Substrate processing method and substrate processing apparatus

Abstract

This invention relates to a substrate processing method and apparatus for removing organic films from a substrate, providing a substrate processing method and apparatus capable of reducing the burden of chemical solutions and wastewater treatment, and efficiently removing organic films from a substrate. The substrate processing method for removing organic films from a substrate includes: a) a step of introducing ozone-containing gas into a substrate processing chamber, thereby filling the space above the substrate within the substrate processing chamber with ozone-containing gas; b) after step a), a step of starting a spray of a heated chemical solution containing sulfuric acid onto the substrate via the space; c) a step of continuing the spraying initiated in step b); and d) a step of stopping the spraying that continued in step c).

Description

Technical Field

[0001] This invention relates to a substrate processing method and a substrate processing apparatus for removing organic films from a substrate. The substrates include, for example, substrates for FPD (Flat Panel Display) devices such as semiconductor wafers, liquid crystal display devices, and organic EL (Electroluminescence) display devices, substrates for optical discs, substrates for magnetic disks, substrates for optical disc drives, substrates for photomasks, ceramic substrates, and substrates for solar cells. Background Technology

[0002] Semiconductor device manufacturing processes typically require substrate cleaning. Typically, this cleaning process removes unwanted organic films (typically resist films) from the substrate. For example, according to Japanese Patent Application Publication No. 2016-181677 (Patent Document 1), the substrate surface is cleaned using a sulfuric acid / hydrogen peroxide mixture (SPM) as the cleaning agent. However, this process consumes a large amount of SPM. SPM is sometimes difficult to reuse effectively, resulting in high costs and a heavy waste disposal burden. Therefore, in recent years, research has been conducted on substrate processing methods that can reduce material costs and waste disposal burdens. One such method is SOM cleaning, which uses a sulfuric acid and ozone mixture (SOM) instead of SPM as the cleaning agent. By mixing sulfuric acid and ozone, persulfate ions (S₂O₈) are generated. 2- ) as an active species (etchant).

[0003] For example, according to Japanese Patent Application Publication No. 2013-150007 (Patent Document 2), sulfuric acid containing tiny bubbles of ozone gas is supplied to a substrate from a nozzle. Furthermore, according to US Patent No. 6,869,487 (Patent Document 3), by controlling the thickness of the liquid layer on the substrate, ozone is allowed to reach the surface of the substrate through diffusion across the liquid layer.

[0004] Existing technical documents

[0005] Patent Document 1: Japanese Patent Application Publication No. 2016-181677

[0006] Patent Document 2: Japanese Patent Application Publication No. 2013-150007

[0007] Patent Document 3: US Patent No. 6,869,487 Summary of the Invention

[0008] The problem that the invention aims to solve

[0009] Ozone has a relatively long half-life, approximately 90 minutes in air at 150°C, but a very short half-life, less than 10 seconds in sulfuric acid at 150°C. Thus, ozone readily and rapidly decomposes in sulfuric acid. Therefore, as in the technology disclosed in Japanese Patent Application Publication No. 2013-150007, if the sulfuric acid already contains ozone before being ejected from the nozzle, a large amount of ozone readily decomposes too early, before reaching the vicinity of the substrate. Correspondingly, the generation of active species based on ozone decomposition also tends to occur too early, resulting in most of the active species being deactivated before reaching the substrate. Therefore, it is difficult to efficiently process substrates utilizing active species. Furthermore, while increasing the ozone concentration by setting the pressure to high to contain ozone in the solution may improve the processing efficiency, it is practically difficult to stably maintain the high pressure required to achieve significant effects.

[0010] According to the aforementioned U.S. Patent No. 6,869,487, ozone diffusion, such as that penetrating the liquid layer on the substrate, is required. However, according to the research of the inventors, diffusion penetrating the liquid layer is almost impossible to achieve. Therefore, it is difficult to perform substrate processing efficiently in this method.

[0011] The present invention was made to solve the above-mentioned problems, and its object is to provide a substrate processing method and substrate processing apparatus that can suppress the burden of pharmaceutical costs and waste liquid treatment, and can efficiently remove organic films from the substrate.

[0012] Methods for solving problems

[0013] The first aspect of the present invention is a substrate processing method for removing an organic film from a substrate, comprising the following steps: a) a step of introducing ozone-containing gas into a substrate processing chamber to fill at least the space above the substrate within the substrate processing chamber with ozone-containing gas; b) a step of, after step a), starting a spraying of a heated solution containing sulfuric acid onto the substrate via the space; c) a step of continuing the spraying initiated in step b); and d) a step of stopping the spraying that continued in step c).

[0014] The second aspect of the present invention is a substrate processing method of the first aspect, wherein step a) includes a step of confirming that the measured value of at least one of the pressure and ozone concentration in the substrate processing chamber is above a predetermined threshold.

[0015] The third aspect of the present invention is a substrate processing method of the first or second aspect, wherein after the introduction of ozone gas into the substrate processing chamber is performed in step a), the introduction is continued in steps b) and c).

[0016] The fourth aspect of the present invention is a substrate processing method of the first or second aspect, wherein after the introduction of ozone-containing gas into the substrate processing chamber is performed in step a), the introduction is stopped before step c).

[0017] The fifth aspect of the present invention is a substrate processing method of any one of the first to fourth aspects, wherein the liquid sprayed in step c) is divided into a first liquid that is received and recovered by a cup portion surrounding the substrate and a second liquid that is recovered outside the cup portion, and the second liquid is re-sprayed in a manner that does not contain the first liquid.

[0018] The sixth aspect of the present invention is a substrate processing apparatus for removing an organic film from a substrate, the substrate processing apparatus comprising: a substrate processing chamber; a substrate holding section that holds the substrate in the substrate processing chamber; an ozone supply section that supplies ozone-containing gas into the substrate processing chamber; an atomizing nozzle that sprays a liquid medicine onto the substrate; a liquid medicine supply section having a heater that supplies the liquid medicine heated by the heater to the atomizing nozzle; and a control section that, after controlling the ozone supply section to fill the space in the substrate processing chamber at least above the substrate with ozone-containing gas, controls the liquid medicine supply section to start spraying the liquid medicine onto the substrate through the space.

[0019] Invention Effects

[0020] According to the first and sixth aspects of the present invention, firstly, ozone is mixed with a heated pharmaceutical solution containing sulfuric acid instead of hydrogen peroxide. This allows for easy and efficient reuse of the pharmaceutical solution. Therefore, the burden of pharmaceutical solution costs and wastewater treatment can be reduced. Secondly, this mixing takes place in the space above the substrate. This avoids premature ozone decomposition before it reaches the vicinity of the substrate, while using sulfuric acid at a high temperature that readily decomposes ozone. Therefore, the active species generated by ozone decomposition reach the substrate in a high proportion before deactivation. Furthermore, this mixing is performed by spraying the pharmaceutical solution into ozone-containing gas. Spraying imparts a large surface area to the pharmaceutical solution, thereby promoting the reaction between the pharmaceutical solution and the surrounding ozone. Therefore, the reaction between the pharmaceutical solution and ozone proceeds rapidly without significant dependence on ozone diffusion into the pharmaceutical solution. As a result, a large number of active species are generated after this mixing. As described above, this large number of active species reaches the substrate in a high proportion before deactivation. Therefore, the process of removing organic films from the substrate using active species can be performed efficiently. Fourthly, at the time of spraying the pharmaceutical solution, the aforementioned space is already filled with ozone-containing gas. Therefore, the reaction between the liquid medicine and ozone in this space becomes active from the start of the liquid medicine spraying. Thus, the amount of liquid medicine required for treatment can be controlled. Based on the above, the burden of liquid medicine costs and wastewater treatment can be reduced, and organic films can be removed from the substrate with high efficiency.

