Substrate processing method and substrate processing apparatus

Abstract

To provide a substrate processing method and a substrate processing apparatus that can remove an organic film from a substrate with high efficiency while suppressing the burden of chemical costs and waste liquid treatment.SOLUTION: A substrate processing method for removing an organic film from a substrate includes the steps of a) introducing an ozone-containing gas into a substrate processing chamber to fill at least a space above the substrate in the substrate processing chamber with the ozone-containing gas, b) after the step a), starting spraying a heated chemical solution containing sulfuric acid onto the substrate through the space using a flow of inert gas, c) continuing the spraying started in the step b), and d) stopping the spraying continued in the step c).SELECTED DRAWING: Figure 4

Description

[Technical Field]

[0001] The present invention relates to a substrate processing method and apparatus for removing an organic film from a substrate, including, for example, a semiconductor wafer, a substrate for a FPD (Flat Panel Display) such as a liquid crystal display device or an organic EL (Electroluminescence) display device, 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, etc. [Background technology]

[0002] Semiconductor device manufacturing methods typically require substrate cleaning. Typically, a cleaning process is performed to remove unwanted organic films (typically resist films) from the substrate. For example, according to Japanese Patent Application Laid-Open Publication No. 2016-181677 (Patent Document 1), SPM cleaning is performed on the substrate surface using a sulfuric acid / hydrogen peroxide mixture (SPM) as a chemical solution. However, this process consumes a large amount of SPM. SPM is difficult to reuse efficiently, resulting in high chemical costs and wastewater treatment burdens. Therefore, in recent years, substrate processing methods that can reduce material costs and wastewater treatment burdens have been investigated. One such method is SOM cleaning, which uses a sulfuric acid and ozone mixture (SOM) as a chemical solution instead of SPM. By mixing sulfuric acid and ozone, peroxodisulfate ions (SO2, SO8) are generated as active species (etchants). 2- ) is generated.

[0003] For example, Japanese Patent Laid-Open No. 2013-150007 (Patent Document 2) discloses that sulfuric acid containing microbubbles of ozone gas is supplied to a substrate from a nozzle. Also, U.S. Patent No. 6,869,487 (Patent Document 3) discloses that ozone reaches the surface of the substrate by diffusing through the liquid layer by controlling the thickness of the liquid layer on the substrate. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2016-181677 [Patent Document 2] Japanese Patent Application Laid-Open No. 2013-150007 [Patent Document 3] U.S. Patent No. 6,869,487 Summary of the Invention [Problem to be solved by the invention]

[0005] The half-life of ozone is relatively long, for example, about 90 minutes in air at 150°C, but is very short, less than 10 seconds, in sulfuric acid at 150°C. Thus, ozone decomposes rapidly in sulfuric acid. Therefore, when ozone is already incorporated into sulfuric acid before it is ejected from a nozzle, as in the technology of JP 2013-150007 A, much of the ozone is likely to decompose too early before reaching the vicinity of the substrate. Correspondingly, activated species generated by ozone decomposition also tend to occur too early, resulting in many of the activated species being deactivated before reaching the substrate. This makes it difficult to perform substrate processing using activated species with high efficiency. While increasing the ozone concentration by increasing the pressure at which ozone is incorporated into the chemical solution may improve processing efficiency, it is practically difficult to stably maintain the high pressure required to achieve significant results.

[0006] According to the above-mentioned U.S. Patent No. 6,869,487, ozone diffusion through the liquid layer on the substrate is required. However, according to the investigations of the present inventors, diffusion through the liquid layer is not very likely to occur. Therefore, even with this method, it is difficult to perform substrate processing with high efficiency.

[0007] The present invention has been made to solve the above-mentioned problems, and an object of the present invention is to provide a substrate processing method and a substrate processing apparatus that can remove organic films from substrates with high efficiency while reducing the burden of chemical costs and waste liquid treatment. [Means for solving the problem]

[0008] A first aspect of the present invention is a substrate processing method for removing an organic film from a substrate, comprising: a) introducing an ozone-containing gas into a substrate processing chamber to fill at least a space above the substrate in the substrate processing chamber with the ozone-containing gas; b) after step a), starting spraying a heated chemical solution containing sulfuric acid onto the substrate through the space; c) continuing the spraying started in step b); and d) stopping the spraying that was continued in step c).

[0009] A second aspect of the present invention is the substrate processing method of the first aspect, wherein step a) includes a step of confirming that at least one of the measured values ​​of the pressure and the ozone concentration in the substrate processing chamber is equal to or greater than a predetermined threshold value.

[0010] A third aspect of the present invention is a substrate processing method according to the first or second aspect, wherein after the introduction of an ozone-containing gas into the substrate processing chamber is performed in step a), the introduction is continued in steps b) and c).

[0011] A fourth aspect of the present invention is the substrate processing method of the first or second aspect, wherein after the introduction of the ozone-containing gas into the substrate processing chamber is performed in step a), the introduction is stopped before step c).

[0012] A fifth aspect of the present invention is a substrate processing method according to any one of the first to fourth aspects, wherein the chemical liquid sprayed in step c) is separated into a first liquid that is collected by being received in a cup portion surrounding the substrate, and a second liquid that is collected outside the cup portion, and the second liquid is re-sprayed without containing the first liquid.

[0013] A sixth aspect of the present invention is a substrate processing apparatus for removing an organic film from a substrate, comprising: a substrate processing chamber; a substrate holding unit for holding the substrate in the substrate processing chamber; an ozone supply unit for supplying an ozone-containing gas into the substrate processing chamber; an atomization nozzle for spraying a chemical solution onto the substrate; a chemical solution supply unit having a heater and supplying the chemical solution heated by the heater to the atomization nozzle; and a control unit for controlling the ozone supply unit to fill at least a space above the substrate in the substrate processing chamber with ozone-containing gas, and then controlling the chemical solution supply unit to start spraying the chemical solution onto the substrate through the space. [Effects of the Invention]

[0014] According to the first and sixth aspects of the present invention, first, ozone, rather than hydrogen peroxide solution, is mixed with a heated chemical solution containing sulfuric acid. This facilitates efficient reuse of the chemical solution. This reduces the cost of the chemical solution and the burden of waste solution treatment. Second, the mixing is performed in the space above the substrate. This prevents ozone from decomposing too early before reaching the vicinity of the substrate, even when using high-temperature sulfuric acid, which easily decomposes ozone. Therefore, a high proportion of activated species generated by ozone decomposition reaches the substrate before deactivation. Meanwhile, the mixing is performed by spraying the chemical solution into an ozone-containing gas. The spraying provides a large surface area to the chemical solution, thereby accelerating the reaction between the chemical solution and the surrounding ozone. Therefore, the reaction between the chemical solution and ozone proceeds quickly without relying heavily on the diffusion of ozone into the chemical solution. As a result, a large amount of activated species is generated immediately after the mixing. As described above, a high proportion of these activated species reach the substrate before deactivation. Therefore, a process for removing an organic film from a substrate using activated species can be performed with high efficiency. Fourth, the space is already filled with ozone-containing gas when the chemical solution is sprayed. This activates the reaction between the chemical solution and ozone in the space from the start of spraying the chemical solution. This reduces the amount of chemical solution required for processing. As a result, organic films can be removed from substrates with high efficiency while reducing the cost of chemical solution and the burden of waste liquid treatment.

[0015] According to the second aspect of the present invention, spraying is started after it is confirmed that at least one of the pressure and the ozone concentration in the substrate processing chamber is equal to or greater than a predetermined threshold, thereby more reliably ensuring that the amount of ozone in the space is sufficient at the start of spraying the chemical solution.

