Substrate processing method and substrate processing apparatus

Abstract

A substrate processing method and a substrate processing apparatus are provided. The substrate processing method includes: a sulfuric acid immersion process of immersing a plurality of substrates in a sulfuric acid liquid contained in a sulfuric acid tank; a carrying process of taking out the plurality of substrates from the sulfuric acid tank and carrying the plurality of substrates to an ozone gas processing unit; and an ozone exposure process of exposing the plurality of substrates carried to the ozone gas processing unit to an ozone-containing gas. The ozone gas processing unit can also include a gas processing chamber that accommodates the plurality of substrates. The ozone exposure process can also include a process of exposing the plurality of substrates to the ozone-containing gas by arranging the plurality of substrates taken out from the sulfuric acid tank in a processing space in the gas processing chamber.

Description

[0001] Cross-referencing

[0002] This application claims priority based on Japanese Patent Application No. 2021-155177, filed on September 24, 2021, the entire contents of which are incorporated herein by reference. Technical Field

[0003] This invention relates to a substrate processing method and an apparatus for processing substrates. Substrates that can be processed include, for example, semiconductor wafers, substrates for FPD (Flat Panel Display) devices such as liquid crystal display devices and organic EL (Electroluminescence) display devices, substrates for optical discs, substrates for magnetic disks, substrates for optical discs, substrates for photomasks, ceramic substrates, and substrates for solar cells. Background Technology

[0004] In the substrate processing apparatus disclosed in US2014 / 0045339A1, ozone gas is supplied to sulfuric acid through piping, causing the ozone to dissolve in the sulfuric acid to form sulfuric acid ozone. By mixing sulfuric acid and ozone, persulfate (S₂O₈) is generated. 2- ) as an active species (etchant).

[0005] In the substrate processing apparatus of US2014 / 0045339A1, sulfuric acid ozone flows through a sulfuric acid ozone supply pipe into a water mixing section and mixes with water, thereby forming a sulfuric acid ozone / water mixture. This sulfuric acid ozone / water mixture is then sprayed from a sulfuric acid ozone / water nozzle onto the substrate. By supplying the sulfuric acid ozone / water mixture to the surface of the substrate while it is being rotated, the resist on the substrate surface is removed. Summary of the Invention

[0006] In the substrate processing apparatus disclosed in US2014 / 0045339A1, the dilution heat generated by mixing water with sulfuric acid ozone causes the temperature of the sulfuric acid ozone / water mixture to become higher than the temperature of the sulfuric acid ozone before mixing. Therefore, even if a relatively low-temperature sulfuric acid ozone is used as the sulfuric acid ozone before mixing, a sulfuric acid ozone / water mixture at the temperature required to remove the resist can be supplied to the surface of the substrate. Furthermore, by maintaining a relatively low temperature for the sulfuric acid ozone before mixing, a large amount of ozone gas can be dissolved in the sulfuric acid ozone before mixing.

[0007] However, in the apparatus described in US2014 / 0045339A1, the concentration of persulfate, which has oxidizing power, is reduced by mixing sulfuric acid, ozone, and water. Therefore, it is possible that sufficient oxidizing power may not be obtained.

[0008] One embodiment of the present invention provides a substrate processing method and a substrate processing apparatus capable of rapidly and thoroughly removing organic films such as resists from a substrate.

[0009] An embodiment of the present invention provides a substrate processing method, which includes a sulfuric acid immersion step of immersing multiple substrates in a sulfuric acid bath containing sulfuric acid liquid, a transport step of removing the multiple substrates from the sulfuric acid bath and transporting the multiple substrates to an ozone gas treatment unit, and an ozone exposure step of exposing the multiple substrates transported to the ozone gas treatment unit to ozone containing ozone gas.

[0010] According to this method, an ozone gas treatment unit is used to expose multiple substrates, which have been immersed in a sulfuric acid-containing liquid in a single step, to ozone gas. This allows ozone in the ozone gas to dissolve in the sulfuric acid-containing liquid adhering to the multiple substrates after they have been removed from the sulfuric acid-containing liquid, thereby generating persulfate in the sulfuric acid-containing liquid.

