Substrate processing apparatus and substrate processing method

Abstract

This substrate processing apparatus includes a first liquid supply system, a second liquid supply system, and a nozzle. The first liquid supply system includes a first pipe connected to the nozzle and supplies a first liquid to the nozzle through the first pipe. The second liquid supply system includes a plurality of second sub-pipes respectively connected to a plurality of mutually different portions of a liquid flow passage formed by the nozzle and the first pipe. The period of removal processing for removing an unnecessary film formed on a substrate includes a first period and a second period. In the first period, a second liquid is supplied to the liquid flow passage from the second sub-pipe connected to a portion other than the most downstream portion of the liquid flow passage. In the second period, the second liquid is supplied to the liquid flow passage from the second sub-pipe connected to the most downstream portion of the liquid flow passage.

Description

Substrate processing apparatus and substrate processing method

[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.

[0002] Substrate processing apparatuses are used to perform various processes on substrates such as semiconductor substrates, substrates for FPDs (Flat Panel Displays) 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, and 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, the substrate having the resist film is held in a horizontal position by a spin chuck and rotated around a vertical axis. In this state, an SPM nozzle is positioned above the rotating substrate, and SPM is supplied from the SPM nozzle toward the center of rotation of the substrate. The SPM is a sulfuric acid (H ２ SO ４ ) and hydrogen peroxide (H ２ O ２ The resist film on the substrate is peeled off and removed from one surface of the substrate by the oxidizing power of the SPM.

[0004] Japanese Patent Application Laid-Open No. 2008-4819

[0005] When SPM is supplied onto a substrate having a resist film, multiple portions of the resist film are not necessarily removed uniformly. If the supply time of SPM to the substrate is extended in order to reliably 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 an improvement in substrate processing efficiency.

[0007] A substrate processing apparatus according to one aspect of the present invention is a substrate processing apparatus that performs a removal process to remove an unnecessary film formed on one surface of a substrate using a processing liquid containing Caro's acid, wherein the Caro's 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, and the substrate processing apparatus includes a nozzle that discharges the processing liquid onto the one surface of the substrate, a first liquid supply system that includes a first pipe connected to the nozzle and supplies the first liquid to the nozzle through the first pipe, and three or more second pipes that are respectively connected to three or more different portions of a liquid flow path formed by the nozzle and the first pipe. the control unit performs a first control operation to prevent the second liquid from flowing through the downstream pipe and to allow the second liquid to flow through at least two upstream pipes among the plurality of upstream pipes during a first period during the removal process for one substrate, and a second control operation to allow the second liquid to flow through the downstream pipe and to prevent the second liquid from flowing 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 for performing a removal process to remove an unnecessary film formed on one surface of a substrate using a processing liquid containing Caro's acid, wherein the Caro's 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, and the substrate processing apparatus includes a nozzle that ejects the processing liquid onto the one surface of the substrate, a first liquid supply system that includes a first pipe connected to the nozzle and supplies the first liquid to the nozzle through the first pipe, and three or more liquid flow paths formed by the nozzle and the first pipe, each connected to three or more different portions of the liquid flow path. and a second liquid supply system including a plurality of second pipes and supplying the second liquid to the liquid flow path through any of the plurality of second pipes, wherein 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 step of performing a first control during a first period during the removal process for one substrate, in which the second liquid is not circulated through the downstream pipe and the second liquid is circulated through at least two upstream pipes of the plurality of upstream pipes; and a step of performing a second control during a second period during the removal process for the one substrate, in which the second liquid is circulated through the downstream pipe and the second liquid is not circulated through the plurality of upstream pipes.

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

[0010] Fig. 1 is a schematic diagram showing the configuration of a substrate processing apparatus according to an embodiment of the present invention. Fig. 2 is a plan view of the substrate processing apparatus for explaining the functions of the nozzle support unit and nozzle movement device of Fig. 1. Fig. 3 is a block diagram showing the configuration of a control system of the substrate processing apparatus of Fig. 1. Fig. 4 is a schematic diagram showing the results of a film removal experiment on a first sample substrate. Fig. 5 is a schematic diagram showing the results of a film removal experiment on a second sample substrate. Fig. 6 is a diagram showing an example of operating conditions stored in the storage device of Fig. 3. Fig. 7 is a flowchart showing an example of a film removal process performed by the control unit of Fig. 1.

[0011] A substrate processing apparatus and a substrate processing method according to an embodiment of the present invention will be described below with reference to the drawings. In the following description, the term "substrate" refers to a substrate for a flat panel display (FPD) used in a liquid crystal display device or an organic electroluminescence (EL) display device, a semiconductor substrate, an optical disk substrate, a magnetic disk substrate, a magneto-optical disk substrate, a photomask substrate, a ceramic substrate, a solar cell substrate, or the like.