[0016] According to the third aspect of the present invention, the introduction of an ozone-containing gas is continued during the spraying of the chemical solution. This compensates for the decrease in ozone concentration in the substrate processing chamber due to the decomposition of ozone. Therefore, the progress of the substrate processing can be kept approximately constant throughout the entire spraying period of the chemical solution.

[0017] According to the fourth aspect of the present invention, the introduction of the ozone-containing gas is stopped while the chemical solution is being sprayed, thereby making it possible to reduce the consumption of the ozone-containing gas.

[0018] According to the fifth aspect of the present invention, a portion of the sprayed chemical solution is re-sprayed. This makes it possible to further reduce the burden of chemical solution costs and waste liquid treatment. Furthermore, by not including the chemical solution received in the cup portion in the re-sprayed chemical solution, it is possible to avoid re-spraying of contaminated chemical solution on the substrate.

[0019] Objects, features, aspects, and advantages associated with the technology disclosed herein will become more apparent from the detailed description set forth below and the accompanying drawings. [Brief explanation of the drawings]

[0020] [Figure 1] 1 is a plan view schematically showing a configuration of a substrate processing system in each embodiment of the present invention. [Figure 2] 2 is a block diagram conceptually showing the configuration of a control unit shown in FIG. 1. FIG. [Figure 3] 2 is a flow chart schematically showing a substrate processing method using the substrate processing system of FIG. 1. [Figure 4] 1 is a cross-sectional view schematically showing a configuration of a substrate processing apparatus according to a first embodiment. [Figure 5] 1 is a flow chart schematically showing a substrate processing method in accordance with the first embodiment. [Figure 6] FIG. 10 is a cross-sectional view schematically showing the configuration of a substrate processing apparatus according to a second embodiment. [Figure 7] 10 is a flow chart schematically showing a substrate processing method according to a second embodiment. [Figure 8] FIG. 11 is a cross-sectional view schematically showing the configuration of a substrate processing apparatus according to a third embodiment. [Figure 9] 9 is a block diagram schematically showing the configuration of a gas / liquid supply unit and a gas / liquid discharge unit provided in the substrate processing apparatus shown in FIG. 8. FIG. [Figure 10]10 is a cross-sectional view schematically showing a step of a substrate processing method in accordance with a third embodiment. [Figure 11] FIG. 11 is a plan view schematically showing a step of a substrate processing method in accordance with a third embodiment. [Figure 12] 10 is a cross-sectional view schematically showing a step of a substrate processing method in accordance with a third embodiment. [Figure 13] 10 is a cross-sectional view schematically showing a step of a substrate processing method in accordance with a third embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0021] Hereinafter, embodiments will be described with reference to the accompanying drawings. In the following embodiments, detailed features are shown for the purpose of explaining the technology, but they are merely examples and not all of them are necessarily essential features for enabling the embodiments. The drawings are schematic, and for the sake of convenience, components may be omitted or simplified as appropriate. Furthermore, the relative sizes and positions of components shown in different drawings are not necessarily accurately depicted and may be changed as appropriate. Hatching may be used in drawings such as plan views that are not cross-sectional views to facilitate understanding of the embodiments. In the following description, similar components are denoted by the same reference numerals, and their names and functions are also the same. Therefore, detailed descriptions of them may be omitted to avoid duplication. In the following description, when a component is described as "comprising," "including," or "having," it is not an exclusive expression that excludes the existence of other components, unless otherwise specified.

[0022] <Substrate processing system> 1 is a plan view schematically showing an example of the configuration of a substrate processing system 1. The substrate processing system 1 includes a load port LP, an indexer robot IR, a center robot CR, a controller 10, and at least one processing unit 110 (four processing units in FIG. 1). The substrate processing system 1 is for removing an organic film (e.g., a resist film) from a substrate W.

[0023] Each processing unit 110 is for processing a substrate W (wafer). The processing unit 110 is a single-wafer type apparatus that can be used for substrate processing. The control unit 10 can control the operation of each component in the substrate processing system 1. The carrier C is a container that stores substrates W. The load port LP is a container holding mechanism that holds multiple carriers C. The indexer robot IR can transport substrates W between the load port LP and the substrate platform PS. The center robot CR can transport substrates W between the substrate platform PS and the processing unit 110. With the above configuration, the indexer robot IR, the substrate platform PS, and the center robot CR function as a transport mechanism that transports substrates W between each processing unit 110 and the load port LP.

[0024] An unprocessed substrate W is removed from the carrier C by the indexer robot IR. The unprocessed substrate W is then transferred to the center robot CR via the substrate platform PS. The center robot CR loads the unprocessed substrate W into the processing unit 110. The processing unit 110 then processes the substrate W. The substrate W that has been processed in the processing unit 110 is removed from the processing unit 110 by the center robot CR. The processed substrate W then passes through other processing units 110 as necessary, and is then transferred to the indexer robot IR via the substrate platform PS. The indexer robot IR loads the processed substrate W into the carrier C. In this manner, the substrate W is processed.

[0025] FIG. 2 is a conceptual diagram illustrating an example of the configuration of the control unit 10 shown in FIG. 1. The control unit 10 controls the processing unit 110, load port LP, indexer robot IR, center robot CR, and the like shown in FIG. 1. The control unit 10 may be configured by a general computer having electrical circuits. Specifically, the control unit 10 includes a central processing unit (CPU) 1011, a read-only memory (ROM) 1012, a random access memory (RAM) 1013, a storage device 1014, an input unit 1016, a display unit 1017, and a communication unit 1018, as well as a bus line 1015 interconnecting these units.

[0026] The ROM 1012 stores a basic program. The RAM 1013 is used as a work area when the CPU 1011 performs predetermined processing. The storage device 1014 is composed of a nonvolatile storage device such as a flash memory or a hard disk drive. The input unit 1016 is composed of various switches or a touch panel, and receives input setting instructions such as processing recipes from an operator. The display unit 1017 is composed of, for example, a liquid crystal display device and lamps, and displays various information under the control of the CPU 1011. The communication unit 1018 has a data communication function via a local area network (LAN), etc.

[0027] 3 is a flow diagram schematically illustrating a substrate processing method using the substrate processing system 1 of FIG. 1. In step S11 (FIG. 3), the indexer robot IR and the center robot CR sequentially use the substrate W having the organic film to be removed thereon to load the substrate W from the carrier C into the substrate processing chamber of the processing unit 110. In step S12 (FIG. 3), a process of removing the organic film from the substrate W (details of which will be described later) is performed. In step S13 (FIG. 3), a rinse liquid is supplied to the substrate W, thereby performing a rinse process on the substrate W. In step S14 (FIG. 3), the substrate W is dried. In step S15 (FIG. 3), the center robot CR and the indexer robot IR sequentially use the substrate W to unload the substrate W from the substrate processing chamber of the processing unit 110 into the carrier C.

[0028] The storage device 1014 has preset therein a plurality of modes for controlling each component in the substrate processing system 1 of FIG. 1. When the CPU 1011 executes the processing program 1014P, one of the above-described modes is selected, and each component is controlled in that mode. The processing program 1014P may be stored in a recording medium. By using this recording medium, the processing program 1014P can be installed in the control unit 10. Furthermore, some or all of the functions executed by the control unit 10 do not necessarily have to be realized by software, but may be realized by hardware such as a dedicated logic circuit.

[0029] <First Embodiment> 4, in the first embodiment, a substrate processing apparatus 111 for removing an organic film (e.g., a resist film) from a substrate W is applied as at least one of the processing units 110 (FIG. 1). The substrate processing apparatus 111 includes a chamber 12 (substrate processing chamber), a spin chuck 14 (substrate holder), an ozone supply unit 200, a chemical liquid supply unit 300, a nitrogen supply unit 350 (inert gas supply unit), a two-fluid nozzle 171 (atomization nozzle), a nozzle moving mechanism 172, a cup unit 161, a waste liquid unit 320, and an exhaust unit 190.

