concentrically from the center (central portion) to the periphery (peripheral portion) of the substrate W caused by the method for generating the processing solution. Then, the inventor considered that the resist film can be efficiently removed by switching the portions (MP1, MP2, MP3) where sulfuric acid and hydrogen peroxide water merge during the removal process of the substrate W.

[0064] <4>An example of the operating conditions stored in the storage device 64 As described above, in order to switch the method for generating the processing solution among a plurality of methods during the removal process of one substrate W, it is necessary to set the operating conditions of the substrate processing apparatus 100 for each method for generating the processing solution.

[0065] FIG. 6 is a diagram showing an example of operation conditions stored in the storage device 64 of FIG. 3. In this example, a substrate W of the same type as the first sample substrate and the second sample substrate of FIGS. 4 and 5 is used as the substrate W to be subjected to the removal process. Also, during the removal process of one substrate W, it is assumed that the method for generating the processing liquid is switched between two methods. Specifically, during the first period of the period in which the removal process is performed on one substrate W, the processing liquid is generated by one generation method, and during the second period after the first period, the processing liquid is generated by the other generation method. In this case, operation conditions corresponding to the first period and the second period are set respectively.

[0066] In the upper part of FIG. 6, two operation conditions set so as to correspond to the first period and the second period during the removal process are shown using a table. Also, in the lower part of FIG. 6, a configuration diagram of the processing liquid supply device 3 is shown to facilitate understanding of the table. As shown in the lower part of FIG. 6, in the following description, when distinguishing the plurality of second sub-pipes 23, 24, 25 of the processing liquid supply device 3, the second sub-pipe 23 is referred to as "pipe A", the second sub-pipe 24 is referred to as "pipe B", and the second sub-pipe 25 is referred to as "pipe C".

[0067] In the example in the upper part of FIG. 6, the opening and closing states of the valves 12a, 23a, 24a, 25a of the first pipe 12, pipe A, pipe B, and pipe C are set to "open", "open", "open", and "closed" during the first period. When the processing liquid supply device 3 is controlled according to this operation condition, hydrogen peroxide water is supplied to the sulfuric acid or the mixed liquid flowing through the first pipe 12 in the first part MP1 and the second part MP2 of the liquid flow path. Thereby, during the first period, on the substrate W, for example, the resist film is sequentially removed from the outer peripheral portion of the substrate W toward the central portion of the substrate W. That is, the resist film of the outer portion R2 of the substrate W is preferentially removed (see FIG. 4).

[0068] In the example in the upper part of FIG. 6, the opening and closing states of the valves 12a, 23a, 24a, and 25a of the first pipe 12, pipe A, pipe B, and pipe C are set to "open", "closed", "closed", and "open" during the second period. When the processing liquid supply device 3 is controlled according to this operating condition, hydrogen peroxide water is supplied to the sulfuric acid flowing through the first pipe 12 in the third part MP3 of the liquid flow path. Thereby, during the second period, on the substrate W, for example, the resist film is sequentially removed from the central part of the substrate W toward the outer peripheral part of the substrate W. That is, the resist film on the inner part R1 of the substrate W is preferentially removed (see FIG. 5).

[0069] According to the above operating conditions, the portion of the resist film preferentially removed is changed between the first period and the second period. Therefore, by appropriately determining the first period and the second period, the time for removing the resist film from the entire surface of one side of the substrate W can be shortened. The first period and the second period considered appropriate for shortening the removal process can be obtained, for example, by experiments or simulations. Also, the relationship between the position on the substrate W where the resist film is preferentially removed and the method of selecting the portions (MP1, MP2, MP3) where sulfuric acid and hydrogen peroxide water merge is associated by prior experiments. In this embodiment, at each concentric position of the substrate W, a method of selecting the portions (MP1, MP2, MP3) where sulfuric acid and hydrogen peroxide water merge so that the resist film is preferentially removed is required.

[0070] <5> Film removal process by the control unit 6 FIG. 7 is a flowchart showing an example of the film removal process by the control unit 6 in FIG. 1. The film removal process described below is performed by the CPU 61 of the control unit 6 executing a film removal program stored in the storage device 64 on the RAM 62.