[0012] The substrate processing apparatus described below is a single-wafer type substrate processing apparatus, and is used for a removal process for removing an unnecessary film (resist film in this example) formed on one surface (main surface) of a substrate. In the removal process according to this embodiment, a substrate having an unnecessary film formed on one surface thereof is rotated in a horizontal position. SPM (sulfuric acid hydrogen peroxide mixture) is supplied as a processing liquid onto one surface of the substrate. SPM is a mixture of sulfuric acid (H ２ SO ４ ) and hydrogen peroxide (H ２ O ２ ) and Caro's acid (H ２ SO ５ Caro's acid is produced by a chemical reaction between sulfuric acid and hydrogen peroxide. It has strong oxidizing power and reacts with unwanted films to dissolve them, thereby peeling and removing the unwanted films from one side of the substrate.

[0013] 1 is a schematic diagram showing the configuration of a substrate processing apparatus according to one 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 unit 4, a nozzle moving device 5, a control unit 6, and an operation unit 9.

[0014] The substrate processing apparatus 100 is at least partially installed 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 installed at the bottom of the chamber so that its rotation shaft protrudes upward. The spin base 1b has a disk shape and is attached horizontally to the upper end of the rotation shaft of the spin motor 1a. Multiple chuck pins 1c are installed on the upper surface of the spin base 1b and hold the peripheral edge of the substrate W. The spin motor 1a operates with the multiple chuck pins 1c holding the substrate W. This causes the substrate W to rotate around a vertical axis.

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

[0016] A cup 2 is provided to surround the spin chuck 1. The cup 2 is supported so as to be movable up and down by a cup lifting device 2D. 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, which will be described later).

[0017] The processing liquid supply device 3 is mainly composed 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 an agitation unit 12c. The first liquid supply source 11 is a supply source of sulfuric acid and is composed of a factory utility facility or a liquid delivery device including 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 agitation unit 12c are provided in the first liquid supply source 11 so as to be aligned 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, and when open, allows the liquid to flow through the first pipe 12, and when closed, blocks the liquid from flowing through the first pipe 12. The adjustment unit 12b includes a flow adjuster such as a motorized 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 motorized needle valve. The agitation unit 12c is, for example, an in-line mixer, and generates a vortex or the like in the first pipe 12 to mix the multiple types of liquid (sulfuric acid and hydrogen peroxide solution in this example) flowing through the first pipe 12.

[0019] In this embodiment, of the liquid flow path 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 a first portion MP1. The portion located between the stirring unit 12c and the nozzle 30 is called a second portion MP2, and the portion located at the nozzle 30 is called a third portion MP3.

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

[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 multiple (two in this example) branch sections aligned from upstream to downstream. The upstream ends of the second sub-pipes 23, 24, and 25 are connected to the upstream branch section of the second main pipe 22, the downstream branch section of the second main pipe 22, and the downstream end of the second main pipe 22, respectively. Meanwhile, the downstream ends of the second sub-pipes 23, 24, and 25 are connected to the first portion MP1, the second portion MP2, and the third portion MP3 of the liquid flow path, respectively.

[0022] The second sub-pipe 23 is provided with a valve 23a and an adjustment unit 23b lined up in this order from upstream to downstream. The second sub-pipe 24 is provided with a valve 24a and an adjustment unit 24b lined up in this order from upstream to downstream. The second sub-pipe 25 is provided with a valve 25a and an adjustment unit 25b lined up in this order from upstream to downstream.

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

[0024] In the processing liquid supply device 3, a portion of the components of the first liquid supply system 10 and a portion of the components 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] 2 is a plan view of the substrate processing apparatus 100 for explaining the functions of the nozzle support unit 4 and the nozzle moving device 5 in FIG. 2. As shown in the upper part of FIG. 2, rails 5r are provided on 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. Furthermore, a straight line passing through the center of rotation of the spin chuck 1 and extending in the rail direction in a plan view is referred to as a virtual line VL.

[0026] The arm member 7, which supports a part of the processing liquid supply device 3, has, for example, a rod shape and supports the nozzle 30 at its tip. The nozzle support unit 4 supports the arm member 7 so that the nozzle 30 is positioned on the imaginary line VL, and is provided on a rail 5r so as to be movable in the rail direction. A motor, which constitutes a part of the nozzle moving device 5, is attached to the nozzle support unit 4. As a result, the nozzle support unit 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 offset 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 overlapping the rotation center of the spin chuck 1 in a plan view. When the substrate processing apparatus 100 is in a standby state where a removal process is not being 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 a removal process, 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 so that the outlet of the nozzle 30 faces the center of rotation of the spin chuck 1. In this embodiment, the center of the substrate W held by the spin chuck 1 is located on a vertical axis passing through the center of rotation of the spin chuck 1. As a result, in this embodiment, when the nozzle 30 is held at the processing position PP, the outlet of the nozzle 30 faces the center of the substrate W.

