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 a substrate processing apparatus for removing an organic film from a substrate, which may include, for example, a semiconductor wafer, a substrate for FPD (Flat Panel Display) such as a liquid crystal display device and 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] A manufacturing method of a semiconductor device usually requires a process for cleaning a substrate. Typically, a cleaning process is performed to remove an unnecessary organic film (typically a resist film) from the substrate. For example, according to JP 2016-181677 A (Patent Document 1), SPM cleaning is performed on the surface of a substrate using a sulfuric acid / hydrogen peroxide mixture (SPM) as a chemical solution. However, this process consumes a large amount of SPM. Since SPM is difficult to reuse efficiently, the burden of chemical costs and waste liquid treatment is large. Therefore, in recent years, a substrate processing method that can reduce the burden of material costs and the burden of waste liquid treatment has been studied. As one of such methods, SOM cleaning, which uses a sulfuric acid and ozone mixture (SOM) as a chemical solution instead of SPM, is being studied. By mixing sulfuric acid and ozone, peroxodisulfate ions (SO2O8 2- ) is generated.

[0003] For example, according to JP 2013-150007 A (Patent Document 2), sulfuric acid containing microbubbles of ozone gas is supplied to a substrate from a nozzle. Also, according to U.S. Patent No. 6,869,487 (Patent Document 3), ozone is allowed to reach the surface of the substrate by diffusion through the liquid layer by controlling the thickness of the liquid layer on the substrate. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2016-181677 A [Patent Document 2] JP 2013-150007 A [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 is easily decomposed quickly in sulfuric acid. Therefore, as in the technology of JP 2013-150007 A, when ozone is already contained in sulfuric acid before it is discharged from the nozzle, a lot of ozone is easily decomposed at an excessively early point before it reaches the vicinity of the substrate. Correspondingly, the generation of active species by decomposition of ozone is also easily performed at an excessively early point, and as a result, many of the active species are deactivated before they reach the substrate. Therefore, it is difficult to perform substrate processing using active species with high efficiency. In addition, if the ozone concentration is increased by increasing the pressure at which ozone is contained in the chemical solution, the processing efficiency may be increased accordingly, but it is practically difficult to stably maintain the high pressure state required to obtain a significant effect.

[0006] According to the above-mentioned U.S. Patent No. 6,869,487, ozone diffusion is required to penetrate the liquid layer on the substrate. However, according to the study by 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 an organic film from a substrate 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) a step of 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), a step of starting spraying a heated chemical solution containing sulfuric acid onto the substrate through the space; c) a step of continuing the spraying started in the step b); and d) a step of stopping the spraying continued in the step c).

[0009] A second aspect of the present invention is the substrate processing method of the first aspect, wherein the 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 an 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 which is received in a cup portion surrounding the substrate and recovered, and a second liquid which is recovered 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, the apparatus 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; a spraying 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 spraying 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 an ozone-containing gas, and then controlling the chemical solution supply unit to start spraying the chemical solution onto the substrate through the space. Effect of the Invention

[0014] According to the first and sixth aspects of the present invention, firstly, ozone, not hydrogen peroxide solution, is mixed into the heated chemical solution containing sulfuric acid. This makes it easier to efficiently reuse the chemical solution. Therefore, it is possible to suppress the burden of chemical solution costs and the load of waste liquid treatment. Secondly, the mixing is performed in the space above the substrate. This prevents the decomposition of ozone at an excessively early point before it reaches the vicinity of the substrate, even though high-temperature sulfuric acid that easily decomposes ozone is used. Therefore, the activated species generated by the decomposition of ozone reach the substrate before deactivation at a high rate. On the other hand, the mixing is performed by spraying the chemical solution into the ozone-containing gas. The spraying provides the chemical solution with a large surface area, which promotes the reaction between the chemical solution and the ozone around it. 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, this large amount of activated species reaches the substrate at a high rate before deactivation. Therefore, the process of removing an organic film from a substrate using activated species can be performed with high efficiency. Fourth, when the chemical solution is sprayed, the space is already filled with ozone-containing gas. This activates the reaction between the chemical solution and ozone in the space from the start of spraying the chemical solution. This makes it possible to reduce the amount of chemical solution required for processing. As a result, it is possible to remove organic films from substrates with high efficiency while reducing the burden of chemical solution costs and waste liquid processing.