[0021] According to a second aspect of the invention, spraying begins after confirming that at least one of the measured values ​​of pressure and ozone concentration within the substrate processing chamber is above a predetermined threshold. Therefore, at the start time of spraying the chemical solution, the amount of ozone in the aforementioned space can be made more reliably sufficient.

[0022] According to a third aspect of the present invention, ozone-containing gas is continuously introduced during the spraying of the chemical solution. This compensates for the decrease in ozone concentration in the substrate processing chamber caused by ozone decomposition. Therefore, the substrate processing can be maintained at a substantially constant rate throughout the entire chemical spraying process.

[0023] According to a fourth aspect of the present invention, the introduction of ozone-containing gas is stopped during the spraying of the pharmaceutical solution. This suppresses the consumption of ozone-containing gas.

[0024] According to a fifth aspect of the present invention, a portion of the sprayed pharmaceutical solution is re-sprayed. This further reduces the burden of pharmaceutical solution costs and wastewater treatment. Furthermore, by ensuring that the re-sprayed pharmaceutical solution does not contain the pharmaceutical solution received by the cup portion, re-spraying of pharmaceutical solution contaminated on the substrate can be avoided.

[0025] The objectives, features, situation, and advantages related to the technology disclosed in this application will become clearer through the following detailed description and accompanying drawings. Attached Figure Description

[0026] Figure 1 This is a top view that schematically illustrates the structure of the substrate processing system according to various embodiments of the present invention.

[0027] Figure 2 It is a conceptual representation Figure 1 The diagram shows the structure of the control unit.

[0028] Figure 3 It is a general indication that the use of Figure 1 A flowchart of the substrate processing method of the substrate processing system.

[0029] Figure 4 This is a cross-sectional view that schematically shows the structure of the substrate processing apparatus of Embodiment 1.

[0030] Figure 5 This is a flowchart that roughly illustrates the substrate processing method of Embodiment 1.

[0031] Figure 6 This is a cross-sectional view that schematically shows the structure of the substrate processing apparatus of Embodiment 2.

[0032] Figure 7 This is a flowchart that roughly illustrates the substrate processing method of Embodiment 2.

[0033] Figure 8 This is a cross-sectional view that schematically shows the structure of the substrate processing apparatus of Embodiment 3.

[0034] Figure 9 This is a general representation of the setting at Figure 8 A block diagram showing the structure of the gas-liquid supply section and the gas-liquid discharge section of the substrate processing apparatus.

[0035] Figure 10 This is a cross-sectional view that schematically illustrates one step of the substrate processing method of Embodiment 3.

[0036] Figure 11 This is a top view that schematically illustrates one step of the substrate processing method of Embodiment 3.

[0037] Figure 12 This is a cross-sectional view that schematically illustrates one step of the substrate processing method of Embodiment 3.

[0038] Figure 13 This is a cross-sectional view that schematically illustrates one step of the substrate processing method of Embodiment 3.

[0039] Explanation of reference numerals in the attached figures

[0040] 10: Control Department

[0041] 12: Chamber (Substrate Processing Chamber)

[0042] 14: Rotary chuck (substrate holding part)

[0043] 17: Cover

[0044] 110: Processing Unit

[0045] 111-113: Substrate processing apparatus

[0046] 161: Cup section

[0047] 171: Dual-fluid nozzle (atomizing nozzle)

[0048] 200: Ozone Supply Department

[0049] 250: Pressure gauge

[0050] 300: Medicine Supply Department

[0051] 301: Sulfuric Acid Tank

[0052] 302: Pressure Adjustment Section

[0053] 303: Heater

[0054] 310: Three-way valve

[0055] 350: Nitrogen Supply Department

[0056] 881: Atomizing Nozzle

[0057] LR1: First liquid

[0058] LR2: Second liquid

[0059] W: substrate Detailed Implementation

[0060] The following is a reference to the appendix. Figure 1 The embodiments will be described below. In the following embodiments, detailed features are shown for technical explanation, but these are illustrative and not all are essential features for implementing the embodiments. The accompanying drawings are schematic; for ease of explanation, structures are appropriately omitted or simplified in the drawings. Furthermore, the size and positional relationships of structures shown in different drawings may not be accurately described and can be appropriately changed. Additionally, in drawings such as top views (not sectional views), shaded lines are sometimes used to facilitate understanding of the embodiments. Furthermore, in the following descriptions, the same reference numerals are used to illustrate the same structural elements, and their names and functions are also assumed to be the same. Therefore, detailed descriptions of them are sometimes omitted to avoid repetition. Furthermore, in the following descriptions, when a structural element is described as "having," "comprising," or "having," unless otherwise specified, this does not imply an exclusionary statement excluding the existence of other structural elements.

[0061] <Substrate Processing System>

[0062] Figure 1 This is a top view schematically illustrating an example of the structure of a substrate processing system 1. The substrate processing system 1 includes: a loading port LP, an indexing robot IR, a central robot CR, a control unit 10, and at least one processing unit 110. Figure 1 (There are 4 processing units in the middle). The substrate processing system 1 is used to remove organic films (e.g., resist films) from the substrate W.

[0063] Each processing unit 110 is used to process a substrate W (wafer). The processing unit 110 is a monolithic device capable of substrate processing. The control unit 10 can control the operation of each structure in the substrate processing system 1. The carrier C is a receiving container for holding the substrate W. Additionally, the loading port LP is a receiving container holding mechanism that holds multiple carriers C. The indexing robot IR can move the substrate W between the loading port LP and the substrate placement unit PS. The central robot CR can move the substrate W between the substrate placement unit PS and the processing unit 110. Through the above structure, the indexing robot IR, the substrate placement unit PS, and the central robot CR function as a transport mechanism for moving the substrate W between each processing unit 110 and the loading port LP.

[0064] The unprocessed substrate W is removed from the carrier C by the indexing robot IR. The unprocessed substrate W is then transferred to the central robot CR via the substrate placement unit PS. The central robot CR moves the unprocessed substrate W into the processing unit 110. The processing unit 110 processes the substrate W. The substrate W, processed in the processing unit 110, is removed from the processing unit 110 by the central robot CR. The processed substrate W, as needed, is then transferred to the indexing robot IR via the substrate placement unit PS after passing through another processing unit 110. The indexing robot IR moves the processed substrate W into the carrier C. Through the above process, processing of the substrate W is performed.

[0065] Figure 2 It is a conceptual representation Figure 1 The diagram shows an example of the structure of the control unit 10. The control unit 10 controls... Figure 1 The processing unit 110, loading port LP, indexing robot IR, and central robot CR are shown. The control unit 10 can be configured as a general computer with 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 1015 connecting them to each other.

[0066] ROM 1012 stores the basic program. RAM 1013 is used as the working area for CPU 1011 to perform predetermined processing. Storage device 1014 is composed of non-volatile storage devices such as flash memory or hard disk. Input unit 1016 is composed of various switches or touch panels, etc., and receives input setting instructions such as processing procedures from the operator. Display unit 1017 is composed of, for example, a liquid crystal display device and lights, and displays various information under the control of CPU 1011. Communication unit 1018 has data communication function via local area network (LAN) or the like.

[0067] Figure 3 It is a general indication that the use of Figure 1 A flowchart of the substrate processing method of the substrate processing system 1. In step S11 ( Figure 3 In step S12, the substrate W with the organic film to be removed is moved from the carrier C into the substrate processing chamber of the processing unit 110 by sequentially using the indexing robot IR and the central robot CR. Figure 3 In step S13, the organic film is removed from the substrate W (details will be described later). Figure 3 In step S14, the substrate W is rinsed by supplying rinsing fluid to the substrate W. Figure 3 In step S15, the substrate W is dried. Figure 3 In the process, the central robot CR and the indexing robot IR are used in sequence to move the substrate W from the substrate processing chamber of the processing unit 110 to the carrier C.