[0029] During the removal process, the processing liquid is ejected from the ejection port of the nozzle 30 of the processing liquid supply device 3 toward one surface of the substrate W. After colliding with one surface of the substrate W (more precisely, one surface of the substrate W or the resist film covering one surface of the substrate W), the ejected processing liquid spreads radially from the center of the substrate W toward the outer circumferential edge thereof due to centrifugal force.

[0030] 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 a rinse liquid to the rinse nozzle. After the resist film has been removed by the processing liquid, the rinse nozzle ejects the rinse liquid toward one surface of the substrate W on which the processing liquid remains. This removes the processing liquid from the substrate W (rinsing process). The control unit 6 and the operation unit 9 will be described in detail later.

[0031] <2> Control System of Substrate Processing Apparatus The control system of the substrate processing apparatus 100 will be described together with the configuration of the control unit 6 and 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 a work area for the CPU 61. The ROM 63 stores a system program. 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. The storage device 64 also stores operating conditions of the substrate processing apparatus 100 related to the removal process. The operating conditions will be described in detail later.

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

[0034] The CPU 61 executes the film removal program to control the operation of each part of the substrate processing apparatus 100 during the removal process. Specifically, the control unit 6 controls the spin motor 1 a to rotate the substrate W while the substrate W is placed on the spin base 1 b and held by a plurality of chuck pins 1 c.

[0035] Furthermore, the control unit 6 controls the cup lifting device 2D so that the cup 2 is held in the lower position when the substrate W is placed on the spin chuck 1, when the substrate W is removed from the spin chuck 1, and when no removal process is being performed. Here, the lower position refers to the position of the cup 2 when the upper end of the cup 2 is lower than the substrate W held by the spin chuck 1.

[0036] Furthermore, the control unit 6 controls the cup lifting device 2D so that the cup 2 is held in the upper position during the removal process. Here, the upper position refers to the position of the cup 2 when the upper end of the cup 2 is higher than the substrate W held by the spin chuck 1 and the inner peripheral surface of the cup 2 faces the outer peripheral edge of the substrate W in a horizontal plane. In this case, the processing liquid splashed 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 a drain pipe.

[0037] Furthermore, 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 while the removal process is being performed. Furthermore, 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 while the removal process is not being performed.

[0038] As described above, the operating conditions of the substrate processing apparatus 100 for 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 multiple valves 12a, 23a, 24a, and 25a and the multiple adjustment units 12b, 23b, 24b, and 25b of the processing liquid supply device 3 based on the operating conditions stored in the storage device 64. In this case, in the processing liquid supply device 3, while sulfuric acid is flowing through the first pipe 12, hydrogen peroxide solution 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. As a result, the sulfuric acid and the hydrogen peroxide solution are mixed in the liquid flow path to generate a processing liquid (SPM).

[0039] 1 includes a keyboard and a pointing device and is configured to be operable by the user. The user can input the above-mentioned operating conditions by operating the operating unit 9. When the operating conditions are input via the operating unit 9, the control unit 6 stores the input operating conditions in the storage device 64.

[0040] <3> Changes in state when a film on a substrate W is removed As explained in the section on the problem to be solved by the invention, in a resist film removal process, even if a processing liquid containing Caro's acid is supplied onto one surface of a substrate W, multiple portions of the resist film on one surface of the substrate W are not necessarily removed uniformly. The inventors have focused on this point and hypothesized that the method of generating the processing liquid may contribute to the non-uniformity of the removal of the resist film. Therefore, the inventors conducted the following film removal experiment using the processing liquid supply device 3 having the configuration shown in FIG. 1 above.

[0041] First, the inventors prepared two sample substrates on which resist films were formed using a common method. In the following description, the two sample substrates will be referred to as the first sample substrate and the second sample substrate, respectively. The inventors then supplied treatment solutions prepared using different methods to the first sample substrate and the second sample substrate, and observed changes in the resist films on each substrate during the supply of the treatment solutions.

[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 in a horizontal position and rotated by the spin chuck 1. The inventor also opened the three valves 12a, 23a, and 24a of the processing liquid supply device 3 shown in Figure 1 and closed the valve 25a.