[0015] According to the second aspect of the present invention, spraying is started after it is confirmed 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, so that the amount of ozone in the space can be more reliably made sufficient at the start of spraying the chemical liquid.

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

[0017] According to the fourth aspect of the present invention, the introduction of the ozone-containing gas is stopped during the spraying of the chemical solution, thereby making it possible to suppress the consumption of the ozone-containing gas.

[0018] According to the fifth aspect of the present invention, a part of the sprayed chemical liquid is re-sprayed. This makes it possible to further reduce the burden of chemical liquid costs and waste liquid treatment. In addition, by not including the chemical liquid received in the cup part in the chemical liquid to be re-sprayed, it is possible to avoid re-spraying of the contaminated chemical liquid 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 description of the drawings]

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

[0021] Hereinafter, the embodiments will be described with reference to the attached 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 the embodiment to be feasible. The drawings are shown in a schematic manner, and for the convenience of explanation, the configuration may be omitted or simplified as appropriate in the drawings. In addition, the interrelationship between the size and position of the configurations shown in different drawings is not necessarily described accurately, and may be changed as appropriate. In addition, hatching may be added to drawings such as plan views that are not cross-sectional views in order to make it easier to understand the contents of the embodiment. In addition, in the following description, similar components are illustrated with 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 addition, in the following description, when a certain component is described as "having", "including", or "having", unless otherwise specified, it is not an exclusive expression that excludes the existence of other components.

[0022] <Substrate processing system> 1 is a plan view illustrating a schematic configuration example 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 device 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 contains the substrate W. The load port LP is a container holding mechanism that holds a plurality of carriers C. The indexer robot IR can transport the substrate W between the load port LP and the substrate platform PS. The center robot CR can transport the substrate 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 the substrate W between each processing unit 110 and the load port LP.

[0024] The unprocessed substrate W is removed from the carrier C by the indexer robot IR. The unprocessed substrate W is then handed over to the center robot CR via the substrate placement part 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 is then passed through other processing units 110 as necessary, and then handed over to the indexer robot IR via the substrate placement part 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 diagram conceptually illustrating an example of the configuration of the control unit 10 shown in FIG. 1. The control unit 10 controls the processing unit 110, the load port LP, the indexer robot IR, the center robot CR, and the like, which are shown in FIG. 1. The control unit 10 may be configured by a general computer having an electric circuit. 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, and a bus line 1015 that interconnects these units.

[0026] The ROM 1012 stores a basic program. The RAM 1013 is used as a working area when the CPU 1011 performs a predetermined process. The storage device 1014 is composed of a non-volatile 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 a lamp, 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) or the like.

[0027] 3 is a flow diagram that illustrates a schematic of a substrate processing method using the substrate processing system 1 of FIG. 1. In step S11 (FIG. 3), the substrate W having an organic film to be removed is loaded from the carrier C into the substrate processing chamber of the processing unit 110 by using the indexer robot IR and the center robot CR in sequence. In step S12 (FIG. 3), a process of removing the organic film from the substrate W (described in detail later) is performed. In step S13 (FIG. 3), a rinsing liquid is supplied to the substrate W, thereby performing a rinsing process on the substrate W. In step S14 (FIG. 3), the substrate W is dried. In step S15 (FIG. 3), the substrate W is unloaded from the substrate processing chamber of the processing unit 110 to the carrier C by using the center robot CR and the indexer robot IR in sequence.

[0028] A plurality of modes for controlling each component in the substrate processing system 1 of FIG. 1 are preset in the storage device 1014. When the CPU 1011 executes the processing program 1014P, one of the above-mentioned 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. In addition, some or all of the functions executed by the control unit 10 do not necessarily need to be realized by software, and may be realized by hardware such as a dedicated logic circuit.