[0068] The storage device 1014 is pre-configured with a specific feature. Figure 1 The substrate processing system 1 has multiple control modes for each structure. The CPU 1011 executes a processing program 1014P, selects one of the multiple modes, and controls each structure in that mode. Furthermore, the processing program 1014P can also be stored in a recording medium. If this recording medium is used, the processing program 1014P can be installed in the control unit 10. Additionally, some or all of the functions performed by the control unit 10 may not need to be implemented in software; they can also be implemented in hardware such as dedicated logic circuits.

[0069] <Implementation Method 1>

[0070] Reference Figure 4 In this embodiment 1, as a processing unit 110 ( Figure 1At least one of the following is used in a substrate processing apparatus 111 for removing an organic film (e.g., a resist film) from a substrate W: a chamber 12 (substrate processing chamber), a rotary chuck 14 (substrate holding section), an ozone supply section 200, a chemical supply section 300, a nitrogen supply section 350 (inactive gas supply section), a dual-fluid nozzle 171 (atomizing nozzle), a nozzle moving mechanism 172, a cup section 161, a waste liquid section 320, and an exhaust section 190.

[0071] The rotary chuck 14 holds the substrate W within the chamber 12. The rotary chuck 14 has: a rotary base 143; a rotary motor 144 that rotates the rotary base 143 via a rotary shaft; and a substrate attraction mechanism 145 that fixes the substrate W to the rotary base 143 by attracting the substrate W on the rotary base 143.

[0072] The ozone supply unit 200 supplies ozone-containing gas into the chamber 12. For this purpose, the ozone supply unit 200 has a pipe connected to the space within the chamber 12 via a valve. The end of this pipe, constituting the ozone-containing gas supply port, is installed in the chamber 12, preferably at a height near the upper surface of the substrate W, for example, it can be located slightly higher than the upper surface of the substrate W. The ozone supply unit 200 may include a gas source for supplying oxygen or air and an ozone generating device for ozonating the gas from the gas source. The ozone concentration in the ozone-containing gas supplied from the ozone supply unit 200 is preferably 100 g / m³. 3 Above and 400g / m 3 The following is more preferably 250g / m 3 Above and 400g / m 3 The pressure of the ozone-containing gas supplied by the ozone supply unit 200 can be 0.1 MPa or more and 0.3 MPa or less.

[0073] The drug supply unit 300 includes a sulfuric acid tank 301, a pressure regulating unit 302, and a heater 303. The drug supply unit 300 supplies a sulfuric acid-containing drug solution, heated by the heater 303, to a two-fluid nozzle 171. The temperature of the heated drug solution is preferably 70°C to 200°C. The pressure regulating unit 302 adjusts the supply pressure to the two-fluid nozzle 171. The pressure regulating unit 302 can be a pump or a regulator. The supply pressure of the drug solution to the two-fluid nozzle 171 is higher than the threshold pressure described later.

[0074] The nitrogen supply unit 350 supplies nitrogen (N2) as an inactive gas to the dual-fluid nozzle 171. The nitrogen supply pressure to the dual-fluid nozzle 171 is higher than the threshold pressure described later.

[0075] The dual-fluid nozzle 171 is an atomizing nozzle that sprays a liquid medicine onto the substrate W. Through spraying, the liquid medicine is supplied to the chamber 12 as fine particles FM. During spraying, the dual-fluid nozzle 171 utilizes a high-speed flow of gas supplied from the nitrogen supply unit 350, making it easier to produce finer particles FM of the sprayed liquid medicine compared to a single-fluid nozzle. This further increases the surface area of ​​the sprayed liquid medicine. Furthermore, if the desired spraying can also be achieved using a single-fluid nozzle, the dual-fluid nozzle 171 can be replaced with a single-fluid nozzle that atomizes the liquid medicine without using the nitrogen supply unit 350. The nozzle moving mechanism 172 moves the dual-fluid nozzle 171 horizontally. The nozzle moving mechanism 172 may have an arm supporting the dual-fluid nozzle 171 and an actuator driving the arm.

[0076] The cup portion 161 surrounds the substrate W and the rotating base 143 that holds the substrate W on its sides. When the substrate W is rotated by the rotary motor 144, the liquid sprayed onto the substrate W is thrown around the substrate W. When the liquid is supplied onto the substrate W, the upper end of the upward-opening cup portion 161 is positioned higher than the rotating base 143. Therefore, the liquid discharged around the substrate W is received by the cup portion 161. Furthermore, the liquid collected by the cup portion 161, namely the first liquid LR1, is transported to the waste liquid portion 320. In addition, the liquid collected outside the cup portion 161 from the sprayed liquid, namely the second liquid LR2, can be returned to the liquid supply portion 300 through a pipe equipped with a valve. This pipe is connected to the pipe of the liquid supply portion 300 through a three-way valve 310. By switching the three-way valve 310, the state of the liquid supply unit 300 using the liquid in the sulfuric acid tank 301 and the state of the liquid supply unit 300 using the second liquid LR2 can be switched. In addition, the cup part 161 can also be configured so that when this function is not needed, it can be lowered further than the rotating base 143 by means of the cup moving mechanism (not shown).

[0077] The exhaust section 190 has a pipe connected to the space inside the chamber 12 via a valve. With the valve open, the exhaust section 190 discharges the atmosphere inside the chamber 12 to the outside of the chamber 12. The end of this pipe constituting the exhaust port of the chamber 12 is located at... Figure 4 The middle part is installed in chamber 12, but it can also be installed in cup 161 instead. The exhaust part 190 preferably has an ozone removal device.

[0078] Control Unit 10 ( Figure 1 The control unit 10 controls each part of the substrate processing apparatus 111. In this embodiment, after the ozone supply unit 200 controls the ozone-containing gas to fill the space above the substrate W in the chamber 12, the control unit 10 controls the liquid supply unit 300 to start spraying the liquid onto the substrate W through the space. Furthermore, the control unit 10 can be considered as part of the substrate processing apparatus 111.

[0079] The following is about step S12 ( Figure 3 The corresponding process, utilizing substrate processing apparatus 111 ( Figure 4 The SOM cleaning process for removing the organic film from the substrate W will be described in more detail.

[0080] The substrate W is held by a rotating chuck 14. In step ST10 ( Figure 5 In step ST20, the ozone supply unit 200 begins to introduce ozone-containing gas into the chamber 12. Figure 5 In this process, ozone-containing gas is introduced to fill the space above at least the substrate W within the chamber 12. Whether the chamber 12 is completely filled with ozone gas is defined as whether at least one of the pressure and ozone concentration within the chamber 12 is above a threshold value. The threshold pressure is preferably 0.1 MPa or higher and 0.3 MPa or lower. The threshold concentration is preferably 100 g / m³. 3 Above and 400g / m 3 The following is more preferably 250g / m 3 Above and 400g / m 3 Below. Furthermore, in this embodiment, it is not necessarily necessary to obtain a measured value compared to a threshold, but it is also possible to confirm that the measured value is above the threshold. In this case, for measurement, a pressure gauge 250 (described later) is installed in chamber 12. Figure 6 Or an ozone concentration meter.

[0081] In step ST40 described later ( Figure 5 Before step ST20, the substrate W is rotated by rotating chuck 14. After step ST40, the substrate W is rotated by rotating chuck 14. Figure 5 In this process, the liquid supply unit 300 supplies heated liquid containing sulfuric acid to the dual-fluid nozzle 171, and the nitrogen supply unit supplies nitrogen gas. Thus, the heated liquid containing sulfuric acid is sprayed onto the substrate W through a space already filled with ozone gas, as described above. The sulfuric acid in the sprayed liquid reacts with ozone in the space, thereby generating active species, specifically S2O8. 2- In step ST50 ( Figure 5 Continue spraying through the steps described above, starting with ST40.