[0071] The film removal process by the control unit 6 is started, for example, in response to an untreated substrate W (a substrate W with a resist film formed on the entire surface of one side) being carried into the chamber of the substrate processing apparatus 100 and placed on the spin chuck 1. In the initial state, it is assumed that the cup 2 is in the lower position and the plurality of nozzles 30 are in the standby position WP. Also, it is assumed that all of the plurality of valves 12a, 23a, 24a, 25a of the processing liquid supply device 3 are maintained in the closed state. Further, it is assumed that the storage device 64 of the control unit 6 stores two operating conditions of the processing liquid supply device 3 corresponding to the first period and the second period during the removal process, respectively.

[0072] When the film removal process is started, the CPU 61 controls the cup lifting device 2D to move the cup 2 from the lower position to the upper position (step S11). Also, the CPU 61 controls the spin motor 1a to rotate the substrate W held by the plurality of chuck pins 1c on the spin base 1b (step S12). Further, the CPU 61 controls the nozzle moving device 5 to move the nozzle 30 of the processing liquid supply device 3 from the standby position WP to the processing position PP (step S13).

[0073] Subsequently, the CPU 61 reads the operating conditions corresponding to the first period and the second period stored in the storage device 64 (step S14). Next, during the predetermined first period, the CPU 61 controls the plurality of valves 12a, 23a, 24a, 25a and the plurality of adjustment units 12b, 23b, 24b, 25b of the processing liquid supply device 3 based on the operating conditions corresponding to the first period (step S15). Thereby, a part of the resist film on one surface of the substrate W is preferentially removed compared to the other part of the resist film on one surface of the substrate W.

[0074] When the first period ends, the CPU 61 controls the plurality of valves 12a, 23a, 24a, 25a and the plurality of adjustment units 12b, 23b, 24b, 25b of the processing liquid supply device 3 based on the operating conditions corresponding to the second period (step S16). Thereby, the other part of the resist film on one surface of the substrate W is preferentially removed compared to the part of the resist film on one surface of the substrate W.

[0075] When the second period ends, the CPU 61 stops the supply of the processing liquid by closing the plurality of valves 12a, 23a, 24a, 25a of the processing liquid supply device 3 (step S17).

[0076] Next, the CPU 61 moves the nozzle 30 of the processing liquid supply device 3 from the processing position PP to the standby position WP by controlling the nozzle moving device 5 (step S18). Further, the CPU 61 performs a rinsing process and a drying process on the substrate W from which the resist film has been removed by controlling a rinsing liquid supply system (not shown) and controlling the spin motor 1a (step S19). The drying process in step S19 is a so-called spin drying process in which the substrate W after the rinsing process is rotated at a high speed to dry the substrate W.

[0077] After the drying process in step S19 ends, the CPU 61 stops the rotation of the substrate W by controlling the spin motor 1a (step S20). Further, the CPU 61 moves the cup 2 from the upper position to the lower position by controlling the cup lifting device 2D (step S21), and ends a series of processes.

[0078] <6>Effect (a) In the substrate processing apparatus 100 described above, during the first period of the removal process for one substrate W, sulfuric acid and hydrogen peroxide solution are mixed in the first part MP1 and the second part MP2 of the liquid flow path. On the other hand, sulfuric acid and hydrogen peroxide solution are not mixed in the third part MP3 of the liquid flow path. The first part MP1 and the second part MP2 are located at positions greatly separated from the downstream end of the liquid flow path (the discharge port of the nozzle 30). The processing liquid obtained by the mixing is supplied to one substrate W. At this time, the processing liquid supplied to one substrate W is referred to as the first processing liquid.

[0079] Also, during the second period of the removal process for one substrate W, sulfuric acid and hydrogen peroxide solution are mixed in the third part MP3 of the liquid flow path. On the other hand, sulfuric acid and hydrogen peroxide solution are not mixed in the first part MP1 and the second part MP2 of the liquid flow path. The third part MP3 is located at a position close to the downstream end of the liquid flow path (the discharge port of the nozzle 30). The treatment liquid obtained by the mixing is supplied to one substrate W. At this time, the treatment liquid supplied to one substrate W is called the second treatment liquid.

[0080] When the first treatment liquid is supplied to one surface of one substrate W, among a plurality of parts of one substrate W, the resist film is easily removed in the first part, and the resist film is difficult to be removed in other parts. Also, when the second treatment liquid is supplied to one surface of one substrate W, among a plurality of parts of one substrate W, the resist film is easily removed in a second part different from the first part, and the resist film is difficult to be removed in other parts. Therefore, by appropriately setting the first period and the second period, the time required to remove the resist film from the entire one surface of one substrate W can be shortened. As a result, the processing efficiency of the substrate W is improved.