[0029] <Embodiment 1> 4, in the first embodiment, as at least one of the processing units 110 (FIG. 1), a substrate processing apparatus 111 for removing an organic film (e.g., a resist film) from a substrate W is applied. The substrate processing apparatus 111 includes a chamber 12 (substrate processing chamber), a spin chuck 14 (substrate holding unit), 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 shaft, 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 in the chamber 12 via a valve. An end of the pipe constituting a supply port for the ozone-containing gas is attached to the chamber 12, and the height position of the pipe 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 the 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 It is preferable that the thickness is less than 250 g / m 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 atomizing nozzle that sprays the chemical onto the substrate W. By being sprayed, the chemical is supplied into the chamber 12 as fine particles FM. During spraying, the two-fluid nozzle 171 uses a high-speed flow of gas supplied from the nitrogen supply unit 350 to easily make the particles FM of the sprayed chemical finer than in the case of a one-fluid nozzle. This makes it possible to increase the surface area of ​​the sprayed chemical. Note that, if the desired spraying can be performed using a one-fluid nozzle, a one-fluid nozzle that atomizes the chemical without using the nitrogen supply unit 350 may be used as the atomizing nozzle instead of the two-fluid nozzle 171. The nozzle moving mechanism 172 moves the two-fluid nozzle 171 horizontally. The nozzle moving mechanism 172 may have an arm that supports the two-fluid nozzle 171 and an actuator that drives the arm.

[0035] The cup section 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 section 161 that opens upward is disposed above the spin base 143. Therefore, the chemical liquid discharged around the substrate W is received by the cup section 161. Then, the first liquid LR1, which is the chemical liquid that is received and collected by the cup section 161, is sent to the waste liquid section 320. In addition, the second liquid LR2, which is the chemical liquid that is collected outside the cup section 161, of the sprayed chemical liquid can return to the chemical liquid supply section 300 through a pipe provided with a valve. The pipe is connected to the pipe of the chemical liquid supply section 300 by a three-way valve 310. By switching the three-way valve 310, a state in which the chemical liquid supply unit 300 uses the chemical liquid in the sulfuric acid tank 301 and a state in which the chemical liquid supply unit 300 uses the second liquid LR2 are switched. 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 connected to the space in the chamber 12 via a valve. When the valve is open, the exhaust unit 190 exhausts the atmosphere in the chamber 12 to the outside of the chamber 12. The end of this pipe constituting the exhaust port of the chamber 12 is attached to the chamber 12 in FIG. 4, but may be attached to the cup portion 161 instead. 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 regarded as a part of the substrate processing apparatus 111.

[0038] In the following, the SOM cleaning for removing an organic film from the substrate W by the substrate processing apparatus 111 (FIG. 4), which corresponds to step S12 (FIG. 3), 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 ozone-containing gas is introduced to fill at least the space above the substrate W in the chamber 12 with the ozone-containing gas. Whether or not the chamber 12 is filled with the ozone-containing gas may be defined by whether or not at least one of the pressure and the ozone concentration in the chamber 12 is equal to or higher than a threshold value. The threshold pressure is preferably equal to or higher than 0.1 MPa and equal to or lower than 0.3 MPa. The threshold concentration is preferably 100 g / m 3 More than 400g / m 3 It is preferable that the thickness is less than 250 g / m 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 for confirming that the measured value is equal to or greater than the threshold value may be performed. 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] Prior to step ST40 (FIG. 5) described later, the spin chuck 14 starts to rotate 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 SO8. 2- In step ST50 (FIG. 5), the spraying started in step ST40 is continued.

[0041] In step ST60 (FIG. 5), the spraying continued in step ST50 is stopped. Specifically, the chemical supply unit 300 stops the supply of the chemical liquid to the two-fluid nozzle 171, and the nitrogen supply unit 350 stops the supply of the nitrogen gas. The timing at which the spraying is stopped may be, for example, a time point after a predetermined time from the time point at which the spraying is started. 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), the 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 the introduction of the ozone-containing gas.