[0082] In step ST60 ( Figure 5In step ST10 and ST20, the spraying that continued in step ST50 is stopped. Specifically, for the dual-fluid nozzle 171, the liquid supply unit 300 stops supplying liquid, and the nitrogen supply unit 350 stops supplying nitrogen. The timing for stopping the spraying can be set, for example, to a point in time after a preset time elapsed from the start of the spraying. As another example, the timing for stopping the spraying can also be determined by referring to a monitoring unit used to monitor the progress of the substrate processing. In this embodiment, in steps ST10 and ST20... Figure 5 After ozone-containing gas is introduced into chamber 12 in step ST40 and ST50, this introduction continues. In other words, new ozone-containing gas is continuously supplied during the spraying process. Simultaneously or subsequently in step ST60, in step ST30, the ozone supply unit 200 stops introducing ozone-containing gas.

[0083] SOM cleaning is performed as described above. Furthermore, the SOM cleaning described above is sufficient as long as it removes at least partially the organic film from the substrate. If, at a later time point after SOM cleaning, some organic film remains, additional cleaning can be performed. This additional substrate treatment can be, for example, SPM cleaning or SC1 cleaning. This is also true in other embodiments described later.

[0084] ST50 will be processed through the above steps. Figure 5 The sprayed pharmaceutical solution is divided into a first liquid LR1, which is received and recovered by the cup portion 161 surrounding the substrate W, and a second liquid LR2, which is recovered outside the cup portion 161. Afterwards, the second liquid LR2 can be re-sprayed without the first liquid LR1. Specifically, by switching the three-way valve 310, the pharmaceutical solution supply unit 300 can switch from using the pharmaceutical solution in the sulfuric acid tank 301 to using the second liquid LR2. The re-spraying of the second liquid LR2 can be performed on the substrate W that was treated in the recovery of the second liquid LR2, or it can be performed on other substrates W. These features can also be applied to Embodiment 2 described later.

[0085] <Implementation Method 2>

[0086] Reference Figure 6 In this embodiment 2, as a processing unit 110 ( Figure 1 At least one of the following is used in a substrate processing apparatus 112 for removing an organic film from a substrate W: substrate processing apparatus 112. The substrate processing apparatus 112, in addition to substrate processing apparatus 111 ( Figure 4 In addition to the structure of embodiment 1), it also has a pressure gauge 250 for measuring the pressure inside the chamber 12.

[0087] The following section addresses the steps related to step S12 ( Figure 3 The corresponding process, utilizing substrate processing apparatus 112 ( Figure 6The SOM cleaning process for removing the organic film from the substrate W will be described in more detail.

[0088] The substrate W is held by a rotating chuck 14. In step ST10 ( Figure 7 In step ST20, the ozone supply unit 200 begins introducing ozone-containing gas into the chamber 12. Figure 7 In this embodiment, ozone-containing gas is introduced to fill the space above at least the substrate W within the chamber 12. In step ST20, it is confirmed that the pressure measured by the pressure gauge 250 is above a predetermined threshold pressure. Alternatively, the ozone concentration within the chamber 12 may be confirmed to be above a predetermined threshold concentration, either together with or instead of this confirmation. In this case, an ozone concentration meter (not shown) is installed in the chamber 12. Furthermore, the preferred ranges for the threshold pressure and threshold concentration are the same as those described in Embodiment 1.

[0089] Following step ST20 above, in step ST30 ( Figure 7 In step ST30, the ozone supply unit 200 stops the introduction of ozone-containing gas. In other words, the introduction of ozone-containing gas is stopped after confirming that at least one of the pressure or ozone concentration within chamber 12 is sufficiently high. This step ST30 is performed before step ST50, which is described later. Alternatively, step ST30 can also be performed before step ST40, which is described later.

[0090] In step ST40 ( Figure 7 Before step ST20, the substrate W is rotated by rotating chuck 14. After step ST40 above, in step ST40... Figure 7 In this process, the liquid supply unit 300 supplies heated liquid containing sulfuric acid to the dual-fluid nozzle 171, and the nitrogen supply unit supplies nitrogen gas. Thus, the heated liquid containing sulfuric acid is sprayed onto the substrate W through a space already filled with ozone gas, as described above. The sulfuric acid in the sprayed liquid reacts with ozone in the space, thereby generating active species, specifically S2O8. 2- In step ST50 ( Figure 7 Continue spraying through the steps described above, starting with ST40.

[0091] In step ST60 ( Figure 7 In step ST50, the spraying is stopped. Specifically, for the dual-fluid nozzle 171, the liquid supply unit 300 stops supplying liquid, and the nitrogen supply unit 350 stops supplying nitrogen. The timing for stopping the spraying can be set, for example, to a point in time after a predetermined time elapsed from the start of the spraying. As another example, the timing for stopping the spraying can also be determined by referring to a monitoring unit used to monitor the progress of the substrate processing.

[0092] In this embodiment, in steps ST10 and ST20 ( Figure 7 After ozone-containing gas is introduced into chamber 12, the introduction is stopped before step ST50. In other words, there is a period during the spraying process during which no new ozone-containing gas is replenished. Alternatively, the introduction can also be stopped before step ST40. In other words, no new ozone-containing gas can be replenished at all during the spraying process.

[0093] <Implementation Method 3>

[0094] Reference Figure 8 In this embodiment 3, as a processing unit 110 ( Figure 1 At least one of the following is used in a substrate processing apparatus 113 for removing an organic film from a substrate W: The substrate processing apparatus 113 is a monolithic device that processes generally circular substrates W one by one. Figure 8 In the cross-section of a portion of the substrate processing apparatus 113, the shading is omitted (the same applies in other sectional views).

[0095] The substrate processing apparatus 113 includes: a chamber 12, a top plate 123, a chamber opening and closing mechanism 131, a substrate holding part 14, a substrate rotating mechanism 15, a liquid receiving part 16, and a cover 17. The cover 17 covers the top and sides of the chamber 12.

[0096] The chamber 12 has a chamber body 121 and a chamber cover 122. The chamber 12 is generally cylindrical about a central axis J1 in the vertical direction. The chamber body 121 has a chamber bottom 210 and a chamber sidewall 214. The chamber bottom 210 has: a generally circular plate-shaped central portion 211, a generally cylindrical inner sidewall 212 extending downward from the outer edge of the central portion 211, a generally annular plate-shaped annular bottom 213 extending radially outward from the lower end of the inner sidewall 212, a generally cylindrical outer sidewall 215 extending upward from the outer edge of the annular bottom 213, and a generally annular plate-shaped base 216 extending radially outward from the upper end of the outer sidewall 215.

[0097] The chamber sidewall portion 214 is annular about the central axis J1. The chamber sidewall portion 214 protrudes upward from the inner edge of the base portion 216. As described later, the component forming the chamber sidewall portion 214 also serves as part of the liquid receiving portion 16. In the following description, the space surrounded by the chamber sidewall portion 214, the outer sidewall portion 215, the annular bottom 213, the inner sidewall portion 212, and the outer edge of the central portion 211 is referred to as the lower annular space 217.

[0098] When the substrate W is supported by the substrate support portion 141 (described later) of the substrate holding portion 14, the lower surface 92 of the substrate W faces the upper surface of the central portion 211 of the chamber bottom 210. In the following description, the central portion 211 of the chamber bottom 210 will be referred to as the "lower surface facing portion 211", and the upper surface 211a of the central portion 211 will be referred to as the "facing surface 211a". Details of the lower surface facing portion 211 will be described later.

[0099] The chamber cover 122 is a generally circular plate-shaped portion perpendicular to the central axis J1, encompassing the upper part of the chamber 12. The chamber cover 122 closes the upper opening of the chamber body 121. Figure 8 In the middle, it indicates the state in which the chamber cover 122 is separated from the chamber body 121. When the chamber cover 122 closes the upper opening of the chamber body 121, the outer edge of the chamber cover 122 is in contact with the upper part of the chamber side wall 214.