[0081] (b) The first pipe 12 of the treatment liquid supply device 3 is provided with a stirring part 12c. During the first period of the removal process, hydrogen peroxide solution is supplied from two second sub-pipes 23, 24 to two parts (the first part MP1 and the second part MP2) of the liquid flow path sandwiching the stirring part 12c.

[0082] In this case, during the first period, sulfuric acid and hydrogen peroxide solution merge upstream of the stirring part 12c and flow into the stirring part 12c. In the stirring part 12c, the chemical reaction between sulfuric acid and hydrogen peroxide solution is promoted by stirring the liquid passing through the inside of the stirring part 12c, and a certain amount of peracetic acid is generated.

[0083] Thereafter, hydrogen peroxide solution further merges into the mixed liquid that has passed through the stirring part 12c. In this case, a further chemical reaction occurs between the newly added hydrogen peroxide solution and the sulfuric acid in the mixed liquid. Thereby, it becomes possible to supply a treatment liquid having a high peracetic acid concentration to one surface of the substrate W.

[0084] <7>Other embodiments (a) In the substrate processing apparatus 100 according to the above embodiment, in the removal process, a first period and a second period are set to switch the method of generating the processing liquid, but the present invention is not limited thereto.

[0085] In one removal process for one substrate W, the processing liquid may be generated by three or more methods. For example, in addition to the first period corresponding to the first generation method of the processing liquid and the second period corresponding to the second generation method of the processing liquid, a third period corresponding to the third generation method of the processing liquid may be set. Thus, when the first period, the second period, and the third period are set, the storage device 64 stores the operation conditions corresponding to the first period, the second period, and the third period, respectively.

[0086] Alternatively, in addition to the first, second, and third periods corresponding to the first, second, and third generation methods of the processing liquid, a fourth period corresponding to the fourth generation method of the processing liquid may be set. Thus, when the first, second, third, and fourth periods are set, the storage device 64 stores the operation conditions corresponding to the first, second, third, and fourth periods, respectively.

[0087] (b) In the substrate processing apparatus 100 according to the above embodiment, in the removal process, the operation of the processing liquid supply device 3 is controlled such that the first period and the second period are arranged in chronological order in this order, but the present invention is not limited thereto.

[0088] In the substrate processing apparatus 100, during the removal process, the operation of the processing liquid supply device 3 may be controlled such that the second period and the first period are arranged in this order in time series. In this case, according to the operating conditions of FIG. 6, from the start point of the removal process, during the second period, the opening and closing states of the valves 12a, 23a, 24a, and 25a of the first pipe 12, pipe A, pipe B, and pipe C are "open", "open", "closed", and "closed". Thereafter, during the first period, the opening and closing states of the valves 12a, 23a, 24a, and 25a of the first pipe 12, pipe A, pipe B, and pipe C are "open", "open", "open", and "closed".

[0089] (c) In the processing liquid supply device 3 of the substrate processing apparatus 100 according to the above embodiment, the first liquid supply source 11 is a supply source of sulfuric acid, and the second liquid supply source 21 is a supply source of hydrogen peroxide water. However, the present invention is not limited thereto. In the above processing liquid supply device 3, the first liquid supply source 11 may be a supply source of hydrogen peroxide water, and the second liquid supply source 21 may be a supply source of sulfuric acid.

[0090] (d) The first pipe 12 of the processing liquid supply device 3 according to the above embodiment is provided with a stirring unit 12c, but the stirring unit 12c may not be provided.

[0091] (e) The second liquid supply system 20 of the processing liquid supply device 3 according to the above embodiment has three second sub-pipes 23, 24, and 25 as pipes for mixing hydrogen peroxide water with sulfuric acid. However, the present invention is not limited thereto. The second liquid supply system 20 may have only two second sub-pipes, or may have four or more second sub-pipes. When the second liquid supply system 20 has four or more second sub-pipes, mixing of sulfuric acid and hydrogen peroxide water can be performed at four or more portions of the liquid flow path formed by the first pipe 12 and the nozzle 30. Thereby, the degree of freedom of the operating conditions that can be set for generating the processing liquid is improved.