[0030] The spin chuck 14 holds the substrate W in the chamber 12. The spin chuck 14 has a spin base 143, a spin motor 144 that rotates the spin base 143 via a spin axis, and a substrate suction mechanism 145 that fixes the substrate W to the spin base 143 by sucking the substrate W onto the spin base 143.

[0031] The ozone supply unit 200 supplies an ozone-containing gas into the chamber 12. For this purpose, the ozone supply unit 200 has a pipe connected to the space inside the chamber 12 via a valve. The end of the pipe, which constitutes the supply port for the ozone-containing gas, is attached to the chamber 12, and its height position is preferably near the height position of the upper surface of the substrate W, and may be, for example, slightly higher than the height position of the upper surface of the substrate W. The ozone supply unit 200 may have a gas source that supplies oxygen or air, and an ozone generator that ozonizes the gas from this gas source. The ozone concentration in the ozone-containing gas supplied from the ozone supply unit 200 is 100 g / m 3 More than 400g / m 3 Preferably, it is 250 g / m or less. 3 More than 400g / m 3 The pressure of the ozone-containing gas supplied by the ozone supply unit 200 may be 0.1 MPa or more and 0.3 MPa or less.

[0032] The chemical liquid supply unit 300 has a sulfuric acid tank 301, a pressure adjustment unit 302, and a heater 303. The chemical liquid supply unit 300 supplies the chemical liquid containing sulfuric acid heated by the heater 303 to the two-fluid nozzle 171. The temperature to which the chemical liquid is heated is preferably 70°C or higher and 200°C or lower. The pressure adjustment unit 302 adjusts the supply pressure to the two-fluid nozzle 171. The pressure adjustment unit 302 may be a pump or a regulator. The supply pressure of the chemical liquid to the two-fluid nozzle 171 is set higher than a threshold pressure, which will be described later.

[0033] The nitrogen supply unit 350 supplies nitrogen (N2) gas as an inert gas to the two-fluid nozzle 171. The supply pressure of the nitrogen gas to the two-fluid nozzle 171 is set higher than a threshold pressure, which will be described later.

[0034] The two-fluid nozzle 171 is an atomization nozzle that sprays the chemical solution onto the substrate W. By spraying, the chemical solution is supplied into the chamber 12 as fine particles FM. During spraying, the two-fluid nozzle 171 utilizes a high-speed flow of gas supplied from the nitrogen supply unit 350 to more easily atomize the particles FM of the sprayed chemical solution than with a single-fluid nozzle. This increases the surface area of ​​the sprayed chemical solution. Note that if the desired spraying can be achieved with a single-fluid nozzle, a single-fluid nozzle that atomizes the chemical solution without using the nitrogen supply unit 350 may be used as the atomization nozzle instead of the two-fluid nozzle 171. The nozzle movement mechanism 172 moves the two-fluid nozzle 171 horizontally. The nozzle movement mechanism 172 may include an arm that supports the two-fluid nozzle 171 and an actuator that drives the arm.

[0035] The cup portion 161 surrounds the sides of the substrate W and the spin base 143 that holds it. When the chemical liquid is sprayed toward the substrate W while the spin motor 144 is rotating the substrate W, the chemical liquid supplied onto the substrate W is scattered around the substrate W. When the chemical liquid is supplied onto the substrate W, the upper end of the cup portion 161, which opens upward, is positioned above the spin base 143. Therefore, the chemical liquid discharged around the substrate W is received by the cup portion 161. The first liquid LR1, which is the chemical liquid received and recovered in the cup portion 161, is sent to the waste liquid section 320. The second liquid LR2, which is the chemical liquid recovered outside the cup portion 161, of the sprayed chemical liquid can return to the chemical liquid supply unit 300 through a pipe provided with a valve. This pipe is connected to the pipe of the chemical liquid supply unit 300 by a three-way valve 310. By switching the three-way valve 310, the chemical liquid supply unit 300 is switched between a state in which the chemical liquid in the sulfuric acid tank 301 is used and a state in which the chemical liquid supply unit 300 is used second liquid LR2. Note that the cup unit 161 may be configured to be lowered below the spin base 143 by a cup moving mechanism (not shown) when this function is not required.

[0036] The exhaust unit 190 has a pipe that is connected to the space inside the chamber 12 via a valve. When the valve is open, the exhaust unit 190 exhausts the atmosphere inside the chamber 12 to the outside of the chamber 12. The end of this pipe that constitutes the exhaust port of the chamber 12 is attached to the chamber 12 in FIG. 4, but it may instead be attached to the cup portion 161. The exhaust unit 190 preferably has an ozone removal device.

[0037] The control unit 10 (FIG. 1) controls each unit of the substrate processing apparatus 111. In this embodiment, the control unit 10 controls the ozone supply unit 200 to fill at least the space above the substrate W in the chamber 12 with an ozone-containing gas, and then controls the chemical liquid supply unit 300 to start spraying a chemical liquid onto the substrate W through the space. The control unit 10 may be considered as part of the substrate processing apparatus 111.

[0038] In the following, SOM cleaning, which is a process corresponding to step S12 (FIG. 3) and removes an organic film from the substrate W by the substrate processing apparatus 111 (FIG. 4), will be described in more detail.

[0039] The substrate W is held by the spin chuck 14. In step ST10 (FIG. 5), the ozone supply unit 200 starts introducing an ozone-containing gas into the chamber 12. In step ST20 (FIG. 5), the introduction of the ozone-containing gas fills at least the space above the substrate W in the chamber 12 with the ozone-containing gas. Whether the chamber 12 is filled with the ozone-containing gas may be defined by whether at least one of the pressure and ozone concentration in the chamber 12 is equal to or greater than a threshold. The threshold pressure is preferably equal to or greater than 0.1 MPa and equal to or less than 0.3 MPa. The threshold concentration is preferably equal to or greater than 100 g / m 3 More than 400g / m 3 Preferably, it is 250 g / m or less. 3 More than 400g / m 3 It is more preferable that the measured value is equal to or less than the threshold value. In this embodiment, it is not necessary to obtain a measured value to be compared with the threshold value, but a process may be performed to confirm that the measured value is equal to or greater than the threshold value. In this case, a pressure gauge 250 (see FIG. 6) or an ozone concentration meter, which will be described later, is provided in the chamber 12 for the measurement.

[0040] Before step ST40 (FIG. 5) described later, the spin chuck 14 starts rotating the substrate W. After step ST20 described above, in step ST40 (FIG. 5), the chemical supply unit 300 supplies a heated chemical containing sulfuric acid to the two-fluid nozzle 171, and the nitrogen supply unit supplies nitrogen gas. This starts spraying the heated chemical containing sulfuric acid onto the substrate W through the space already filled with the ozone-containing gas as described above. The sulfuric acid in the sprayed chemical reacts with ozone in the space to generate active species, specifically SO2O8. 2- In step ST50 (FIG. 5), the spraying started in step ST40 is continued.

[0041] In step ST60 (FIG. 5), the spraying that was continued in step ST50 is stopped. Specifically, the chemical liquid supply unit 300 stops supplying the chemical liquid to the two-fluid nozzle 171, and the nitrogen supply unit 350 stops supplying the nitrogen gas. The timing at which the spraying is stopped may be, for example, a predetermined time after the start of the spraying. As another example, the timing at which the spraying is stopped may be determined by referring to a monitor means for grasping the progress of the substrate processing. In this embodiment, after the ozone-containing gas is introduced into the chamber 12 in steps ST10 and ST20 (FIG. 5), this introduction is continued in steps ST40 and ST50. In other words, new ozone-containing gas is continuously replenished during the spraying. Simultaneously with or after step ST60, in step ST30, the ozone supply unit 200 stops introducing the ozone-containing gas.