[0042] The SOM cleaning is performed as described above. The above-mentioned SOM cleaning may be a substrate treatment that at least partially removes the organic film, and if a portion of the organic film remains immediately after the SOM cleaning, an 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 later.

[0043] The chemical liquid sprayed in step ST50 (FIG. 5) is separated into a first liquid LR1 that is received by the cup portion 161 surrounding the substrate W and collected, and a second liquid LR2 that is collected outside the cup portion 161. Thereafter, the second liquid LR2 may be re-sprayed without containing the first liquid LR1. Specifically, 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, by switching the three-way valve 310. The second liquid LR2 may be re-sprayed onto the substrate W that was being processed while the second liquid LR2 was being collected, or onto another substrate W. These features may also be applied to the second embodiment 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 has 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] In the following, the SOM cleaning for removing an organic film from the substrate W by the substrate processing apparatus 112 (FIG. 6), which corresponds to step S12 (FIG. 3), will be described in more detail.

[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 to fill 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 measured pressure value obtained by the pressure gauge 250 is equal to or higher than a predetermined threshold pressure. In addition to or instead of this confirmation, it may be confirmed that the measured ozone concentration value in the chamber 12 is equal to or higher 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 the above 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] Prior to step ST40 (FIG. 7), the spin chuck 14 starts to rotate 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 SO8. 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 time point a predetermined time after the time point at which the spraying is started. 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.

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

[0051] <Embodiment 3> 8, in the third embodiment, a substrate processing apparatus 113 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 113 is a single-wafer type apparatus for processing substantially disk-shaped substrates W one by one. In FIG. 8, hatching is omitted in cross sections of a portion of the configuration of the substrate processing apparatus 113 (this is also true for 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 section 16, and a cover 17. The cover 17 covers the chamber 12 from above and sides.

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

[0054] The chamber sidewall 214 is annular about the central axis J1. The chamber sidewall 214 protrudes upward from the inner edge of the base portion 216. The member forming the chamber sidewall 214 also serves as part of the liquid receiving portion 16, as described below. In the following description, a 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 a 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 is referred to as the "lower surface facing part 211," and the upper surface 211a of the central part 211 is 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. Figure 8 shows a state in which the chamber lid 122 is 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 lifts and lowers the chamber lid 122. When the chamber lid 122 moves in the vertical direction by the chamber opening / closing mechanism 131, 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) in the chamber 12. In other words, the upper opening of the chamber body 121 is closed by the chamber lid 122, thereby sealing the chamber space 120.

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

[0059] The top plate 123 has a generally circular plate shape 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 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 from the outer periphery of the substrate W over the entire circumference.

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

[0061] The substrate rotating mechanism 15 shown in FIG. 8 is a so-called hollow motor. The substrate rotating 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 in 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 outside the chamber 12 (i.e., outside the chamber space 120), i.e., radially outward. In this embodiment, the stator portion 151 is fixed to the outer wall portion 215 and the 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 a magnetic force acting between the stator portion 151 and the rotor portion 152, the rotor portion 152 floats in 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 the entire circumference. The cup portion moving mechanism 162 moves the cup portion 161 in the up-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 position in the circumferential direction from the above-mentioned 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-down direction. The cup opposing portion 163 is a part of a member forming the chamber side wall portion 214. The cup opposing portion 163 has an annular liquid receiving recess 165 positioned radially outside the chamber side wall portion 214.

[0063] The cup portion 161 includes a side wall portion 611, an upper surface portion 612, and a bellows 617. The side wall 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 spreads radially inward and radially outward from the upper end of the side wall portion 611. The lower portion of the side wall portion 611 is located within the liquid receiving recess 165 of the cup opposing portion 163. The cross-sectional shape of the side wall portion 611 is different between a portion (the portion on the right side in FIG. 8) in which a nozzle unit 188 (described later) is housed and the other portion (the portion on the left side in FIG. 8). The portion on the right side in FIG. 8 of the side wall portion 611 is slightly thinner in the radial direction than the portion on the left side in FIG. 8.