[0092] (f) In the above-described embodiment, an example in which sulfuric acid and hydrogen peroxide water are mixed in the first part MP1 and the second part MP2 of the liquid flow path during the removal process has been described, but the present invention is not limited thereto. During the first period of the removal process, sulfuric acid and hydrogen peroxide water may be mixed in all parts of the first part MP1, the second part MP2, and the third part MP3 of the liquid flow path. Alternatively, during the first period of the removal process, sulfuric acid and hydrogen peroxide water may be mixed in the first part MP1 and the third part MP3 of the liquid flow path, or sulfuric acid and hydrogen peroxide water may be mixed in the second part MP2 and the third part MP3 of the liquid flow path.

[0093] (g) In the film removal process according to the above-described embodiment, after the treatment liquid containing chromic acid is supplied to the substrate W, the rinsing process and the drying process are performed in this order, but the present invention is not limited thereto. The substrate processing apparatus 100 may include a supply apparatus (SC1 supply apparatus) that supplies a mixed liquid (SC1) of ammonia water and hydrogen peroxide water to the substrate W held by the spin chuck 1 as another treatment liquid. In this case, between the above-described rinsing process and drying process, supply and stop of SC1 to the substrate W by the SC1 supply apparatus and an additional rinsing process for washing away the SC1 remaining on the substrate W may be performed.

[0094] <8> Correspondence between each part of the embodiment and each component of the claims Hereinafter, an example of the correspondence between each component of the claims and each component of the embodiment will be described. As each component of the claims, various other elements having the configuration or function described in the claims can also be used.

[0095] In the above-described embodiment, the resist film is an example of an unnecessary film, the substrate processing apparatus 100 is an example of a substrate processing apparatus, the nozzle 30 is an example of a nozzle, the first pipe 12 is an example of a first pipe, the first liquid supply system 10 is an example of a first liquid supply system, and the first part MP1, the second part MP2, and the third part MP3 of the liquid flow path are examples of three or more different parts of the liquid flow path.

[0096] Further, the second sub-pipes 23, 24, and 25 of the second liquid supply system 20 are examples of a plurality of second pipes, the second liquid supply system 20 is an example of a second liquid supply system, the second liquid supply system 20 is an example of a second liquid supply system, and the control unit 6 is an example of a control unit.

[0097] Also, the second sub-pipe 25 is an example of a downstream pipe, the second sub-pipes 23 and 24 are examples of a plurality of upstream pipes, the stirring unit 12c is an example of a stirring unit, the spin chuck 1 is an example of a rotation holding unit, the nozzle support unit 4 is an example of a nozzle support unit, the valves 23a, 24a, and 25a are examples of a plurality of on-off valves, the control of the processing liquid supply device 3 under the operating conditions corresponding to the first period is an example of a first control, and the control of the processing liquid supply device 3 under the operating conditions corresponding to the second period is an example of a second control.

[0098] <9>Summary of Embodiment (Item 1) The substrate processing apparatus according to Item 1 is a substrate processing apparatus that performs a removal process for removing an unnecessary film formed on one surface of a substrate with a processing liquid containing caroic acid, wherein the caroic acid is generated by mixing one of sulfuric acid and hydrogen peroxide solution as a first liquid and the other of sulfuric acid and hydrogen peroxide solution as a second liquid, the substrate processing apparatus includes a nozzle that discharges the processing liquid onto the one surface of the substrate, a first liquid supply system including a first pipe connected to the nozzle, and supplying the first liquid to the nozzle through the first pipe, a second liquid supply system including three or more second pipes respectively connected to three or more different portions among the liquid flow paths formed by the nozzle and the first pipe, and supplying the second liquid to the liquid flow path through any one of the plurality of second pipes, and a control unit that controls the second liquid supply system, wherein the plurality of second pipes include a downstream pipe connected to the most downstream portion among the plurality of portions of the liquid flow path and a plurality of upstream pipes excluding the downstream pipe. During a first period of the removal process for one substrate, the control unit performs first control to cause the second liquid not to flow through the downstream pipe and to cause the second liquid to flow through at least two of the plurality of upstream pipes. During a second period of the removal process for the one substrate, the control unit performs second control to cause the second liquid to flow through the downstream pipe and not to cause the second liquid to flow through the plurality of upstream pipes.