[0100] The chamber opening and closing mechanism 131 allows the chamber cover 122, which is a movable part of the chamber 12, to move vertically relative to the chamber body 121, which is another part of the chamber 12. The chamber opening and closing mechanism 131 is a cover lifting mechanism that raises and lowers the chamber cover 122. When the chamber cover 122 moves vertically via the chamber opening and closing mechanism 131, the top plate 123 also moves vertically along with the chamber cover 122. The chamber cover 122 contacts the chamber body 121 to close the upper opening, and the chamber cover 122 is pressed towards the chamber body 121, thereby forming a sealed chamber space 120 (see reference) within the chamber 12. Figure 13 In other words, the upper opening of the chamber body 121 is closed by the chamber cover 122, thereby sealing the chamber space 120.

[0101] A substrate holding portion 14 is disposed in the chamber space 120 to hold the substrate W in a horizontal state. That is, the substrate W is held by the substrate holding portion 14 with its upper surface 91 perpendicular to the central axis J1 facing upward. The substrate holding portion 14 has the aforementioned substrate support portion 141 that supports the outer edge of the substrate W from below (i.e., the portion near the outer periphery), and a substrate pressing portion 142 that presses down on the outer edge of the substrate W supported by the substrate support portion 141 from above. The substrate support portion 141 has a support base 413 that is generally annular about the central axis J1, and a plurality of first contact portions 411 fixed to the upper surface of the support base 413. The substrate pressing portion 142 has a plurality of second contact portions 421 fixed to the lower surface of the top plate 123. The circumferential positions of the plurality of second contact portions 421 are actually different from the circumferential positions of the plurality of first contact portions 411.

[0102] The top plate 123 is a generally circular plate perpendicular to the central axis J1. The top plate 123 is positioned below the chamber cover 122 and above the substrate support 141. The top plate 123 has a central opening. 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 from the outer periphery of the substrate W.

[0103] exist Figure 8 In the shown state, the top plate 123 is supported by being suspended by the chamber cover 122. The chamber cover 122 has a generally annular plate holding portion 222 at its center. The plate holding portion 222 has a generally cylindrical cylindrical portion 223 centered on a central axis J1 and a generally circular plate-shaped flange portion 224 centered on the central axis J1. The flange portion 224 extends radially inward from the lower end of the cylindrical portion 223. The top plate 123 has an annular holding portion 237. The holding portion 237 has a generally cylindrical cylindrical portion 238 centered on the central axis J1 and a generally circular plate-shaped flange portion 239 centered on the central axis J1. The cylindrical 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 cylindrical portion 238. The cylindrical portion 238 is located radially inward of 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 is opposed to the flange portion 224 in the vertical direction. The lower surface of the flange portion 239 of the held portion 237 is in contact with the upper surface of the flange portion 224 of the plate holding portion 222, thereby the top plate 123 is mounted on the chamber cover portion 122 in a manner that it is suspended from the chamber cover portion 122.

[0104] Figure 8The substrate rotation mechanism 15 shown is a so-called hollow motor. The substrate rotation mechanism 15 has an annular stator portion 151 centered on a central axis J1 and an annular rotor portion 152. The rotor portion 152 includes a generally annular permanent magnet. The surface of the permanent magnet is molded from PTFE resin. The rotor portion 152 is disposed within a lower annular space 217 in the chamber space 120 of the chamber 12. A support base 413 for a substrate support portion 141 is mounted on the upper part of the rotor portion 152 via a connecting member. The support base 413 is disposed above the rotor portion 152. The stator portion 151 is disposed outside the chamber 12 (i.e., outside the chamber space 120) around the rotor portion 152, i.e., radially outward. In this embodiment, the stator portion 151 is fixed to the outer wall portion 215 of the chamber bottom 210 and the base portion 216, located below the liquid receiving portion 16. The stator section 151 includes a plurality of coils arranged circumferentially around the central axis J1. By supplying current to the stator section 151, a rotational force centered on the central axis J1 is generated between the stator section 151 and the rotor section 152. As a result, the rotor section 152 rotates horizontally around the central axis J1. Due to the magnetic force acting between the stator section 151 and the rotor section 152, the rotor section 152 is suspended within the chamber 12 without directly or indirectly contacting the chamber 12, and the substrate W and the substrate support section 141 rotate together in a suspended state around the central axis J1.

[0105] 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 annularly centered on a central axis J1 and located radially outward of the chamber 12. The cup portion moving mechanism 162 moves the cup portion 161 vertically. The cup portion moving mechanism 162 is positioned radially outward of the cup portion 161. The cup portion moving mechanism 162 is located at a position different in the circumferential direction from the chamber opening / closing mechanism 131 described above. The cup opposing portion 163 is located below the cup portion 161 and is vertically opposed to the cup portion 161. The cup opposing portion 163 is part of the component forming the chamber sidewall portion 214. The cup opposing portion 163 has an annular liquid receiving recess 165 located radially outward of the chamber sidewall portion 214.

[0106] The cup portion 161 includes a sidewall portion 611, an upper surface portion 612, and a bellows 617. The sidewall portion 611 is generally cylindrical about a central axis J1. The upper surface portion 612 is generally annular about a central axis J1, extending radially inward and radially outward from the upper end of the sidewall portion 611. The lower part of the sidewall portion 611 can be located within the liquid receiving recess 165 of the cup opposing portion 163. The cross-sectional shape of the sidewall portion 611 is as described later in the section housing the nozzle unit 188. Figure 8 The right side of the middle) and other parts ( Figure 8 The left side portion (of the middle part) is different. The side wall portion 611 Figure 8 The radial thickness of the right side portion is greater than Figure 8 The left side is slightly thinner.

[0107] The bellows 617 is a generally cylindrical tube centered on the central axis J1, capable of expanding and contracting in the vertical direction. The bellows 617 is arranged radially outwardly around the sidewall portion 611, covering its entire circumference. The bellows 617 is formed of a material that prevents the passage of gas and liquid. The upper end of the bellows 617 is connected to the lower surface of the outer edge of the upper surface portion 612, covering its entire circumference. 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 between the bellows 617 and the upper surface portion 612 is sealed to prevent the passage of gas and liquid. The lower end of the bellows 617 is indirectly connected to the chamber body 121 via the cup-opposing portion 163. The connection between the lower end of the bellows 617 and the cup-opposing portion 163 also prevents the passage of gas and liquid.

[0108] An upper nozzle 181 is fixed at the center of the chamber cover 122. The upper nozzle 181 can be inserted into the opening at the center of the top plate 123. The upper nozzle 181 has a liquid spray outlet at the center and spray outlets around it. A lower nozzle 182 is installed at the center of the opposing portion 211 on the lower surface of the chamber bottom 210. A plurality of gas ejection nozzles 180a are also installed on the opposing portion 211 on the lower surface. The plurality of gas ejection nozzles 180a are arranged at equal angular intervals in the circumferential direction centered on the central axis J1, for example. Furthermore, the positions of the upper nozzle 181 and the lower nozzle 182 are not necessarily limited to the central portion; for example, they can also be located opposite the outer edge of the substrate W.

[0109] A nozzle unit 188 is mounted on the upper surface 612 of the cup portion 161. The nozzle unit 188 includes an atomizing nozzle 881 for spraying liquid and a nozzle support 882. The nozzle support 882 is a rod-shaped component extending in a generally horizontal direction. One end of the nozzle support 882, i.e., the fixed end, is mounted to the lower surface of the upper surface 612 of the cup portion 161. The atomizing nozzle 881 is fixed to the other end of the nozzle support 882, i.e., the free end. Alternatively, as a variation, a dual-fluid nozzle 171 may be provided instead of the single-fluid nozzle 881. Figure 4 ) and nitrogen supply unit 350 ( Figure 4 ).