[0064] The bellows 617 is substantially cylindrical with the central axis J1 as the center, and is expandable and contractable in the vertical direction. The bellows 617 is provided on the radially outer side of the sidewall portion 611, all around the periphery of the sidewall portion 611. The bellows 617 is made 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 all around. In other words, the upper end of the bellows 617 is indirectly connected to the sidewall portion 611 via the upper surface portion 612. The connection portion between the bellows 617 and the upper surface portion 612 is sealed, and the passage of gas or liquid is prevented. The lower end of the bellows 617 is indirectly connected to the chamber main body 121 via the cup facing portion 163. The connection portion 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 an opening in the center of the top plate 123. The upper nozzle 181 has a liquid discharge port in the center and ejection 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 ejection nozzles 180a are further attached to the lower surface facing portion 211. The plurality of gas ejection nozzles 180a are arranged, for example, at equal angular intervals in the circumferential direction centered on 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 portion 612 of the cup portion 161. The nozzle unit 188 includes an atomizing nozzle 881 that sprays a chemical solution, and a nozzle support portion 882. The nozzle support portion 882 is a rod-shaped member extending in a substantially horizontal direction. One end of the nozzle support portion 882, which is a fixed end, is attached to the lower surface of the upper surface portion 612 of the cup portion 161. The atomizing nozzle 881 is fixed to the other end, which is a free end, of the nozzle support portion 882. As a modified example, instead of the atomizing nozzle 881 that is a single-fluid nozzle, a two-fluid nozzle 171 (FIG. 4) may be provided together with the nitrogen supply portion 350 (FIG. 4).

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

[0068] 9 is a block diagram showing a gas / liquid supply unit and a gas / liquid exhaust unit included in the substrate processing apparatus 113. 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 heating gas supply unit 187 in addition to the nozzle unit 188, the gas ejection nozzle 180a, the upper nozzle 181, and the lower nozzle 182 described above. 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 connected to the upper nozzle 181 via a valve, respectively. 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 a part of a gas supply unit that supplies gas to the inside of the chamber 12. The multiple gas ejection nozzles 180a are connected to the heating gas supply unit 187 via a valve.

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

[0070] The chemical liquid supplying 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 supplying unit 184 supplies deionized water (DIW) onto the substrate W via the upper nozzle 181 or the lower nozzle 182. The IPA supplying 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 supplying unit that supplies processing liquids other than the above-mentioned processing liquids (the above-mentioned chemical liquids, deionized water, and IPA).

[0071] The ozone supplying 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 supplying 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 supplying unit 187 is nitrogen gas, but may be other gas than nitrogen gas. When a heated inert gas is used in the heated gas supplying unit 187, explosion-proof measures in the substrate processing apparatus 113 can be simplified or are not required.

[0072] As shown in FIG. 8, a plurality of first engagement parts 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 parts 242 are arranged in the circumferential direction on the upper surface of the support base 413. In reality, the first engagement parts 241 and the second engagement parts 242 are arranged at different positions in the circumferential direction from the plurality of first contact parts 411 of the substrate support part 141 and the plurality of second contact parts 421 of the substrate pressing part 142. It is preferable that three or more sets of these engagement parts are provided, and in this embodiment, four sets are provided. A recess that is recessed upward is provided at the lower part of the first engagement part 241. The second engagement part 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), in a state where the chamber lid 122 is located above and away from the chamber body 121 and the cup part 161 is located below and away from the chamber lid 122, the substrate W is carried into the chamber 12 by an external transport mechanism and supported from below by the substrate support part 141. Hereinafter, the state of the chamber 12 and the cup part 161 shown in FIG. 10 will be referred to as an "open state". The opening between the chamber lid 122 and the chamber side wall part 214 is annular about the central axis J1, and will be referred to as an "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 the substrate W (i.e., radially outward). In step S11, the substrate W is carried in 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 facing portion 163. The space 160 is a substantially annular space surrounding the entire outer periphery of the chamber 12. In the following description, the space 160 is 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 omitted from illustration in order to make it easier to understand the accommodated state of the nozzle unit 188. The bellows 617 is 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 located at the position shown in Fig. 8, the nozzle unit 188 is rotated by the support portion rotation mechanism 891 and moves 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 161 is lowered by the cup portion movement mechanism 162 to the position shown in Fig. 10. As the cup portion 161 is lowered, the side space 160 becomes smaller.