[0099] In the substrate processing apparatus, during a first period of the removal process for one substrate, the first liquid flowing through the first pipe and the second liquid flowing through at least two upstream pipes are mixed at a plurality of positions away from the discharge port of the nozzle and supplied to the one substrate. The processing liquid supplied to the substrate at this time is referred to as the first processing liquid.

[0100] Also, during a second period of the removal process for one substrate, the first liquid flowing through the first pipe and the second liquid flowing through the downstream pipe are mixed at a position close to the discharge port of the nozzle and supplied to the one substrate. The processing liquid supplied to the substrate at this time is referred to as the second processing liquid.

[0101] When the first processing liquid is supplied to one surface of the substrate, among the plurality of portions of the substrate, the film is easily removed at the first portion, and the film is difficult to be removed at other portions. Also, when the second processing liquid is supplied to one surface of the substrate, among the plurality of portions of the substrate, the film is easily removed at a second portion different from the first portion, and the film is difficult to be removed at other portions. Therefore, by appropriately setting the first period and the second period, the time required to remove the film from the entire one surface of the substrate can be shortened. As a result, the processing efficiency of the substrate is improved.

[0102] (Item 2) In the substrate processing apparatus according to Item 1, the substrate processing apparatus further includes a stirring unit provided in the first pipe, and in the first control, the control unit may cause the second liquid to flow through two upstream pipes connected to two portions of the liquid flow path sandwiching the stirring unit.

[0103] In this case, during the first period, the first liquid and the second liquid merge upstream of the stirring unit and flow into the stirring unit. By stirring the first liquid and the second liquid, the chemical reaction between the first liquid and the second liquid is promoted, and a certain amount of calor acid is generated.

[0104] Thereafter, the second liquid further merges into the mixed liquid that has passed through the stirring unit. In this case, a further chemical reaction occurs between the newly added second liquid and the first liquid in the mixed liquid. Thereby, it becomes possible to supply a treatment liquid having a high calor acid concentration to one surface of the substrate.

[0105] (Item 3) In the substrate processing apparatus according to Item 1 or Item 2, the substrate processing apparatus a rotation holding unit that rotates while holding the one substrate during the removal process of the one substrate; During the removal process of the one substrate, a nozzle support unit that supports the nozzle at a position above the one substrate may be further provided so that the discharge port of the nozzle faces the rotation center of the one substrate.

[0106] In this case, during the removal process of one substrate, the treatment liquid is supplied to the rotation center of one surface of the substrate. The treatment liquid supplied to the rotation center of the substrate spreads toward the outer peripheral end of the substrate by centrifugal force. Thereby, the treatment liquid is supplied to the entire one surface of the substrate.

[0107] (Item 4) In the substrate processing apparatus according to any one of Items 1 to 3, the second liquid supply system further includes a plurality of on-off valves provided in the plurality of second pipes respectively, The control unit may control the flow state of the liquid in the plurality of second pipes by controlling the opening and closing states of the plurality of on-off valves.

[0108] In this case, the state of the treatment liquid supplied to the substrate can be adjusted with a simple configuration.

[0109] (Item 5) The substrate processing method according to Item 5 is A substrate processing method using a substrate processing apparatus for performing a removal process of removing an unnecessary film formed on one surface of a substrate with a processing liquid containing a caro acid, wherein the caro acid is generated by mixing one of sulfuric acid and hydrogen peroxide solution as a first liquid and the other of sulfuric acid and hydrogen peroxide solution as a second liquid, the substrate processing apparatus includes, a nozzle for discharging the processing liquid onto the one surface of the substrate, a first liquid supply system including a first pipe connected to the nozzle and supplying the first liquid to the nozzle through the first pipe, a second liquid supply system including three or more second pipes respectively connected to three or more different portions of a liquid flow path formed by the nozzle and the first pipe, and supplying the second liquid to the liquid flow path through any one of the plurality of second pipes, the plurality of second pipes include a downstream pipe connected to the most downstream portion of the plurality of portions of the liquid flow path and a plurality of upstream pipes excluding the downstream pipe, the substrate processing method includes, performing first control of not flowing the second liquid through the downstream pipe and flowing the second liquid through at least two of the plurality of upstream pipes during a first period of the removal process for one substrate, performing second control of flowing the second liquid through the downstream pipe and not flowing the second liquid through the plurality of upstream pipes during a second period of the removal process for the one substrate. A substrate processing method.