[0110] A nozzle moving mechanism 189 is provided on the upper part of the cup portion 161. The nozzle moving mechanism 189 is fixed to the upper surface of the upper 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 rotating mechanism 891 and a support portion lifting mechanism 892. The support portion rotating mechanism 891 passes through the upper surface portion 612 of the cup portion 161 and connects to the fixed end of the nozzle support portion 882, causing the nozzle support portion 882 and the atomizing nozzle 881 to rotate together in a generally horizontal direction with the fixed end as the center. The through portion of the cup portion 161 based on the support portion rotating mechanism 891 is sealed to prevent the passage of gas and liquid. The support portion lifting mechanism 892 moves the fixed end of the nozzle support portion 882 in the vertical direction, thereby raising and lowering the nozzle support portion 882 and the atomizing nozzle 881. The nozzle moving mechanism 189 moves together with the cup portion 161 in the vertical direction via the cup portion moving mechanism 162.

[0111] Figure 9 This is a block diagram showing the gas-liquid supply section and gas-liquid discharge section of the substrate processing apparatus 113. In addition to the nozzle unit 188, gas ejection nozzle 180a, upper nozzle 181, and lower nozzle 182 described above, the gas-liquid supply section also includes: an ozone supply section 200, a liquid supply section 300, a pure water supply section 184, an IPA supply section 185, and a heating gas supply section 187. The liquid supply section 300 is connected to the nozzle unit 188 via a valve. The pure water supply section 184 and the IPA supply section 185 are each connected to the upper nozzle 181 via valves. The lower nozzle 182 is connected to the pure water supply section 184 via a valve. The upper nozzle 181 is also connected to the ozone supply section 200 via a valve. The upper nozzle 181 is part of the gas supply section that supplies gas to the interior of the chamber 12. Multiple gas ejection nozzles 180a are connected to the heating gas supply section 187 via valves.

[0112] A first discharge path 191, connected to the liquid receiving recess 165 of the liquid receiving section 16, is connected to a gas-liquid separator 193. The gas-liquid separator 193 is connected to an outer exhaust section 194, a liquid recovery section 195, and a drain section 196 via valves. A second discharge path 192, connected to the bottom 210 of the chamber, is connected to a gas-liquid separator 197. The gas-liquid separator 197 is connected to an inner exhaust section 198 and a drain section 199 via valves.

[0113] For example, in substrate processing device 111 ( Figure 4As described in Embodiment 1), the liquid supply unit 300 supplies a heated liquid containing sulfuric acid. The pure water supply unit 184 supplies pure water (DIW: deionized water) to the substrate W via the upper nozzle 181 or the lower nozzle 182. The IPA supply unit 185 supplies isopropanol (IPA) to the substrate W via the upper nozzle 181. In the substrate processing apparatus 113, a processing liquid supply unit that supplies processing liquids other than the above-mentioned processing liquids (the above-mentioned liquid, pure water, and IPA) may also be provided.

[0114] For example, in substrate processing device 111 ( Figure 4 As described in Embodiment 1), the ozone supply unit 200 supplies ozone-containing gas into the chamber 12. In this embodiment, this supply is performed via the upper nozzle 181. The heating gas supply unit 187 supplies heated gas (e.g., an inactive gas heated to a high temperature of 160-200°C) to the lower surface 92 of the substrate W via multiple gas ejection nozzles 180a. In this embodiment, the gas used in the heating gas supply unit 187 is nitrogen, but it can also be a gas other than nitrogen. Furthermore, when heated inactive gas is used in the heating gas supply unit 187, the explosion-proof measures in the substrate processing apparatus 113 can be simplified or eliminated.

[0115] like Figure 8 As shown, a plurality of first engaging portions 241 are arranged circumferentially on the lower surface of the outer edge of the top plate 123, and a plurality of second engaging portions 242 are arranged circumferentially on the upper surface of the support base 413. In practice, the first engaging portions 241 and second engaging portions 242 are positioned circumferentially at different locations with the plurality of first contact portions 411 of the substrate support portion 141 and the plurality of second contact portions 421 of the substrate pressing portion 142. Preferably, three or more sets of these engaging portions are provided; in this embodiment, four sets are provided. A recessed portion facing upwards is provided at the lower part of the first engaging portion 241. The second engaging portions 242 protrude upwards from the support base 413.

[0116] The following describes the use of substrate processing apparatus 113 ( Figure 8 and Figure 9 The substrate processing method for removing the organic film from the substrate W is described.

[0117] like Figure 10 As shown, in step S11 ( Figure 3 In this configuration, with the chamber cover 122 separated from the chamber body 121 and positioned above, and the cup portion 161 separated from the chamber cover 122 and positioned below, the substrate W is moved into the chamber 12 by an external transport mechanism and supported from below by the substrate support portion 141. Hereinafter, Figure 10The state of the shown chamber 12 and cup portion 161 is referred to as the "open state". The opening between the chamber cover portion 122 and the chamber sidewall portion 214 is annular with the central axis J1 as its center, and is referred to below as the "annular opening 81". In the substrate processing apparatus 113, the chamber cover portion 122 is separated from the chamber body 121, thereby forming an annular opening 81 around the substrate W (i.e., radially outward). In step S11, the substrate W is moved in through the annular opening 81.

[0118] When the substrate W is loaded, the nozzle unit 188 is pre-accommodated in the space 160 formed between the cup portion 161 and the cup opposing portion 163. The space 160 is a generally annular space that surrounds the outer periphery of the chamber 12 throughout its entire circumference. In the following description, the space 160 will be referred to as the "lateral space 160". Figure 11 This is a top view of the substrate processing apparatus 113. Figure 11 To facilitate understanding of the housing state of the nozzle unit 188, the illustrations of the chamber cover 122, cup 161, etc., are omitted. Additionally, the bellows 617 is marked with a shading line.

[0119] like Figure 11 As shown, the nozzle support 882 of the nozzle unit 188 is curved radially outward when viewed from above. In other words, the nozzle unit 188 is generally arc-shaped. In the lateral space 160, the nozzle unit 188 extends along the bellows 617 and the side wall 611 of the cup portion 161 (see reference 160). Figure 10 Configure it in the way of ).

[0120] When housing the nozzle unit 188, the cup portion 161 is located at Figure 8 In the indicated position, the nozzle unit 188 is rotated using the support rotation mechanism 891 and moved outward through the annular opening 81. Thus, the nozzle unit 188 is housed in the lateral space 160 between the cup portion 161 and the cup opposing portion 163. Then, the cup portion 161 is lowered to the indicated position using the cup portion moving mechanism 162. Figure 10 As shown in the diagram, the lateral space 160 decreases as the cup portion 161 descends.

[0121] When the substrate W is moved in, the cup portion 161 moves from... Figure 10 The position shown rises to Figure 12 The position shown is located radially outside the annular opening 81 throughout the entire circumference. In the following description, Figure 12 The state of chamber 12 and cup 161 shown is referred to as the "first closed state". Figure 8 The same applies to the state of the other two. Additionally, [the following will be implemented]. Figure 12 The position of the cup portion 161 shown is called the "liquid receiving position". Figure 10The position of the cup portion 161 shown is called the "retracted position". The cup portion moving mechanism 162 moves the cup portion 161 vertically between the liquid receiving position radially outside the annular opening 81 and the retracted position which is lower than the liquid receiving position.

[0122] In the cup portion 161 located at the liquid receiving position, the side wall portion 611 is radially opposed to the annular opening 81. Furthermore, the upper surface of the inner edge of the upper surface portion 612 is in contact with the lip seal 232 at the lower end of the outer edge of the chamber cover portion 122 throughout its entire circumference. A sealing portion preventing the passage of gas and liquid is formed between the chamber cover portion 122 and the upper surface portion 612 of the cup portion 161. Thus, a sealed space (hereinafter referred to as "expanded sealed space 100") is formed, surrounded by the chamber body 121, the chamber cover portion 122, the cup portion 161, and the cup-opposing portion 163. The expanded sealed space 100 is a space formed by the connection between the chamber space 120 between the chamber cover 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.