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

[0044] 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. Furthermore, hydrogen peroxide solution is supplied from the second liquid supply source 21 to the first portion MP1 of the liquid flow path through the second main pipe 22 and the second sub-pipe 23. As a result, the sulfuric acid and hydrogen peroxide solution join in the first portion MP1, and the resulting mixture is sent to the agitation unit 12c. In the agitation unit 12c, the liquid (in this example, a mixture of sulfuric acid and hydrogen peroxide solution) flowing inside the agitation unit 12c is agitated. Furthermore, hydrogen peroxide solution is supplied from the second liquid supply source 21 to the second portion MP2 of the liquid flow path through the second main pipe 22 and the second sub-pipe 24. As a result, the mixture and new hydrogen peroxide solution join in the second portion MP2, and the resulting mixture is sent to the nozzle 30 as the processing liquid.

[0045] The inventors used a camera to capture images of one surface of the first sample substrate every 60 seconds from the start of supplying the treatment liquid to the first sample substrate, and confirmed the change over time of the resist film during the removal treatment of the first sample substrate based on the captured images.

[0046] Fig. 4 is a schematic diagram showing the results of a film removal experiment on a first sample substrate. The upper part of Fig. 4 shows a plan view of the first sample substrate 60 seconds after the start of supplying the treatment liquid. The middle part of Fig. 4 shows a plan view of the first sample substrate 120 seconds after the start of supplying the treatment liquid. The lower part of Fig. 4 shows a plan view of the first sample substrate 180 seconds after the start of supplying the treatment liquid.

[0047] Each plan view in Fig. 4 is a schematic representation of an image of the first sample substrate obtained by imaging the first sample substrate. In each of the plan views in the upper, middle, and lower rows in Fig. 4, the resist film present on one surface of the first sample substrate is shown by a dot pattern.

[0048] In the following description, the ratio (proportion) of the area of ​​the portion from which the resist film has been removed to the area of ​​the entire surface of the substrate is referred to as the resist film removal rate. Furthermore, an inner portion R1 and an outer portion R2 are defined on one surface 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 approximately two-thirds of the radius of the substrate. The outer portion R2 has an annular shape that includes the outer peripheral edge of the substrate W and surrounds the inner portion R1.

[0049] 4, after 60 seconds had elapsed since the start of supply of the treatment liquid, almost no resist film had been removed from the entire first sample substrate, and the removal rate of the resist film on the first sample substrate at this time was approximately 4%.

[0050] As shown in the middle of Figure 4, 120 seconds after the start of supply of the treatment liquid, the resist film on the inner portion R1 of the first sample substrate was almost completely removed. However, the resist film on the outer portion R2 of the first sample substrate was completely removed. At this time, the removal rate of the resist film on the first sample substrate was approximately 58%.

[0051] As shown in the lower part of Figure 4, after 180 seconds had elapsed since the start of supply of the treatment liquid, the resist film in the inner portion R1 of the first sample substrate had been removed over a wider area than after 120 seconds had elapsed. Furthermore, within the inner portion R1 of the first sample substrate, the areas from which the resist film had been removed were dispersed relatively uniformly. At this time, the removal rate of the resist film on the first sample substrate was approximately 76%.

[0052] Next, with the second sample substrate being held in a horizontal position and rotated by the spin chuck 1, the inventor positioned the nozzle 30 so as to face the center of the substrate W. The inventor also opened the two valves 12a and 25a of the processing liquid supply device 3 shown in Figure 1 and closed the valves 23a and 24a.

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

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

[0055] The inventors used a camera to capture images of one surface of the second sample substrate every 60 seconds from the start of supplying the treatment liquid to the second sample substrate, and observed the change over time of the resist film during the removal process of the second sample substrate based on the captured images.

[0056] Fig. 5 is a schematic diagram showing the results of a film removal experiment on a second sample substrate. The upper part of Fig. 5 shows a plan view of the second sample substrate 60 seconds after the start of supply of the treatment liquid. The middle part of Fig. 5 shows a plan view of the second sample substrate 120 seconds after the start of supply of the treatment liquid. The lower part of Fig. 5 shows a plan view of the second sample substrate 180 seconds after the start of supply of the treatment liquid.

[0057] Each plan view of Fig. 5 is a schematic representation of an image of the second sample substrate obtained by imaging the second sample substrate, similar to each plan view of Fig. 4. In each of the top, middle, and bottom plan views of Fig. 5, the resist film present on one surface of the second sample substrate is shown by a dot pattern.

[0058] 5, after 60 seconds had elapsed since the start of supply of the treatment liquid, the resist film had hardly been removed from the entire second sample substrate, and the removal rate of the resist film on the second sample substrate at this time was approximately 4%.

[0059] 5, after 120 seconds had elapsed since the start of supply of the treatment liquid, the resist film had been sparsely removed from the entire second sample substrate, and the removal rate of the resist film on the second sample substrate at this time was approximately 19%.