[0042] SOM cleaning is performed as described above. Note that the above-described SOM cleaning is sufficient as long as it is a substrate treatment that at least partially removes the organic film. If a portion of the organic film remains immediately after SOM cleaning, additional cleaning may be performed. This additional substrate treatment may be, for example, SPM cleaning or SC1 cleaning. This also applies to other embodiments described below.

[0043] The chemical liquid sprayed in step ST50 (FIG. 5) is separated into a first liquid LR1 that is received in the cup portion 161 surrounding the substrate W and thereby recovered, and a second liquid LR2 that is recovered outside the cup portion 161. Thereafter, the second liquid LR2 may be re-sprayed without containing the first liquid LR1. Specifically, by switching the three-way valve 310, the chemical liquid supply unit 300 may be switched from a state in which the chemical liquid in the sulfuric acid tank 301 is used to a state in which the second liquid LR2 is used. The second liquid LR2 may be re-sprayed onto the substrate W that was being processed while the second liquid LR2 was being recovered, or onto another substrate W. These features may also be applied to the second embodiment, which will be described later.

[0044] <Embodiment 2> 6, in the second embodiment, a substrate processing apparatus 112 for removing an organic film from a substrate W is applied as at least one of the processing units 110 (FIG. 1). The substrate processing apparatus 112 includes a pressure gauge 250 for measuring the pressure inside the chamber 12 in addition to the configuration of the substrate processing apparatus 111 (FIG. 4: first embodiment).

[0045] The SOM cleaning process, which corresponds to step S12 (FIG. 3) and removes an organic film from the substrate W by the substrate processing apparatus 112 (FIG. 6), will be described in more detail below.

[0046] The substrate W is held by the spin chuck 14. In step ST10 (FIG. 7), the ozone supply unit 200 starts introducing an ozone-containing gas into the chamber 12. In step ST20 (FIG. 7), the ozone-containing gas is introduced, filling at least the space above the substrate W in the chamber 12 with the ozone-containing gas. In this embodiment, in step ST20, it is confirmed that the pressure measurement value obtained by the pressure gauge 250 is equal to or greater than a predetermined threshold pressure. In addition to or instead of this confirmation, it may be confirmed that the measured ozone concentration in the chamber 12 is equal to or greater than a predetermined threshold concentration. In this case, an ozone concentration meter (not shown) is provided in the chamber 12. The preferred ranges of the threshold pressure and threshold concentration are the same as those described in the first embodiment.

[0047] After step ST20, in step ST30 (FIG. 7), the ozone supply unit 200 stops the introduction of the ozone-containing gas. In other words, after it is confirmed that at least one of the pressure and the ozone concentration in the chamber 12 is sufficiently high, the introduction of the ozone-containing gas is stopped. This step ST30 is performed before step ST50, which will be described later. Furthermore, this step ST30 may also be performed before step ST40, which will be described later.

[0048] Before step ST40 (FIG. 7), the spin chuck 14 starts rotating the substrate W. After step ST20 described above, in step ST40 (FIG. 7), the chemical supply unit 300 supplies a heated chemical containing sulfuric acid to the two-fluid nozzle 171, and the nitrogen supply unit supplies nitrogen gas. This starts spraying the heated chemical containing sulfuric acid onto the substrate W through the space already filled with the ozone-containing gas as described above. The sulfuric acid in the sprayed chemical reacts with ozone in the space to generate active species, specifically SO 2- In step ST50 (FIG. 7), the spraying started in step ST40 is continued.

[0049] In step ST60 (FIG. 7), the spraying that was continued in step ST50 is stopped. Specifically, the chemical liquid supply unit 300 stops supplying the chemical liquid to the two-fluid nozzle 171, and the nitrogen supply unit 350 stops supplying the nitrogen gas. The timing at which the spraying is stopped may be, for example, a predetermined time after the spraying started. As another example, the timing at which the spraying is stopped may be determined by referring to a monitor means for understanding the progress of the substrate processing.

[0050] In this embodiment, after the ozone-containing gas is introduced into the chamber 12 in steps ST10 and ST20 (FIG. 7), this introduction is stopped before step ST50. In other words, there is a period during spraying during which new ozone-containing gas is not replenished. This introduction may also be stopped before step ST40. In other words, new ozone-containing gas may not be replenished at all during spraying.

[0051] <Third Embodiment> 8, in the third embodiment, a substrate processing apparatus 113 for removing an organic film from a substrate W is used as at least one of the processing units 110 (FIG. 1). The substrate processing apparatus 113 is a single-wafer processing apparatus that processes substantially disk-shaped substrates W one by one. In FIG. 8, hatching is omitted in cross sections of some components of the substrate processing apparatus 113 (the same applies to other cross-sectional views).

[0052] The substrate processing apparatus 113 includes a chamber 12, a top plate 123, a chamber opening / closing mechanism 131, a substrate holder 14, a substrate rotating mechanism 15, a liquid receiving unit 16, and a cover 17. The cover 17 covers the top and sides of the chamber 12.

[0053] The chamber 12 includes a chamber main body 121 and a chamber lid 122. The chamber 12 is generally cylindrical and centered on a central axis J1 that faces the up-down direction. The chamber main body 121 includes a chamber bottom 210 and a chamber side wall 214. The chamber bottom 210 includes a generally disk-shaped central portion 211, a generally cylindrical inner wall 212 that extends downward from the outer edge of the central portion 211, a generally annular plate-shaped annular bottom 213 that extends radially outward from the lower end of the inner wall 212, a generally cylindrical outer wall 215 that extends upward from the outer edge of the annular bottom 213, and a generally annular plate-shaped base 216 that extends radially outward from the upper end of the outer wall 215.

[0054] The chamber sidewall 214 is annular and centered on the central axis J1. The chamber sidewall 214 protrudes upward from the inner edge of the base 216. As will be described later, the member forming the chamber sidewall 214 also serves as part of the liquid receiving portion 16. In the following description, the space surrounded by the chamber sidewall 214, the outer wall 215, the annular bottom 213, the inner wall 212, and the outer edge of the central portion 211 is referred to as the lower annular space 217.

[0055] When the substrate W is supported on the substrate support parts 141 (described later) of the substrate holding part 14, the lower surface 92 of the substrate W faces the upper surface of the central part 211 of the chamber bottom 210. In the following description, the central part 211 of the chamber bottom 210 will be referred to as the "lower surface facing part 211," and the upper surface 211a of the central part 211 will be referred to as the "facing surface 211a." Details of the lower surface facing part 211 will be described later.

[0056] The chamber lid 122 has a generally circular plate shape perpendicular to the central axis J1 and includes the upper part of the chamber 12. The chamber lid 122 closes the upper opening of the chamber body 121. FIG. 8 shows the chamber lid 122 separated from the chamber body 121. When the chamber lid 122 closes the upper opening of the chamber body 121, the outer edge of the chamber lid 122 comes into contact with the upper part of the chamber sidewall 214.

[0057] The chamber opening / closing mechanism 131 moves the chamber lid 122, which is a movable part of the chamber 12, in the vertical direction relative to the chamber body 121, which is another part of the chamber 12. The chamber opening / closing mechanism 131 is a lid lifting mechanism that raises and lowers the chamber lid 122. When the chamber opening / closing mechanism 131 moves the chamber lid 122 in the vertical direction, the top plate 123 also moves in the vertical direction together with the chamber lid 122. The chamber lid 122 comes into contact with the chamber body 121 to close the upper opening, and the chamber lid 122 is further pressed toward the chamber body 121, thereby forming a sealed chamber space 120 (see FIG. 13) within the chamber 12. In other words, the chamber lid 122 closes the upper opening of the chamber body 121, thereby sealing the chamber space 120.