[0123] Next, step S12 (removing the organic film from the substrate W) begins. Figure 3 Specifically, the substrate W is rotated at a constant speed (a lower speed, hereinafter referred to as the "stable speed") by the substrate rotation mechanism 15. And, the rotation of the substrate W from the ozone supply unit 200 (see reference 15) begins. Figure 9 Supply ozone-containing gas to the enlarged enclosed space 100 (in step ST10) Figure 5 (corresponding to), and begins to discharge gas from the expanded sealed space 100 based on the outer exhaust section 194. Thus, after a predetermined time, the expanded sealed space 100 becomes filled with ozone-containing gas (as in step ST20). Figure 5 (Corresponding to). Furthermore, the supply of ozone-containing gas to the enlarged enclosed space 100 and the exhaust of gas from the enlarged enclosed space 100 can also be achieved from... Figure 10 The process is in the open state as shown.

[0124] Next, heated gas is ejected from multiple gas ejection nozzles 180a toward the lower surface 92 of the rotating substrate W. This heats the substrate W. Additionally, a predetermined amount of liquid medicine is supplied from the liquid medicine supply unit 300 to the nozzle unit 188, which is mounted in the cup portion 161 within the side space 160. Thus, pre-dispensing from the atomizing nozzle 881 is performed while the nozzle unit 188 is housed within the side space 160 (i.e., the nozzle unit 188 is entirely located within the side space 160). The pre-dispensed liquid medicine from the atomizing nozzle 881 is received by the liquid receiving recess 165.

[0125] When the pre-dispensing is complete, the nozzle support 882 is rotated using the support rotation mechanism 891 located on the outside of the enlarged sealed space 100, thereby, as Figure 8 As shown, the atomizing nozzle 881 moves upward toward the substrate W via the annular opening 81. Furthermore, the support rotation mechanism 891 is controlled by the control unit 10 to initiate the reciprocating movement of the atomizing nozzle 881 above the substrate W. The atomizing nozzle 881 continues to reciprocate in the horizontal direction along a predetermined movement path connecting the center and outer edge of the substrate W.

[0126] Furthermore, liquid medicine is supplied from the liquid medicine supply unit 300 to the atomizing nozzle 881, and the liquid medicine is sprayed from the horizontally oscillating atomizing nozzle 881 onto the upper surface 91 of the substrate W (as in step ST40). Figure 5 (Corresponding to). The liquid medicine diffuses outwards through the rotation of the substrate W, and the entire upper surface 91 is covered with the liquid medicine. The liquid medicine continues to be sprayed onto the rotating substrate W from the atomizing nozzle 881 that swings in the horizontal direction (as in step ST50). Figure 5 (Correspondingly), the solution can be supplied to the upper surface 91 of the substrate W in a substantially uniform manner. Furthermore, the temperature uniformity of the solution on the substrate W can also be improved. As a result, the uniformity of the solution treatment on the substrate W can be improved.

[0127] During the spraying of the liquid medicine from nozzle unit 188, heated gas is also continuously ejected from gas ejection nozzle 180a. Thus, while heating the substrate W to approximately the desired temperature, the upper surface 91 is cleaned based on the liquid medicine. As a result, the uniformity of the liquid medicine treatment on the substrate W can be further improved.

[0128] In the enlarged sealed space 100, the liquid medicine that splashes from the upper surface 91 of the rotating substrate W is received by the cup portion 161 through the annular opening 81 and guided to the liquid receiving recess 165. The liquid medicine guided to the liquid receiving recess 165 is then... Figure 9 The first discharge path 191 shown flows into the gas-liquid separation section 193. In the liquid recovery section 195, the liquid is recovered from the gas-liquid separation section 193, and after impurities are removed from the liquid through a filter or the like, it is reused.

[0129] When a predetermined time (e.g., 60–120 seconds) has elapsed since the start of the liquid medicine supply, the supply of liquid medicine from the nozzle unit 188 and the supply of heating gas from the gas ejection nozzle 180a are stopped (as per step ST60). Figure 5 (Corresponding). Additionally, stop supplying ozone from the ozone supply department 200 (refer to...). Figure 9 The introduction of ozone-containing gas (with step ST30) Figure 5(Corresponding). Next, the substrate rotation mechanism 15 rotates the substrate W at a speed higher than the stable speed for a specified time (e.g., 1 to 3 seconds) to remove the liquid medicine from the substrate W. Additionally, the nozzle unit 188 rotates via the support rotation mechanism 891, as... Figure 12 As shown, it moves from the chamber space 120 to the side space 160 via the annular opening 81.

[0130] When the nozzle unit 188 moves toward the lateral space 160, the chamber cover 122 and the cup 161 move downwards simultaneously. Furthermore, as... Figure 13 As shown, the lip seal 231 at the lower end of the outer edge of the chamber cover 122 connects with the upper part of the chamber sidewall 214, thereby closing the annular opening 81 and sealing the chamber space 120 in a state isolated from the side space 160. The cup portion 161 and... Figure 10 Similarly, it is located in the retreat position. The lateral space 160 is sealed off from the chamber space 120. Hereinafter, Figure 13 The state of the chamber 12 and the cup portion 161 shown is referred to as the "second sealed state". In the second sealed state, the substrate W is directly opposite the inner wall of the chamber 12, and there are no other liquid receiving portions between them. In addition, the nozzle unit 188 is isolated from the chamber space 120 and housed in the side space 160.

[0131] In the second sealed state, the plurality of second contact portions 421 of the substrate pressing portion 142 contact the outer edge of the substrate W. Multiple 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 base 413 of the substrate support portion 141. Hereinafter, each pair of magnets will 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 engaging portion 241, and the second engaging portion 242. When the substrate pressing portion 142 is in contact with the substrate W, a downward force acts on the top plate 123 by the magnetic force (attraction) acting between the magnet pairs. Thus, the substrate pressing portion 142 presses the substrate W against the substrate support portion 141.

[0132] In the substrate processing apparatus 113, the substrate pressing part 142 presses the substrate W against the substrate support part 141 using the weight of the top plate 123 and the magnetic force of the magnet pair. Thus, the substrate W can be firmly held by clamping it from above and below using the substrate pressing part 142 and the substrate support part 141.

[0133] In the second sealed state, the flange 239 of the held portion 237 separates above the flange 224 of the plate holding portion 222, and the plate holding portion 222 and the held portion 237 are no longer in contact. In other words, the holding of the top plate 123 based on the plate holding portion 222 is released. Therefore, the top plate 123, independent of the chamber cover portion 122, rotates together with the plate holding portion 14 and the plate W held in the plate holding portion 14 via the plate rotating mechanism 15.

[0134] Furthermore, in the second sealed state, the second engaging portion 242 is inserted into the recess at the lower part of the first engaging portion 241. Thus, the top plate 123 engages with the support base 413 of the substrate support portion 141 in the circumferential direction centered on the central axis J1. In other words, the first engaging portion 241 and the second engaging portion 242 are position limiting 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., the relative position in the fixed circumferential direction). When the chamber cover 122 descends, the rotational position of the support base 413 is controlled by the substrate rotation mechanism 15 to engage the first engaging portion 241 and the second engaging portion 242.

[0135] When the chamber space 120 and the side space 160 are independently sealed, the operation stops based on the outer exhaust section 194 (see reference). Figure 9 The gas is discharged, and the gas discharge from the chamber space 120 of the inner exhaust section 198 begins. Pure water, as a rinsing fluid, is supplied to the substrate W via the pure water supply section 184 (step S13). Figure 3 )).