[0060] As shown in the lower part of Figure 5, 180 seconds after the start of supplying the treatment liquid, most of the resist film on the inner portion R1 of the second sample substrate had been removed. However, a relatively large amount of the resist film remained on the outer portion R2 of the second sample substrate. At this time, the removal rate of the resist film on the second sample substrate was approximately 75%.

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

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

[0063] As a result, the inventors discovered that the method of generating the processing liquid contributes to non-uniformity in resist film removal. Based on this discovery, the inventors considered that by switching between multiple processing liquid generation methods during removal processing of one substrate W, it is possible to efficiently remove resist film from the entire surface of one substrate W. More specifically, the inventors focused on the non-uniformity in resist film removal that occurs concentrically from the center (central portion) to the periphery (peripheral portion) of the substrate W, which is caused by the processing liquid generation method. Based on this, the inventors considered that it is possible to efficiently remove resist film by switching the points (MP1, MP2, MP3) where sulfuric acid and hydrogen peroxide solution join during removal processing of the substrate W.

[0064] <4> An example of operating conditions stored in the memory device 64 As described above, in order to switch between multiple processing liquid generation methods during the removal process of one substrate W, it is necessary to set operating conditions for the substrate processing device 100 for each processing liquid generation method.

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

[0066] The upper part of Fig. 6 uses a table to show two operating conditions that are set to correspond to a first period and a second period, respectively, during the removal process. The lower part of Fig. 6 shows a configuration diagram of the processing liquid supply apparatus 3 to facilitate understanding of the table. As shown in the lower part of Fig. 6, in the following description, when distinguishing between the multiple second sub-pipes 23, 24, and 25 of the processing liquid supply apparatus 3, the second sub-pipe 23 will be referred to as "pipe A," the second sub-pipe 24 will be referred to as "pipe B," and the second sub-pipe 25 will be referred to as "pipe C."

[0067] 6 , the open / close states of the valves 12a, 23a, 24a, and 25a of the first pipe 12, pipe A, pipe B, and pipe C are set to be "open," "open," "open," and "closed" during a first period. When the processing liquid supplying device 3 is controlled according to these operating conditions, hydrogen peroxide solution is supplied to the sulfuric acid or mixed liquid flowing through the first pipe 12 in the first portion MP1 and the second portion MP2 of the liquid flow path. As a result, during the first period, the resist film on the substrate W is removed sequentially, for example, from the outer periphery of the substrate W toward the center of the substrate W. That is, the resist film on the outer portion R2 of the substrate W is preferentially removed (see FIG. 4 ).

[0068] 6, the open / close states of the valves 12a, 23a, 24a, and 25a of the first pipe 12, pipe A, pipe B, and pipe C are set to be "open," "closed," "closed," and "open" during the second period. When the processing liquid supply device 3 is controlled according to these operating conditions, hydrogen peroxide solution is supplied to the sulfuric acid flowing through the first pipe 12 in the third portion MP3 of the liquid flow path. As a result, during the second period, the resist film on the substrate W is removed sequentially, for example, from the center of the substrate W toward the outer periphery of the substrate W. That is, the resist film on the inner portion R1 of the substrate W is preferentially removed (see FIG. 5).

[0069] According to the above operating conditions, the portion of the resist film that is preferentially removed changes between the first period and the second period. Therefore, by appropriately determining the first period and the second period, the time required to remove the resist film from the entire surface of the substrate W can be shortened. The first period and the second period that are considered appropriate for shortening the removal process can be determined, for example, by experiment or simulation. Furthermore, the relationship between the position on the substrate W from which the resist film is preferentially removed and the method for selecting the portion (MP1, MP2, MP3) where the sulfuric acid and the hydrogen peroxide solution join can be determined through prior experimentation. In this embodiment, a method for selecting the portion (MP1, MP2, MP3) where the sulfuric acid and the hydrogen peroxide solution join at each concentric position on the substrate W is required, so that the resist film is preferentially removed.

[0070] <5> Film Removal Processing by Control Unit 6 Fig. 7 is a flowchart showing an example of film removal processing by the control unit 6 of Fig. 1. The film removal processing 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 unprocessed substrate W (a substrate W having a resist film formed on the entire surface) being loaded into the chamber of the substrate processing apparatus 100 and placed on the spin chuck 1. In the initial state, the cup 2 is in the lower position, and the plurality of nozzles 30 are in the standby position WP. Also, the plurality of valves 12 a, 23 a, 24 a, 25 a of the processing liquid supply device 3 are all maintained in a closed state. Furthermore, the memory device 64 of the control unit 6 stores two operating conditions for the processing liquid supply device 3, which correspond to a first period and a 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). The CPU 61 also controls the spin motor 1a to rotate the substrate W held by the multiple chuck pins 1c on the spin base 1b (step S12). The CPU 61 also 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] Next, 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, the CPU 61 controls the valves 12 a, 23 a, 24 a, 25 a and the adjusters 12 b, 23 b, 24 b, 25 b of the processing liquid supply device 3 based on the operating conditions corresponding to the first period during the predetermined first period (step S15). As a result, a portion of the resist film on one surface of the substrate W is removed preferentially over other portions of the resist film on the one surface of the substrate W.