[0058] The substrate holding unit 14 is disposed in the chamber space 120 and holds the substrate W in a horizontal position. That is, the substrate W is held by the substrate holding unit 14 with the upper surface 91 facing upward perpendicular to the central axis J1. The substrate holding unit 14 includes the above-mentioned substrate support unit 141 that supports the outer edge of the substrate W (i.e., the portion near the outer edge including the outer edge) from below, and a substrate pressing unit 142 that presses the outer edge of the substrate W supported by the substrate support unit 141 from above. The substrate support unit 141 includes a support unit base 413 that is substantially annular and has a center on the central axis J1, and a plurality of first contact units 411 fixed to the upper surface of the support unit base 413. The substrate pressing unit 142 includes a plurality of second contact units 421 fixed to the lower surface of the top plate 123. The circumferential positions of the plurality of second contact units 421 are actually different from the circumferential positions of the plurality of first contact units 411.

[0059] The top plate 123 has a substantially circular plate shape that is perpendicular to the central axis J1. The top plate 123 is disposed below the chamber lid 122 and above the substrate support 141. The top plate 123 has an opening in the center. When the substrate W is supported by the substrate support 141, the upper surface 91 of the substrate W faces the lower surface of the top plate 123, which is perpendicular to the central axis J1. The diameter of the top plate 123 is larger than the diameter of the substrate W, and the outer periphery of the top plate 123 is located radially outward of the outer periphery of the substrate W along the entire periphery.

[0060] In the state shown in FIG. 8 , the top plate 123 is supported so as to be suspended by the chamber lid 122. The chamber lid 122 has a generally annular plate holding portion 222 in its center. The plate holding portion 222 includes a generally cylindrical tubular portion 223 centered on the central axis J1 and a generally disk-shaped flange portion 224 centered on the central axis J1. The flange portion 224 extends radially inward from the lower end of the tubular portion 223. The top plate 123 includes an annular held portion 237. The held portion 237 includes a generally cylindrical tubular portion 238 centered on the central axis J1 and a generally disk-shaped flange portion 239 centered on the central axis J1. The tubular portion 238 extends upward from the upper surface of the top plate 123. The flange portion 239 extends radially outward from the upper end of the tubular portion 238. The cylindrical portion 238 is located radially inside the cylindrical portion 223 of the plate holding portion 222. The flange portion 239 is located above the flange portion 224 of the plate holding portion 222 and faces the flange portion 224 in the up-down direction. The lower surface of the flange portion 239 of the held portion 237 comes into contact with the upper surface of the flange portion 224 of the plate holding portion 222, whereby the top plate 123 is attached to the chamber lid portion 122 so as to be suspended from the chamber lid portion 122.

[0061] The substrate rotation mechanism 15 shown in FIG. 8 is a so-called hollow motor. The substrate rotation mechanism 15 includes an annular stator portion 151 centered on a central axis J1 and an annular rotor portion 152. The rotor portion 152 includes a substantially annular permanent magnet. The surface of the permanent magnet is molded with PTFE resin. The rotor portion 152 is disposed within the lower annular space 217 in the chamber space 120 of the chamber 12. A support portion base 413 of the substrate support portion 141 is attached to the upper portion of the rotor portion 152 via a connecting member. The support portion base 413 is disposed above the rotor portion 152. The stator portion 151 is disposed around the rotor portion 152, i.e., radially outward, outside the chamber 12 (i.e., outside the chamber space 120). In this embodiment, the stator portion 151 is fixed to an outer wall portion 215 and a base portion 216 of the chamber bottom portion 210 and is located below the liquid receiving portion 16. The stator portion 151 includes a plurality of coils arranged in a circumferential direction around the central axis J1. When a current is supplied to the stator portion 151, a rotational force is generated between the stator portion 151 and the rotor portion 152 around the central axis J1. This causes the rotor portion 152 to rotate in a horizontal state around the central axis J1. Due to the magnetic force acting between the stator portion 151 and the rotor portion 152, the rotor portion 152 floats within the chamber 12 without directly or indirectly contacting the chamber 12, and rotates the substrate W together with the substrate support portion 141 in a floating state around the central axis J1.

[0062] The liquid receiving portion 16 includes a cup portion 161, a cup portion moving mechanism 162, and a cup opposing portion 163. The cup portion 161 is annular about the central axis J1 and is positioned radially outside the chamber 12 over its entire circumference. The cup portion moving mechanism 162 moves the cup portion 161 in the up and down direction. The cup portion moving mechanism 162 is disposed radially outside the cup portion 161. The cup portion moving mechanism 162 is disposed at a different circumferential position from the chamber opening / closing mechanism 131. The cup opposing portion 163 is positioned below the cup portion 161 and faces the cup portion 161 in the up and down direction. The cup opposing portion 163 is part of a member that forms the chamber side wall portion 214. The cup opposing portion 163 has an annular liquid receiving recess 165 that is positioned radially outside the chamber side wall portion 214.

[0063] The cup portion 161 includes a sidewall portion 611, an upper surface portion 612, and a bellows 617. The sidewall portion 611 is substantially cylindrical and centered on the central axis J1. The upper surface portion 612 is substantially annular and centered on the central axis J1, and extends radially inward and radially outward from the upper end of the sidewall portion 611. The lower portion of the sidewall portion 611 is located within the liquid receiving recess 165 of the cup opposing portion 163. The cross-sectional shape of the sidewall portion 611 differs between a portion where a nozzle unit 188 (described later) is housed (the portion on the right in FIG. 8) and the other portion (the portion on the left in FIG. 8). The portion of the sidewall portion 611 on the right in FIG. 8 is slightly thinner in the radial direction than the portion on the left in FIG. 8.

[0064] The bellows 617 has a substantially cylindrical shape centered on the central axis J1 and is expandable and contractible in the vertical direction. The bellows 617 is provided radially outward of the side wall portion 611, extending around the entire periphery of the side wall portion 611. The bellows 617 is formed of a material that does not allow gas or liquid to pass through. The upper end of the bellows 617 is connected to the lower surface of the outer edge of the upper surface portion 612 along the entire periphery. In other words, the upper end of the bellows 617 is indirectly connected to the side wall portion 611 via the upper surface portion 612. The connection between the bellows 617 and the upper surface portion 612 is sealed, preventing the passage of gas or liquid. The lower end of the bellows 617 is indirectly connected to the chamber main body 121 via the cup facing portion 163. The connection between the lower end of the bellows 617 and the cup facing portion 163 also prevents the passage of gas or liquid.

[0065] An upper nozzle 181 is fixed to the center of the chamber lid 122. The upper nozzle 181 can be inserted into a central opening in the top plate 123. The upper nozzle 181 has a liquid discharge port in the center and jet ports around it. A lower nozzle 182 is attached to the center of the lower surface facing portion 211 of the chamber bottom 210. A plurality of gas jet nozzles 180a are further attached to the lower surface facing portion 211. The plurality of gas jet nozzles 180a are arranged, for example, at equal angular intervals in the circumferential direction around the central axis J1. Note that the installation positions of the upper nozzle 181 and the lower nozzle 182 are not necessarily limited to the central portion, and may be, for example, positions facing the outer edge of the substrate W.