[0136] Pure water from the pure water supply unit 184 is continuously supplied to the center of the upper surface 91 and lower surface 92 of the substrate W by being ejected from the upper nozzle 181 and the lower nozzle 182. The pure water diffuses to the outer periphery of the upper surface 91 and lower surface 92 due to the rotation of the substrate W, and then disperses outward from the outer periphery of the substrate W. The pure water dispersed from the substrate W is received by the inner wall of the chamber 12 (i.e., the inner wall of the chamber cover 122 and the inner wall of the chamber sidewall 214), and then... Figure 9 The second discharge path 192, gas-liquid separation section 197, and liquid discharge section 199 shown are discarded (the same applies to the drying process of the substrate W described later). Thus, along with the rinsing process of the upper surface 91 and the cleaning process of the lower surface 92 of the substrate W, the cleaning of the chamber 12 is also substantially performed.

[0137] When a predetermined time has elapsed since the start of pure water supply, the supply of pure water from the pure water supply unit 184 is stopped. Furthermore, within the chamber space 120, the rotational speed of the substrate W is sufficiently higher than the stable rotational speed. As a result, pure water is removed from the substrate W, and the substrate W undergoes a drying process (step S14). Figure 3When a predetermined time has elapsed since the start of drying of substrate W, the rotation of substrate W stops. Regarding the drying process of substrate W, the chamber space 120 can also be depressurized using the internal exhaust section 198 to create a depressurized atmosphere lower than atmospheric pressure. Alternatively, after the supply of pure water from the pure water supply section 184 and before the drying of substrate W, IPA can be supplied to substrate W from the IPA supply section 185 to replace the pure water with IPA on substrate W.

[0138] Then, the chamber cover 122 and the top plate 123 rise, as... Figure 10 As shown, chamber 12 is in the open state. In step S14, the top plate 123 rotates together with the substrate support 141, so almost no liquid remains on the lower surface of the top plate 123, and the liquid will not fall from the top plate 123 onto the substrate W when the chamber cover 122 rises. The substrate W is moved out of the chamber 12 by an external conveying mechanism (step S15). Figure 3 )).

[0139] Furthermore, the chamber opening and closing mechanism 131 does not necessarily need to move the chamber cover 122 in the vertical direction; the chamber body 121 can move in the vertical direction while the chamber cover 122 is fixed. The chamber 12 is not necessarily limited to a generally cylindrical shape and can be of various shapes. The shape and structure of the stator 151 and rotor 152 of the substrate rotation mechanism 15 can be varied. The rotor 152 does not necessarily need to rotate in a suspended state; a guide or other structure that mechanically supports the rotor 152 can be provided inside the chamber 12, and the rotor 152 rotates along the guide. The substrate rotation mechanism 15 does not necessarily need to be a hollow motor; a shaft-rotating type motor can also be used as the substrate rotation mechanism. In the substrate processing apparatus 113, an enlarged sealed space 100 can be formed by connecting the portion other than the upper surface portion 612 of the (outer) cup portion 161 (e.g., the sidewall portion 611) to the chamber cover 122. The shapes of the (outer) cup portion 161 and the inner cup portion 161a can be appropriately varied.

[0140] According to this embodiment 3, the airtightness of the chamber 12 used for ozone treatment can be ensured to a high degree. Furthermore, in the above description, the treatment performed in this embodiment 3... Figure 5 (Implementation Method 1) The same process has been described in detail, but it can also be replaced by... Figure 7 (Implementation Method 2) The same process. In this case, pressure gauge 250 ( Figure 6 : Implementation method 2) and at least one of the ozone concentration meter can be configured to perform chamber 12 ( Figure 8 Measurement of the atmosphere inside.

[0141] The structures and processes described in the above embodiments and variations can be appropriately combined or omitted as long as they do not contradict each other.

Claims

1. A substrate processing method for removing an organic film from a substrate, characterized in that, The substrate processing method includes: a) A process of filling the space above at least the substrate within the substrate processing chamber with ozone gas by introducing ozone gas into the substrate processing chamber. b) After step a), a process of spraying a heated pharmaceutical solution containing sulfuric acid onto the substrate via the space using the flow of an inactive gas begins. c) Continue the spraying process that began in step b); d) Stop the spraying process that was continuing in step c). Step a) includes a step of confirming that at least one of the pressure and ozone concentration in the substrate processing chamber is above a predetermined threshold. Step b) is performed after step a) so that the spraying of the drug solution onto the substrate via the space begins when the measured value is above the threshold. After the introduction of ozone-containing gas into the substrate processing chamber is performed in step a), the introduction continues in steps b) and c).

2. A substrate processing method for removing an organic film from a substrate, characterized in that, The substrate processing method includes: a) A process of filling the space above at least the substrate within the substrate processing chamber with ozone gas by introducing ozone gas into the substrate processing chamber. b) After step a), a process of spraying a heated pharmaceutical solution containing sulfuric acid onto the substrate via the space using the flow of an inactive gas begins. c) Continue the spraying process that began in step b); d) Stop the spraying process that was continuing in step c). Step a) includes a step of confirming that at least one of the pressure and ozone concentration in the substrate processing chamber is above a predetermined threshold. Step b) is performed after step a) so that the spraying of the drug solution onto the substrate via the space begins when the measured value is above the threshold. After the introduction of ozone-containing gas into the substrate processing chamber is performed in step a), the introduction is stopped before step c).

3. The substrate processing method according to claim 1 or 2, characterized in that, The liquid medicine that has been sprayed through step c) is divided into a first liquid that is received and thus recovered by a cup portion surrounding the substrate and a second liquid that is recovered outside the cup portion, and the second liquid is re-sprayed in a manner that does not contain the first liquid.

4. A substrate processing apparatus for removing an organic film from a substrate, characterized in that, The substrate processing apparatus includes: Substrate processing chamber; A substrate holding section holds the substrate in the substrate processing chamber; An ozone supply unit supplies ozone-containing gas into the substrate processing chamber; An atomizing nozzle sprays a liquid medicine onto the substrate using the flow of an inactive gas. The liquid medicine supply unit has a heater that supplies the liquid medicine heated by the heater to the atomizing nozzle; The control unit controls the ozone supply unit to fill the space above at least the substrate within the substrate processing chamber by introducing ozone-containing gas into the substrate processing chamber. When the space is filled with ozone-containing gas, the control unit confirms that at least one of the pressure and ozone concentration in the substrate processing chamber is above a predetermined threshold. After the ozone-containing gas fills the space, the control unit controls the liquid supply unit to start spraying the liquid onto the substrate through the space when the measured value is above the threshold, and continues spraying, and then stops spraying. The control unit controls the ozone supply unit so that after the ozone-containing gas is introduced into the substrate processing chamber, the introduction of the ozone-containing gas continues while the spraying of the liquid solution begins and continues.

5. A substrate processing apparatus for removing an organic film from a substrate, characterized in that, The substrate processing apparatus includes: Substrate processing chamber; A substrate holding section holds the substrate in the substrate processing chamber; An ozone supply unit supplies ozone-containing gas into the substrate processing chamber; An atomizing nozzle sprays a liquid medicine onto the substrate using the flow of an inactive gas. The liquid medicine supply unit has a heater that supplies the liquid medicine heated by the heater to the atomizing nozzle; The control unit controls the ozone supply unit to fill the space above at least the substrate within the substrate processing chamber by introducing ozone-containing gas into the substrate processing chamber. When the space is filled with ozone-containing gas, the control unit confirms that at least one of the pressure and ozone concentration in the substrate processing chamber is above a predetermined threshold. After the ozone-containing gas fills the space, the control unit controls the liquid supply unit to start spraying the liquid onto the substrate through the space when the measured value is above the threshold, and continues spraying, and then stops spraying. The control unit controls the ozone supply unit to stop the introduction of ozone-containing gas into the substrate processing chamber after the introduction of ozone-containing gas has been performed and before the spraying of the liquid medicine continues.

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