[0078] When the substrate W is loaded, the cup portion 161 rises from the position shown in Fig. 10 to the position shown in Fig. 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). Moreover, 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 the retracted position below the liquid receiving position.

[0079] In the cup portion 161 located at the liquid receiving position, the side wall portion 611 faces the annular opening 81 in the radial direction. In addition, the upper surface of the inner edge of the upper surface portion 612 contacts the lip seal 232 at the lower end of the outer edge portion of the chamber lid portion 122 over the entire circumference. A seal portion that prevents the passage of gas or liquid is formed between the chamber lid portion 122 and the upper surface portion 612 of the cup portion 161. As a result, a sealed space (hereinafter referred to as "expanded sealed space 100") surrounded by the chamber body 121, the chamber lid portion 122, the cup portion 161, and the cup opposing portion 163 is formed. The expanded sealed space 100 is a space formed by communicating the chamber space 120 between the chamber lid portion 122 and the chamber body 121 with 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 rotating 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 in 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 in 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 accommodated 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 arranged outside the enlarged sealed space 100 rotates the nozzle support part 882, and the mist nozzle 881 moves above the substrate W through the annular opening 81. Furthermore, the support part rotation mechanism 891 is controlled by the control unit 10, and the mist nozzle 881 starts to move back and forth above the substrate W. The mist nozzle 881 continuously moves back and forth in the horizontal direction along a predetermined movement path connecting 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 horizontally oscillating atomizing nozzle 881 onto the upper surface 91 of the substrate W (corresponding to step ST40 (FIG. 5)). The chemical liquid spreads to the outer periphery due to the rotation of the substrate W, and the entire upper surface 91 is covered with the chemical liquid. By continuing to spray the chemical liquid from the horizontally oscillating atomizing nozzle 881 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. Furthermore, the temperature uniformity of the chemical liquid on the substrate W can also be improved. 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 a 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 a 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] When 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)). Also, the introduction of the ozone-containing gas from the ozone supply unit 200 (see FIG. 9) is stopped (corresponding to step ST30 (FIG. 5)). Next, the substrate rotation mechanism 15 increases the rotation speed of the substrate W to be higher than the steady rotation speed for a predetermined time (e.g., 1 to 3 seconds), and the chemical liquid is removed from the substrate W. Also, 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 through the annular opening 81.

[0087] When the nozzle unit 188 moves to 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 part of the chamber side wall 214, thereby closing the annular opening 81 and sealing the chamber space 120 in a state in which it is isolated from the side space 160. The cup 161 is located at the retracted position as in FIG. 10. The side space 160 is sealed in a state in which it is isolated from the chamber space 120. Hereinafter, the state of the chamber 12 and the cup 161 shown in FIG. 13 is referred to as a "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 exists between them. Also, the nozzle unit 188 is isolated from the chamber space 120 and accommodated in the side space 160.

[0088] In the second sealed state, the second contact portions 421 of the substrate holder 142 contact the outer edge of the substrate W. On the lower surface of the top plate 123 and on the support base 413 of the substrate support 141, a plurality of pairs of magnets (not shown) facing each other in the vertical direction are provided. Hereinafter, each pair of magnets is also 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 holder 142 contacts the substrate W, a downward force is applied to the top plate 123 due to a magnetic force (attractive force) acting between the magnet pairs. As a result, the substrate holder 142 presses the substrate W against the substrate support 141.

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

[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 releases the holding of the top plate 123. Therefore, the top plate 123 is rotated by the substrate rotating mechanism 15 together with the substrate holding portion 14 and the substrate W held by the substrate holding portion 14, independent of the chamber lid portion 122.