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

[0075] When the second period ends, the CPU 61 closes the valves 12a, 23a, 24a, and 25a of the processing liquid supply device 3, thereby stopping the supply of the processing liquid (step S17).

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

[0077] After the drying process in step S19 is completed, the CPU 61 controls the spin motor 1a to stop the rotation of the substrate W (step S20), and controls the cup lifting device 2D to move the cup 2 from the upper position to the lower position (step S21), thereby completing the series of processes.

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

[0079] Furthermore, during a second period during the removal process on one substrate W, sulfuric acid and hydrogen peroxide solution are mixed in a third portion MP3 of the liquid flow path. On the other hand, sulfuric acid and hydrogen peroxide solution are not mixed in the first portion MP1 and the second portion MP2 of the liquid flow path. The third portion MP3 is located close to the downstream end of the liquid flow path (the outlet of the nozzle 30). The processing liquid obtained by the mixing is supplied to the one substrate W. The processing liquid supplied to the one substrate W at this time is referred to as the second processing liquid.

[0080] When the first processing liquid is supplied to one surface of one substrate W, the resist film is easily removed from a first portion of the multiple portions of the substrate W, and is difficult to remove from other portions. Furthermore, when the second processing liquid is supplied to one surface of one substrate W, the resist film is easily removed from a second portion, which is different from the first portion, of the multiple portions of the substrate W, and is difficult to remove from other portions. Therefore, by appropriately setting the first period and the second period, the time required to remove the resist film from the entire 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 processing liquid supply device 3 is provided with an agitation unit 12c. During a first period during the removal process, hydrogen peroxide solution is supplied from two second sub-pipes 23 and 24 to two portions (first portion MP1 and second portion MP2) of the liquid flow path that sandwich the agitation unit 12c.

[0082] In this case, during the first period, sulfuric acid and hydrogen peroxide solution join upstream of agitation unit 12c and flow into agitation unit 12c. In agitation unit 12c, the liquid passing through the inside of agitation unit 12c is agitated, thereby accelerating the chemical reaction between sulfuric acid and hydrogen peroxide solution, and a certain amount of Caro's acid is produced.

[0083] After that, hydrogen peroxide solution is added to the mixed solution that has passed through the agitator 12c. In this case, a further chemical reaction occurs between the newly added hydrogen peroxide solution and the sulfuric acid in the mixed solution. This makes it possible to supply a treatment solution with a high Caro's acid concentration to one side of the substrate W.

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

[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 a first period corresponding to a first processing liquid generation method and a second period corresponding to a second processing liquid generation method, a third period corresponding to a third processing liquid generation method may be set. In this way, when the first period, second period, and third period are set, the memory device 64 stores operating conditions corresponding to the first period, second period, and third period, respectively.

[0086] Alternatively, in addition to the first, second, and third periods corresponding to the first, second, and third methods of generating the treatment liquid, a fourth period corresponding to a fourth method of generating the treatment liquid may be set. In this way, when the first, second, third, and fourth periods are set, the memory device 64 stores operating conditions corresponding to the first, second, third, and fourth periods, respectively.

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

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

[0089] (c) In the processing liquid supply apparatus 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 solution, but the present invention is not limited to this. In the above processing liquid supply apparatus 3, the first liquid supply source 11 may be a supply source of hydrogen peroxide solution and the second liquid supply source 21 may be a supply source of sulfuric acid.

[0090] (d) Although the first pipe 12 of the processing liquid supplying apparatus 3 according to the above embodiment is provided with the agitating section 12c, the agitating section 12c may not be provided.

[0091] (e) Although the second liquid supply system 20 of the processing liquid supply apparatus 3 according to the above embodiment has three second sub-pipes 23, 24, and 25 as piping for mixing sulfuric acid with hydrogen peroxide solution, the present invention is not limited to this. 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, sulfuric acid and hydrogen peroxide solution can be mixed in four or more portions of the liquid flow path formed by the first pipe 12 and the nozzle 30. This increases the degree of freedom in the operating conditions that can be set to generate the processing liquid.