[0066] A nozzle unit 188 is attached to the upper surface 612 of the cup part 161. The nozzle unit 188 includes an atomizing nozzle 881 that sprays the chemical solution, and a nozzle support part 882. The nozzle support part 882 is a rod-shaped member that extends in a substantially horizontal direction. One end of the nozzle support part 882, which is a fixed end, is attached to the lower surface of the upper surface part 612 of the cup part 161. The atomizing nozzle 881 is fixed to the other end, which is a free end, of the nozzle support part 882. As a modified example, instead of the atomizing nozzle 881, which is a single-fluid nozzle, a two-fluid nozzle 171 (FIG. 4) may be provided together with the nitrogen supplier 350 (FIG. 4).

[0067] A nozzle moving mechanism 189 is provided on the top of the cup portion 161. The nozzle moving mechanism 189 is fixed to the top surface of the top surface portion 612 of the cup portion 161 above the fixed end of the nozzle support portion 882. The nozzle moving mechanism 189 includes a support portion rotation mechanism 891 and a support portion elevating mechanism 892. The support portion rotation mechanism 891 penetrates the top surface portion 612 of the cup portion 161 and is connected to the fixed end of the nozzle support portion 882, and rotates the nozzle support portion 882 together with the atomizing nozzle 881 in a substantially horizontal direction around the fixed end. The portion of the cup portion 161 penetrated by the support portion rotation mechanism 891 is sealed to prevent the passage of gas or liquid. The support portion elevating mechanism 892 moves the fixed end of the nozzle support portion 882 up and down, thereby raising and lowering the nozzle support portion 882 and the atomizing nozzle 881. The nozzle moving mechanism 189 is moved up and down together with the cup part 161 by the cup part moving mechanism 162 .

[0068] 9 is a block diagram showing the gas / liquid supply unit and gas / liquid exhaust unit of the substrate processing apparatus 113. In addition to the nozzle unit 188, gas ejection nozzle 180a, upper nozzle 181, and lower nozzle 182, the gas / liquid supply unit includes an ozone supply unit 200, a chemical supply unit 300, a pure water supply unit 184, an IPA supply unit 185, and a heated gas supply unit 187. The chemical supply unit 300 is connected to the nozzle unit 188 via a valve. The pure water supply unit 184 and the IPA supply unit 185 are each connected to the upper nozzle 181 via a valve. The lower nozzle 182 is connected to the pure water supply unit 184 via a valve. The upper nozzle 181 is also connected to the ozone supply unit 200 via a valve. The upper nozzle 181 is part of a gas supply unit that supplies gas to the interior of the chamber 12. The gas ejection nozzles 180a are connected to the heated gas supply unit 187 via a valve.

[0069] The first discharge path 191 connected to the liquid receiving recess 165 of the liquid receiving part 16 is connected to a gas-liquid separation part 193. The gas-liquid separation part 193 is connected to an outer exhaust part 194, a chemical solution recovery part 195, and a drain part 196, each via a valve. The second discharge path 192 connected to the chamber bottom part 210 is connected to a gas-liquid separation part 197. The gas-liquid separation part 197 is connected to an inner exhaust part 198 and a drain part 199, each via a valve.

[0070] The chemical liquid supply unit 300 supplies a heated chemical liquid containing sulfuric acid, as described in the substrate processing apparatus 111 (FIG. 4: embodiment 1). The deionized water supply unit 184 supplies deionized water (DIW) onto the substrate W via the upper nozzle 181 or the lower nozzle 182. The IPA supply unit 185 supplies isopropyl alcohol (IPA) onto the substrate W via the upper nozzle 181. The substrate processing apparatus 113 may be provided with a processing liquid supply unit that supplies a processing liquid other than the above-mentioned processing liquids (the above-mentioned chemical liquids, deionized water, and IPA).

[0071] The ozone supply unit 200 supplies an ozone-containing gas into the chamber 12, as described in the substrate processing apparatus 111 (FIG. 4: Embodiment 1). In this embodiment, the supply is performed via the upper nozzle 181. The heated gas supply unit 187 supplies heated gas (e.g., high-temperature inert gas heated to 160 to 200°C) to the lower surface 92 of the substrate W via a plurality of gas ejection nozzles 180a. In this embodiment, the gas used in the heated gas supply unit 187 is nitrogen gas, but gas other than nitrogen gas may also be used. Note that when heated inert gas is used in the heated gas supply unit 187, explosion prevention measures in the substrate processing apparatus 113 can be simplified or may be unnecessary.

[0072] As shown in FIG. 8, a plurality of first engagement portions 241 are arranged in the circumferential direction on the lower surface of the outer edge of the top plate 123, and a plurality of second engagement portions 242 are arranged in the circumferential direction on the upper surface of the support base 413. In reality, the first engagement portions 241 and the second engagement portions 242 are arranged at different positions in the circumferential direction from the plurality of first contact portions 411 of the substrate support portion 141 and the plurality of second contact portions 421 of the substrate presser portion 142. It is preferable to provide three or more sets of these engagement portions, and in this embodiment, four sets are provided. An upwardly recessed recess is provided at the bottom of the first engagement portion 241. The second engagement portion 242 protrudes upward from the support base 413.

[0073] Hereinafter, a substrate processing method for removing an organic film from the substrate W using the substrate processing apparatus 113 (FIGS. 8 and 9) will be described.

[0074] As shown in FIG. 10, in step S11 (FIG. 3), with the chamber lid 122 positioned above and spaced apart from the chamber body 121 and the cup 161 positioned below and spaced apart from the chamber lid 122, the substrate W is loaded into the chamber 12 by an external transfer mechanism and supported from below by the substrate support 141. Hereinafter, the state of the chamber 12 and the cup 161 shown in FIG. 10 will be referred to as the "open state." The opening between the chamber lid 122 and the chamber sidewall 214 is annular about the central axis J1 and will be referred to as the "annular opening 81" below. In the substrate processing apparatus 113, the chamber lid 122 is moved away from the chamber body 121, thereby forming the annular opening 81 around (i.e., radially outward from) the substrate W. In step S11, the substrate W is loaded through the annular opening 81.

[0075] When the substrate W is loaded, the nozzle unit 188 is accommodated in advance in the space 160 formed between the cup portion 161 and the cup opposing portion 163. The space 160 is a substantially annular space that surrounds the entire outer periphery of the chamber 12. In the following description, the space 160 will be referred to as the "side space 160." FIG. 11 is a plan view of the substrate processing apparatus 113. In FIG. 11, the chamber lid portion 122, the cup portion 161, etc. are not shown in order to make it easier to understand the accommodated state of the nozzle unit 188. The bellows 617 are hatched.

[0076] 11, the nozzle support portion 882 of the nozzle unit 188 is curved so as to be convex radially outward in a plan view. In other words, the nozzle unit 188 is substantially arc-shaped. In the side space 160, the nozzle unit 188 is disposed so that the nozzle support portion 882 is aligned with the bellows 617 and the side wall portion 611 of the cup portion 161 (see FIG. 10).

[0077] When the nozzle unit 188 is accommodated, with the cup portion 161 positioned at the position shown in Fig. 8, the nozzle unit 188 is rotated by the support portion rotation mechanism 891 and moved to the outside of the chamber 12 via the annular opening 81. As a result, the nozzle unit 188 is accommodated in the side space 160 between the cup portion 161 and the cup opposing portion 163. Thereafter, the cup portion moving mechanism 162 lowers the cup portion 161 to the position shown in Fig. 10. As the cup portion 161 lowers, the side space 160 becomes smaller.

[0078] 12, and is positioned radially outside the annular opening 81 over the entire circumference. In the following description, the state of the chamber 12 and the cup portion 161 shown in FIG. 12 will be referred to as the "first sealed state" (the same applies to the state in FIG. 8). Furthermore, the position of the cup portion 161 shown in FIG. 12 will be referred to as the "liquid receiving position," and the position of the cup portion 161 shown in FIG. 10 will be referred to as the "retracted position." The cup portion moving mechanism 162 moves the cup portion 161 up and down between the liquid receiving position radially outside the annular opening 81 and a retracted position below the liquid receiving position.