[0110] In the substrate processing method, during a first period of the removal process for one substrate, the first liquid flowing through the first pipe and the second liquid flowing through at least two upstream pipes are mixed at a plurality of positions away from the discharge port of the nozzle and supplied to the one substrate. At this time, the processing liquid supplied to the substrate is referred to as a first processing liquid.

[0111] Also, during a second period in the removal process for one substrate, the first liquid flowing through the first pipe and the second liquid flowing through the downstream pipe are mixed at a position close to the discharge port of the nozzle and supplied to the one substrate. The processing liquid supplied to the substrate at this time is referred to as the first processing liquid.

[0112] When the first processing liquid is supplied to one surface of the substrate, among a plurality of portions of the substrate, the film is easily removed at the first portion, and the film is difficult to remove at other portions. Also, when the second processing liquid is supplied to one surface of the substrate, among a plurality of portions of the substrate, the film is easily removed at a second portion different from the first portion, and the film is difficult to remove at other portions. Therefore, by appropriately setting the first period and the second period, the time required to remove the film from the entire one surface of the substrate can be shortened. As a result, the processing efficiency of the substrate is improved.

[0113] (Item 6) In the substrate processing method according to Item 5, the substrate processing apparatus further includes a stirring unit provided in the first pipe, the step of performing the first control may include flowing the second liquid through two upstream pipes connected to two portions of the liquid flow path sandwiching the stirring unit.

[0114] In this case, during the first period, the first liquid and the second liquid merge upstream of the stirring unit and flow into the stirring unit. By stirring the first liquid and the second liquid, the chemical reaction between the first liquid and the second liquid is promoted, and a certain amount of caloic acid is generated.

[0115] Thereafter, the second liquid further merges into the mixed liquid that has passed through the stirring unit. In this case, a further chemical reaction occurs between the newly added second liquid and the first liquid in the mixed liquid. Thereby, it becomes possible to supply a processing liquid having a high caloic acid concentration to one surface of the substrate.

[0116] (Item 7) In the substrate processing method according to Item 5 or Item 6, the substrate processing method is, During the removal process of the one substrate, rotating the one substrate while holding it using a rotation holding unit; During the removal process of the one substrate, further including supporting the nozzle at a position above the one substrate using a nozzle support unit such that the discharge port of the nozzle faces the rotation center of the one substrate.

[0117] In this case, during the removal process of the one substrate, the processing liquid is supplied to the rotation center of one surface of the substrate. The processing liquid supplied to the rotation center of the substrate spreads toward the outer peripheral end of the substrate due to centrifugal force. Thereby, the processing liquid is supplied to the entire surface of one side of the substrate.

[0118] (Item 8) In the substrate processing method according to any one of Items 5 to 7, The second liquid supply system further includes a plurality of on-off valves respectively provided in the plurality of second pipes, Each of the step of performing the first control and the step of performing the second control may include controlling the flow state of the liquid in the plurality of second pipes by controlling the open / closed states of the plurality of on-off valves.

[0119] In this case, the state of the processing liquid supplied to the substrate can be adjusted with a simple configuration.

[0120] According to the substrate processing apparatus and the substrate processing method according to the above series of embodiments, since the processing efficiency of the substrate is improved, wasteful consumption of the processing liquid is suppressed. Thereby, it is not necessary to prepare a large amount of processing liquid. Therefore, it is possible to contribute to the reduction of environmental pollution of the earth caused by the processing liquid.

Explanation of Reference Numerals

[0121] 1... Spin chuck, 1a... Spin motor, 1b... Spin base, 1c... Chuck pin, 2... Cup, 2D... Cup lifting device, 3... Processing liquid supply device, 4... Nozzle support part, 5... Nozzle moving device, 5r... Rail, 6... Control part, 7... Arm member, 9... Operation part, 10... First liquid supply system, 11... First liquid supply source, 12... First pipe, 12a, 12d, 23a, 24a, 25a... Valve, 12b, 23b, 24b, 25b... Adjustment part, 12c... Stirring part, 20... Second liquid supply system, 21... Second liquid supply source, 22... Second main pipe, 23, 24, 25... Second sub-pipes, 30... Nozzle, 61... CPU, 62... RAM, 63... ROM, 64... Storage device, 65... CD-ROM, 100... Substrate processing device, MP1... First part, MP2... Second part, MP3... Third part, PP... Processing position, R1... Inner part, R2... Outer part, VL... Virtual line, W... Substrate, WP... Standby position