[0092] (f) In the above embodiment, an example was described in which sulfuric acid and hydrogen peroxide solution were mixed in the first portion MP1 and the second portion MP2 of the liquid flow path during the first period of the removal process, but the present invention is not limited to this. During the first period of the removal process, sulfuric acid and hydrogen peroxide solution may be mixed in all of the first portion MP1, the second portion MP2, and the third portion MP3 of the liquid flow path. Alternatively, during the first period of the removal process, sulfuric acid and hydrogen peroxide solution may be mixed in the first portion MP1 and the third portion MP3 of the liquid flow path, or sulfuric acid and hydrogen peroxide solution may be mixed in the second portion MP2 and the third portion MP3 of the liquid flow path.

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

[0094] <8> Correspondence between each part of the embodiment and each element of the claims The following describes an example of correspondence between each element of the claims and each element of the embodiment. Various other elements having the configuration or function described in the claims can also be used as each element of the claims.

[0095] In the above 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 portion MP1, the second portion MP2 and the third portion MP3 of the liquid flow path are examples of three or more different portions of the liquid flow path.

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

[0097] Furthermore, the second sub-pipe 25 is an example of a downstream pipe, the second sub-pipe 23 and the second sub-pipe 24 are examples of multiple upstream pipes, the stirring unit 12c is an example of an 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 multiple on-off valves, the control of the processing liquid supply device 3 under operating conditions corresponding to the first period is an example of the first control, and the control of the processing liquid supply device 3 under operating conditions corresponding to the second period is an example of the second control.

[0098] <9> Summary of Embodiments (Item 1) The substrate processing apparatus according to item 1 is a substrate processing apparatus that performs a removal process to remove an unnecessary film formed on one surface of a substrate using a processing liquid containing Caro's acid, wherein the Caro's 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, and the substrate processing apparatus comprises: a nozzle that ejects the processing liquid onto the one surface of the substrate; a first liquid supply system that includes a first pipe connected to the nozzle and supplies the first liquid to the nozzle through the first pipe; a second liquid supply system that includes 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 supplies the second liquid to the liquid flow path through any of the second pipes; and a control unit that controls the second liquid supply system, wherein the second pipes include a downstream pipe connected to the most downstream portion of the portions of the liquid flow path, and a plurality of upstream pipes excluding the downstream pipe, The control unit performs a first control during a first period during the removal process for one substrate, which prevents the second liquid from flowing through the downstream piping and allows the second liquid to flow through at least two of the multiple upstream pipings, and performs a second control during a second period during the removal process for the one substrate, which allows the second liquid to flow through the downstream piping and prevents the second liquid from flowing through the multiple upstream pipings.

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

[0100] During a second period during the removal process for a substrate, the first liquid flowing through the first pipe and the second liquid flowing through the downstream pipe are mixed near the nozzle outlet and supplied to the 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, the film is easily removed from a first portion of the substrate, but is difficult to remove from other portions. Furthermore, when the second processing liquid is supplied to one surface of the substrate, the film is easily removed from a second portion of the substrate, which is different from the first portion, but is difficult to remove from other portions. Therefore, by appropriately setting the first period and the second period, the time required to remove the film from the entire surface of the substrate can be shortened. As a result, the substrate processing efficiency is improved.

[0102] (Clause 2) In the substrate processing apparatus according to clause 1, the substrate processing apparatus further includes an agitation unit provided in the first piping, and the control unit may, in the first control, cause the second liquid to flow through two upstream piping connected to two portions of the liquid flow path that sandwich the agitation unit.

[0103] In this case, during the first period, the first liquid and the second liquid join upstream of the stirring section and flow into the stirring section. By stirring the first liquid and the second liquid, a chemical reaction between the first liquid and the second liquid is promoted, and a certain amount of Caro's acid is produced.

[0104] After the mixing section, the second liquid is added to the mixed liquid. In this case, a chemical reaction occurs between the newly added second liquid and the first liquid in the mixed liquid. This allows a treatment liquid with a high Caro's acid concentration to be supplied to the entire surface of the substrate.

[0105] (Clause 3) In the substrate processing apparatus according to clause 1 or 2, the substrate processing apparatus may further include a rotational holding unit that holds and rotates the one substrate during the removal process of the one substrate, and a nozzle support unit that supports the nozzle at a position above the one substrate so that the nozzle outlet faces the center of rotation of the one substrate during the removal process of the one substrate.

[0106] In this case, during removal processing of one substrate, the processing liquid is supplied to the center of rotation of one surface of the substrate. The processing liquid supplied to the center of rotation of the substrate spreads toward the outer peripheral edge of the substrate due to centrifugal force, thereby supplying the processing liquid to the entire surface of the substrate.