[0079] When the cup portion 161 is positioned at the liquid receiving position, the side wall portion 611 faces the annular opening 81 in the radial direction. The upper surface of the inner edge of the top surface portion 612 contacts the lip seal 232 at the lower end of the outer edge of the chamber lid portion 122 along its entire circumference. A seal that prevents the passage of gas or liquid is formed between the chamber lid portion 122 and the top surface portion 612 of the cup portion 161. This forms a sealed space surrounded by the chamber body 121, chamber lid portion 122, cup portion 161, and cup opposing portion 163 (hereinafter referred to as the "expanded sealed space 100"). The expanded sealed space 100 is a single space formed by communication between the chamber space 120 between the chamber lid portion 122 and the chamber body 121 and the side space 160 surrounded by the cup portion 161 and the cup opposing portion 163 via the annular opening 81.

[0080] Next, step S12 (FIG. 3) is started to remove an organic film from the substrate W. Specifically, the substrate rotation mechanism 15 starts rotating the substrate W at a constant rotation speed (a relatively low rotation speed, hereinafter referred to as "steady rotation speed"). Furthermore, the ozone supply unit 200 (see FIG. 9) starts supplying an ozone-containing gas to the expanded sealed space 100 (corresponding to step ST10 (FIG. 5)), and the outer exhaust unit 194 starts exhausting the gas from the expanded sealed space 100. As a result, after a predetermined time has elapsed, the expanded sealed space 100 becomes filled with the ozone-containing gas (corresponding to step ST20 (FIG. 5)). The supply of the ozone-containing gas to the expanded sealed space 100 and the exhaust of the gas from the expanded sealed space 100 may be performed from the open state shown in FIG. 10.

[0081] Next, heated gas is ejected from the multiple gas ejection nozzles 180a toward the lower surface 92 of the rotating substrate W. This heats the substrate W. Also, a predetermined amount of chemical liquid is supplied from the chemical liquid supply unit 300 to the nozzle unit 188 attached to the cup portion 161 in the side space 160. This allows pre-dispensing from the atomizing nozzle 881 to be performed in a state where the nozzle unit 188 is housed in the side space 160 (i.e., a state where the entire nozzle unit 188 is positioned within the side space 160). The chemical liquid pre-dispensed from the atomizing nozzle 881 is received in the liquid receiving recess 165.

[0082] 8, the support part rotation mechanism 891, which is arranged outside the enlarged sealed space 100, rotates the nozzle support part 882, and the atomizing nozzle 881 moves above the substrate W through the annular opening 81. Furthermore, the control unit 10 controls the support part rotation mechanism 891, and the atomizing nozzle 881 starts to move back and forth above the substrate W. The atomizing nozzle 881 continuously moves back and forth horizontally along a predetermined movement path that connects the center and outer edge of the substrate W.

[0083] Then, the chemical liquid is supplied from the chemical liquid supply unit 300 to the atomizing nozzle 881, and the chemical liquid begins to be sprayed from the atomizing nozzle 881, which is swinging horizontally, onto the upper surface 91 of the substrate W (corresponding to step ST40 (FIG. 5)). The chemical liquid spreads to the outer periphery as the substrate W rotates, and the entire upper surface 91 is covered with the chemical liquid. By continuing to spray the chemical liquid from the atomizing nozzle 881, which swings horizontally, onto the rotating substrate W (corresponding to step ST50 (FIG. 5)), the chemical liquid can be supplied approximately uniformly to the upper surface 91 of the substrate W. This can also improve the temperature uniformity of the chemical liquid on the substrate W. As a result, the uniformity of the chemical liquid processing on the substrate W can be improved.

[0084] While the chemical liquid is being sprayed from the nozzle unit 188, the heated gas continues to be ejected from the gas ejection nozzle 180a. This allows the upper surface 91 to be cleaned with the chemical liquid while the substrate W is heated to approximately the desired temperature. As a result, the uniformity of the chemical liquid processing on the substrate W can be further improved.

[0085] In the expanded sealed space 100, the chemical solution splashed from the upper surface 91 of the rotating substrate W is received by the cup portion 161 through the annular opening 81 and is guided to the liquid receiving recess 165. The chemical solution guided to the liquid receiving recess 165 flows into the gas-liquid separation portion 193 through the first discharge path 191 shown in Fig. 9. In the chemical solution recovery portion 195, the chemical solution is recovered from the gas-liquid separation portion 193, and after impurities and the like are removed from the chemical solution through a filter or the like, the chemical solution is reused.

[0086] After a predetermined time (e.g., 60 to 120 seconds) has elapsed since the start of the supply of the chemical liquid, the supply of the chemical liquid from the nozzle unit 188 and the supply of the heated gas from the gas ejection nozzle 180a are stopped (corresponding to step ST60 (FIG. 5)). Furthermore, the introduction of the ozone-containing gas from the ozone supply unit 200 (see FIG. 9) is stopped (corresponding to step ST30 (FIG. 5)). Subsequently, the substrate rotation mechanism 15 increases the rotation speed of the substrate W above the steady rotation speed for a predetermined time (e.g., 1 to 3 seconds), thereby removing the chemical liquid from the substrate W. Furthermore, the support part rotation mechanism 891 rotates the nozzle unit 188, and as shown in FIG. 12, the nozzle unit 188 moves from the chamber space 120 to the side space 160 via the annular opening 81.

[0087] As the nozzle unit 188 moves toward the side space 160, the chamber lid 122 and the cup 161 move downward in synchronization. Then, as shown in FIG. 13 , the lip seal 231 at the lower end of the outer edge of the chamber lid 122 comes into contact with the upper portion of the chamber sidewall 214, closing the annular opening 81 and sealing the chamber space 120 in a state where it is isolated from the side space 160. The cup 161 is positioned in the retracted position, as in FIG. 10 . The side space 160 is sealed in a state where it is isolated from the chamber space 120. Hereinafter, the state of the chamber 12 and the cup 161 shown in FIG. 13 will be referred to as the "second sealed state." In the second sealed state, the substrate W directly faces the inner wall of the chamber 12, and no other liquid receiving portion is present between them. Furthermore, the nozzle unit 188 is housed in the side space 160, isolated from the chamber space 120.

[0088] In the second sealed state, the plurality of second contact portions 421 of the substrate holding portion 142 contact the outer edge of the substrate W. A plurality of pairs of magnets (not shown) facing each other in the vertical direction are provided on the lower surface of the top plate 123 and on the support portion base 413 of the substrate support portion 141. Hereinafter, each pair of magnets will also be referred to as a "magnet pair." In the substrate processing apparatus 113, the plurality of magnet pairs are arranged at equal angular intervals in the circumferential direction at positions different from the first contact portion 411, the second contact portion 421, the first engagement portion 241, and the second engagement portion 242. When the substrate holding portion 142 is in contact with the substrate W, a downward force acts on the top plate 123 due to a magnetic force (attractive force) acting between the magnet pairs. This causes the substrate holding portion 142 to press the substrate W against the substrate support portion 141.

[0089] In the substrate processing apparatus 113, the substrate holding portion 142 presses the substrate W against the substrate support portion 141 using the weight of the top plate 123 and the magnetic force of the magnet pair, thereby firmly holding the substrate W between the substrate holding portion 142 and the substrate support portion 141 from above and below.