Claims

1. A substrate processing apparatus that performs a removal process for removing an unnecessary film formed on one surface of a substrate with a processing liquid containing a peracid, wherein the peracid is generated by mixing one of sulfuric acid and hydrogen peroxide solution as a first liquid and the other of sulfuric acid and hydrogen peroxide solution as a second liquid, the substrate processing apparatus includes: a nozzle that discharges the processing liquid onto the one surface of the substrate; a first liquid supply system including a first pipe connected to the nozzle, and supplying the first liquid to the nozzle through the first pipe; a second liquid supply system including a plurality of second pipes respectively connected to three or more different portions of a liquid flow path formed by the nozzle and the first pipe, and supplying the second liquid to the liquid flow path through any one of the plurality of second pipes; a control unit that controls the second liquid supply system; the plurality of second pipes include a downstream pipe connected to the most downstream portion of the plurality of portions of the liquid flow path, and a plurality of upstream pipes excluding the downstream pipe; during a first period during the removal process for one substrate, the control unit performs first control of not allowing the second liquid to flow through the downstream pipe and allowing the second liquid to flow through at least two of the plurality of upstream pipes, and during a second period during the removal process for the one substrate, the control unit performs second control of allowing the second liquid to flow through the downstream pipe and not allowing the second liquid to flow through the plurality of upstream pipes. A substrate processing apparatus.

2. further comprising a stirring unit provided in the first pipe, in the first control, the control unit allows the second liquid to flow through two upstream pipes connected to two portions of the liquid flow path sandwiching the stirring unit. The substrate processing apparatus according to claim 1.

3. a rotation holding unit that rotates while holding the one substrate during the removal process of the one substrate; further comprising a nozzle support unit that supports the nozzle at a position above the one substrate such that the discharge port of the nozzle faces the rotation center of the one substrate during the removal process of the one substrate. The substrate processing apparatus according to claim 1 or 2.

4. the second liquid supply system further includes a plurality of on-off valves respectively provided in the plurality of second pipes, The substrate processing apparatus according to claim 1 or 2, wherein the control unit controls the flow state of the liquid in the plurality of second pipes by controlling the open / closed states of the plurality of on-off valves.

5. A substrate processing method using a substrate processing apparatus that performs a removal process for removing an unnecessary film formed on one surface of a substrate with a processing liquid containing caloic acid, wherein the caloic acid is generated by mixing one of sulfuric acid and hydrogen peroxide water as a first liquid and the other of sulfuric acid and hydrogen peroxide water as a second liquid, the substrate processing apparatus includes a nozzle that discharges the processing liquid onto the one surface of the substrate, a first liquid supply system including a first pipe connected to the nozzle, and supplying the first liquid to the nozzle through the first pipe, a second liquid supply system including three or more second pipes respectively connected to three or more different portions of a liquid flow path formed by the nozzle and the first pipe, and supplying the second liquid to the liquid flow path through any one of the plurality of second pipes, the plurality of second pipes include a downstream pipe connected to the most downstream portion of the plurality of portions of the liquid flow path, and a plurality of upstream pipes excluding the downstream pipe, the substrate processing method includes a first control step of, during a first period of the removal process for one substrate, not flowing the second liquid through the downstream pipe and flowing the second liquid through at least two of the plurality of upstream pipes; a second control step of, during a second period of the removal process for the one substrate, flowing the second liquid through the downstream pipe and not flowing the second liquid through the plurality of upstream pipes.

6. The substrate processing apparatus further includes a stirring unit provided in the first pipe, the step of performing the first control includes flowing the second liquid through two upstream pipes connected to two portions of the liquid flow path sandwiching the stirring unit.

7. a step of rotating the one substrate while holding the one substrate using a rotation holding unit during the removal process of the one substrate; a step of supporting the nozzle at a position above the one substrate using a nozzle support unit so that a discharge port of the nozzle faces a rotation center of the one substrate during the removal process of the one substrate.

8. The second liquid supply system further includes a plurality of on-off valves respectively provided in the plurality of second pipes, The method for processing a substrate according to claim 5 or 6, wherein each of the step of performing the first control and the step of performing the second control includes controlling a flow state of liquid in the plurality of second pipes by controlling an open / closed state of the plurality of on-off valves.

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