[0091] 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 restricting members that restrict the relative position of the top plate 123 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] When the chamber space 120 and the side space 160 are sealed independently, exhaust of gas by the outer exhaust unit 194 (see FIG. 9) is stopped, and exhaust of gas from within the chamber space 120 by the inner exhaust unit 198 is started. Supply of pure water as a rinsing liquid to the substrate W is started by the pure water supply unit 184 (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 parts of the upper surface 91 and the lower surface 92 of the substrate W. The pure water spreads to the outer periphery of the upper surface 91 and the lower surface 92 due to the rotation of the substrate W, and splashes outward from the outer periphery of the substrate W. The pure water splashed from the substrate W is received by the inner wall of the chamber 12 (i.e., the inner wall of the chamber lid 122 and the chamber side wall 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 in the drying process of the substrate W described later). As a result, the interior of the chamber 12 is essentially cleaned in addition to the rinsing process of the upper surface 91 of the substrate W and the cleaning process of the lower surface 92.

[0094] When 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)). When 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 depressurizing 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 from the IPA supply unit 185 onto the substrate W 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, since the top plate 123 rotates together with the substrate support 141, almost no liquid remains on the underside of the top plate 123, and no liquid drops from the top plate 123 onto the substrate W when the chamber lid 122 is raised. The substrate W is 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 cover 122 in the vertical direction, and may move the chamber body 121 in the vertical direction with the chamber cover 122 fixed. The chamber 12 is not necessarily limited to a substantially cylindrical shape, and may have various shapes. The shape and structure of the stator 151 and the rotor 152 of the substrate rotating mechanism 15 may be changed in various ways. The rotor 152 does not necessarily have to rotate in a floating state, and a structure such as a guide that mechanically supports the rotor 152 may be provided in the chamber 12, and the rotor 152 may rotate along the guide. The substrate rotating mechanism 15 does not necessarily have to be a hollow motor, and a shaft rotating type motor may be used as the substrate rotating mechanism. In the substrate processing apparatus 113, the expanded sealed space 100 may be formed by contacting a portion (for example, a side wall 611) other than the upper surface 612 of the (outer) cup 161 with the chamber cover 122. The shapes of the (outer) cup portion 161 and the inner cup portion 161a may be modified 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 in Fig. 5 (first embodiment) is performed in the third embodiment, a flow similar to that 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 inconsistent. [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 device 161: Cup section 171: Two-fluid nozzle (atomizing nozzle) 200: Ozone supply unit 250: Pressure gauge 300: Chemical supply section 301: Sulfuric acid tank 302: Pressure adjustment section 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 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 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); A substrate processing method comprising:

2. 2. The substrate processing method according to claim 1, The method for processing a substrate, wherein the flow is a high velocity flow.

3. 3. The substrate processing method according to claim 1, further comprising the steps of: The substrate processing method, wherein the step a) includes the step of confirming that at least one of a pressure and an ozone concentration in the substrate processing chamber is equal to or higher than a predetermined threshold value.

4. 4. A substrate processing method according to claim 1, further comprising: 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 step b) and the step c).

5. 4. A substrate processing method according to claim 1, further comprising: A substrate processing method, wherein after the introduction of an ozone-containing gas into the substrate processing chamber in step a), the introduction is stopped before step c).

6. A substrate processing apparatus for removing an organic film from a substrate, comprising: a substrate processing chamber; a substrate holder for holding the substrate within the substrate processing chamber; an ozone supply unit for supplying an ozone-containing gas into the substrate processing chamber; an atomizing nozzle that uses a flow of inert gas to spray the chemical solution onto the substrate; an inert gas supply unit for supplying 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, and then controls the chemical liquid supply unit so as to start spraying the chemical liquid onto the substrate through the space; The substrate processing apparatus includes:

7. 7. The substrate processing apparatus according to claim 6, The substrate processing apparatus, wherein the flow is a high-velocity flow.

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