[0090] In the second sealed state, the flange portion 239 of the held portion 237 is spaced above the flange portion 224 of the plate holding portion 222, and the plate holding portion 222 and the held portion 237 do not come into contact with each other. In other words, the plate holding portion 222 no longer holds the top plate 123. Therefore, the top plate 123 rotates by the substrate rotation mechanism 15 together with the substrate holding portion 14 and the substrate W held by the substrate holding portion 14, independently of the chamber lid portion 122.

[0091] Furthermore, in the second sealed state, the second engagement portion 242 fits into a recess in the lower part of the first engagement portion 241. As a result, the top plate 123 engages with the support portion base 413 of the substrate support portion 141 in the circumferential direction centered on the central axis J1. In other words, the first engagement portion 241 and the second engagement portion 242 are position restriction members that restrict the relative position of the top plate 123 with respect to the substrate support portion 141 in the rotational direction (i.e., fix the relative position in the circumferential direction). When the chamber lid portion 122 descends, the substrate rotation mechanism 15 controls the rotational position of the support portion base 413 so that the first engagement portion 241 and the second engagement portion 242 fit together.

[0092] Once the chamber space 120 and the side space 160 are independently sealed, the outer exhaust unit 194 (see FIG. 9) stops discharging gas, and the inner exhaust unit 198 starts discharging gas from the chamber space 120. The pure water supply unit 184 starts supplying pure water as a rinse liquid to the substrate W (step S13 (FIG. 3)).

[0093] The pure water from the pure water supply unit 184 is discharged from the upper nozzle 181 and the lower nozzle 182 and continuously supplied to the central portions of the upper surface 91 and the lower surface 92 of the substrate W. The pure water spreads to the outer peripheries of the upper surface 91 and the lower surface 92 as the substrate W rotates, and splashes outward from the outer periphery of the substrate W. The pure water splashed from the substrate W is received by the inner walls of the chamber 12 (i.e., the inner walls of the chamber lid 122 and the chamber sidewall 214) and is discarded via the second discharge path 192, the gas-liquid separator 197, and the drain 199 shown in FIG. 9 (the same applies to the drying process of the substrate W described below). This essentially performs the rinsing process of the upper surface 91 of the substrate W and the cleaning process of the lower surface 92, as well as the cleaning of the inside of the chamber 12.

[0094] After a predetermined time has elapsed since the start of the supply of pure water, the supply of pure water from the pure water supply unit 184 is stopped. Then, in the chamber space 120, the rotation speed of the substrate W is made sufficiently higher than the steady rotation speed. As a result, the pure water is removed from the substrate W, and the substrate W is dried (step S14 (FIG. 3)). After a predetermined time has elapsed since the start of drying of the substrate W, the rotation of the substrate W is stopped. The drying process of the substrate W may be performed in a reduced pressure atmosphere lower than atmospheric pressure by decompressing the chamber space 120 by the inner exhaust unit 198. Note that after the supply of pure water by the pure water supply unit 184 and before drying the substrate W, IPA may be supplied onto the substrate W from the IPA supply unit 185 to replace the pure water on the substrate W with IPA.

[0095] Thereafter, the chamber lid 122 and the top plate 123 are raised, and the chamber 12 is opened as shown in Fig. 10. In step S14, the top plate 123 rotates together with the substrate support 141, so that almost no liquid remains on the underside of the top plate 123, and no liquid falls from the top plate 123 onto the substrate W when the chamber lid 122 is raised. The substrate W is then transferred from the chamber 12 by an external transfer mechanism (step S15 (Fig. 3)).

[0096] The chamber opening / closing mechanism 131 does not necessarily have to move the chamber lid 122 up and down; it may move the chamber body 121 up and down while the chamber lid 122 is fixed. The chamber 12 is not necessarily limited to a substantially cylindrical shape and may have various shapes. The shapes and structures of the stator 151 and rotor 152 of the substrate rotation mechanism 15 may be modified in various ways. The rotor 152 does not necessarily have to rotate in a floating state; a structure such as a guide that mechanically supports the rotor 152 may be provided within the chamber 12, and the rotor 152 may rotate along the guide. The substrate rotation mechanism 15 does not necessarily have to be a hollow motor; a rotary shaft motor may be used as the substrate rotation mechanism. In the substrate processing apparatus 113, the expanded sealed space 100 may be formed by contacting a portion of the (outer) cup 161 other than the upper surface 612 (e.g., the side wall 611) with the chamber lid 122. The shapes of the (outer) cup portion 161 and the inner cup portion 161a may be changed as appropriate.

[0097] According to the third embodiment, it is possible to ensure high airtightness of the chamber 12 in which the treatment using ozone is performed. Although the above description has been given in detail of the case where the same flow as that shown in Fig. 5 (first embodiment) is performed in the third embodiment, a flow similar to that shown in Fig. 7 (second embodiment) may be performed instead. In this case, at least one of the pressure gauge 250 (Fig. 6: second embodiment) and the ozone concentration meter may be provided to measure the atmosphere in the chamber 12 (Fig. 8).

[0098] The configurations and steps described in the above embodiments and modifications can be combined or omitted as appropriate as long as they are not mutually contradictory. [Explanation of symbols]

[0099] 10: Control section 12: Chamber (substrate processing chamber) 14: Spin chuck (substrate holder) 17: Cover 110: Processing unit 111 to 113: Substrate processing equipment 161: Cup part 171: Two-fluid nozzle (atomizing nozzle) 200: Ozone supply unit 250: Pressure gauge 300: Chemical supply unit 301: Sulfuric acid tank 302: Pressure adjustment unit 303: Heater 310: Three-way valve 350: Nitrogen supply unit 881: Atomizing nozzle LR1: 1st liquid LR2: 2nd liquid W: Substrate

Claims

1. A substrate processing method for removing an organic film from a substrate, comprising: a) introducing an ozone-containing gas into a substrate processing chamber to fill at least a space above the substrate in the substrate processing chamber with the ozone-containing gas; b) after step a), starting to spray a heated chemical solution containing sulfuric acid onto the substrate through the space using a flow of inert gas; c) continuing the spraying initiated by step b); d) stopping the spraying that has been continued in step c); Equipped with the step a) includes a step of confirming that a measured value of at least one of a pressure and an ozone concentration in the substrate processing chamber is equal to or greater than a predetermined threshold value; The substrate processing method, wherein the step b) is performed after the step a) so as to start spraying the chemical onto the substrate through the space when the measured value is equal to or greater than the threshold value.

2. 2. The substrate processing method according to claim 1, A substrate processing method, wherein after the introduction of an ozone-containing gas into the substrate processing chamber is performed in the step a), the introduction is continued in the steps b) and c).

3. 2. The substrate processing method according to claim 1, A substrate processing method, wherein after the introduction of the ozone-containing gas into the substrate processing chamber is performed in the step a), the introduction is stopped before the step c).

4. A substrate processing apparatus for removing an organic film from a substrate, comprising: a substrate processing chamber; a substrate holder that holds the substrate in the substrate processing chamber; an ozone supply unit that supplies an ozone-containing gas into the substrate processing chamber; an atomizing nozzle that sprays the chemical solution onto the substrate by utilizing a flow of inert gas; an inert gas supply unit that supplies the inert gas to the atomizing nozzle; a chemical liquid supply unit having a heater and supplying the chemical liquid heated by the heater to the atomization nozzle; a control unit that controls the ozone supply unit so as to fill at least a space above the substrate in the substrate processing chamber with an ozone-containing gas; Equipped with the control unit confirms that at least one of a pressure and an ozone concentration measured in the substrate processing chamber is equal to or greater than a predetermined threshold when the space is filled with the ozone-containing gas; The control unit controls the chemical liquid supply unit to start spraying the chemical liquid onto the substrate through the space when the measurement value is greater than or equal to the threshold value after filling the space with the ozone-containing gas.

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