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

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

[0109] (Item 5) A substrate processing method according to item 5 is a substrate processing method using a substrate processing apparatus that performs a removal process to remove an unnecessary film formed on one surface of a substrate using a processing liquid containing Caro's acid, wherein the Caro's 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, and the substrate processing apparatus comprises: a nozzle that ejects the processing liquid onto the one surface of the substrate; a first liquid supply system that includes a first pipe connected to the nozzle and supplies the first liquid to the nozzle through the first pipe; and a second liquid supply system that includes three or more second pipes that are respectively connected to three or more different portions of a liquid flow path formed by the nozzle and the first pipe and supplies the second liquid to the liquid flow path through any of the second pipes, and the second pipes include a downstream pipe connected to the most downstream portion of the portions of the liquid flow path, and a plurality of upstream pipes excluding the downstream pipe, and the substrate processing method comprises: The method includes a step of performing a first control during a first period during the removal process for one substrate, in which the second liquid is not circulated through the downstream pipe and the second liquid is circulated through at least two of the plurality of upstream pipes; and a step of performing a second control during a second period during the removal process for the one substrate, in which the second liquid is circulated through the downstream pipe and the second liquid is not circulated through the plurality of upstream pipes.

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

[0111] During a second period during the removal process for a substrate, the first liquid flowing through the first pipe and the second liquid flowing through the downstream pipe are mixed near the nozzle outlet and supplied to the 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, the film is easily removed from a first portion of the substrate, but is difficult to remove from other portions. Furthermore, when the second processing liquid is supplied to one surface of the substrate, the film is easily removed from a second portion of the substrate, which is different from the first portion, but is difficult to remove from other portions. Therefore, by appropriately setting the first period and the second period, the time required to remove the film from the entire surface of the substrate can be shortened. As a result, the substrate processing efficiency is improved.

[0113] (Item 6) In the substrate processing method according to Item 5, the substrate processing apparatus may further include an agitation unit provided in the first piping, and the step of performing the first control may include circulating the second liquid through two upstream pipings connected to two portions of the liquid flow path that sandwich the agitation unit.

[0114] In this case, during the first period, the first liquid and the second liquid join upstream of the stirring section and flow into the stirring section. By stirring the first liquid and the second liquid, a chemical reaction between the first liquid and the second liquid is promoted, and a certain amount of Caro's acid is produced.

[0115] After the mixing section, the second liquid is added to the mixed liquid. In this case, a chemical reaction occurs between the newly added second liquid and the first liquid in the mixed liquid. This allows a treatment liquid with a high Caro's acid concentration to be supplied to the entire surface of the substrate.

[0116] (Clause 7) In the substrate processing method according to clause 5 or 6, the substrate processing method may further include the steps of: holding and rotating the one substrate using a rotary holder during the removal process of the one substrate; and supporting the nozzle at a position above the one substrate using a nozzle support so that the nozzle outlet faces the center of rotation of the one substrate during the removal process of the one substrate.

[0117] In this case, during removal processing of one substrate, the processing liquid is supplied to the center of rotation of one surface of the substrate. The processing liquid supplied to the center of rotation of the substrate spreads toward the outer peripheral edge of the substrate due to centrifugal force, thereby supplying the processing liquid to the entire surface 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 may further include a plurality of on-off valves respectively provided in the plurality of second pipes, and each of the steps of performing the first control and the second control may include controlling the flow state of the liquid in the plurality of second pipes by controlling the on-off state 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] The substrate processing apparatus and substrate processing method according to the above series of embodiments improves the substrate processing efficiency, thereby reducing wasteful consumption of processing liquid. This eliminates the need to prepare a large amount of processing liquid. This contributes to reducing global environmental pollution caused by processing liquid.

Claims

1. 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 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 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; and a control unit for controlling 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, and 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.

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

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

4. The second liquid supply system further includes a plurality of on-off valves respectively provided in the plurality of second pipes, and the control unit controls the liquid flow state in the plurality of second pipes by controlling the opening and closing states of the plurality of on-off valves. The substrate processing apparatus according to any one of claims 1 to 3.

5. 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 chromic acid, wherein the chromic 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, and 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, 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 a second liquid supply system for supplying the second liquid to the liquid flow path through any one of the plurality of second pipes, the plurality of second pipes including 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 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, and a second control step 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.

6. The substrate processing apparatus further includes a stirring unit provided in the first pipe, and 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. The substrate processing method according to claim 5.

7. While the one substrate is being removed, rotating the one substrate while holding it using a rotation holding unit; and while the one substrate is being removed, supporting the nozzle at a position above the one substrate using a nozzle support unit so that the discharge port of the nozzle faces the rotation center of the one substrate. The substrate processing method according to claim 5 or 6, further comprising the steps.

8. 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 includes 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. The substrate processing method according to any one of claims 5 to 7.

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