[0011] As a result, organic films such as resists can be removed quickly and thoroughly from the substrate.

[0012] Ozone-containing gas contains gaseous ozone (ozone gas), and sulfuric acid-containing liquid contains sulfuric acid. An example of a sulfuric acid-containing liquid is an aqueous solution of sulfuric acid.

[0013] In one embodiment of the present invention, the ozone gas treatment unit includes a gas treatment chamber accommodating a plurality of the substrates. The ozone exposure process includes the step of exposing the plurality of substrates to ozone-containing gas by placing them, which are taken from the sulfuric acid bath, into the treatment space within the gas treatment chamber.

[0014] According to this method, multiple substrates can be exposed to ozone-containing gas almost simultaneously within a processing space. Therefore, organic films can be removed from the substrates more quickly and thoroughly.

[0015] In one embodiment of the present invention, the ozone exposure process includes the following steps: supplying ozone-containing gas to the processing space through a plurality of supply holes that open in the wall portion dividing the processing space, and venting the processing space through a plurality of exhaust holes that open in the wall portion, thereby exposing a plurality of substrates disposed in the processing space to ozone-containing gas.

[0016] According to this method, ozone-containing gas is supplied to the processing space through multiple supply holes that open in the wall of the processing space, and the processing space is vented through multiple exhaust holes that open in the wall. Therefore, even if ozone in the atmosphere is consumed due to dissolution of the sulfuric acid-containing liquid in contact with the substrate, the ozone-containing gas supplied to the processing space can still be used to supply ozone to the atmosphere in contact with the sulfuric acid-containing liquid adhering to the substrate. Therefore, the concentration of ozone in the atmosphere in contact with the sulfuric acid-containing liquid on the substrate can be maintained at a sufficiently high level. Therefore, persulfuric acid can be generated in the sulfuric acid-containing liquid on the substrate.

[0017] In one embodiment of the present invention, in the gas treatment chamber, multiple supply hole rows, each composed of multiple supply holes, are arranged in a predetermined arrangement direction. Furthermore, the ozone exposure process includes a step of arranging multiple substrates in the treatment space such that multiple substrates are arranged in the arrangement direction and each substrate is positioned between the supply hole rows.

[0018] According to this method, ozone-containing gas from each row of supply holes is supplied between the substrates. Therefore, ozone can be adequately supplied to the atmosphere in contact with the sulfuric acid-containing liquid on each substrate, allowing the ozone to fully dissolve in the sulfuric acid-containing liquid on each substrate. As a result, uneven removal of the organic film between the substrates can be reduced.

[0019] In one embodiment of the present invention, the sulfuric acid impregnation process includes a vertical impregnation process in which multiple substrates in a vertical orientation are immersed in a sulfuric acid-containing liquid in the sulfuric acid bath. The substrate processing method further includes an orientation change process in which the orientation of the multiple substrates removed from the sulfuric acid bath is changed from a vertical orientation to a horizontal orientation. Furthermore, the ozone exposure process includes a horizontal exposure process in which the multiple horizontally oriented substrates are exposed to ozone-containing gas.

[0020] According to this method, multiple substrates can be immersed in a sulfuric acid-containing liquid in a vertical orientation. Therefore, multiple substrates can be immersed in the sulfuric acid-containing liquid at approximately the same time. Furthermore, according to this method, after changing the orientation of the multiple substrates from vertical to horizontal, the multiple substrates are exposed to ozone gas. Therefore, uneven thickness of the sulfuric acid-containing liquid at various locations on the substrates caused by the downward movement of the sulfuric acid-containing liquid attached to the vertically oriented substrates due to its own weight can be suppressed. Therefore, uneven removal of the organic film at various locations on the substrates can be reduced.

[0021] In one embodiment of the present invention, the substrate processing method further includes a substrate rotation step, wherein after the orientation change step and before the plurality of substrates are exposed to ozone-containing gas in the ozone exposure step, the plurality of substrates are rotated around a vertical axis passing through the center portion of the plurality of substrates in a horizontal orientation.

[0022] Therefore, excess sulfuric acid-containing liquid can be removed from the substrate, improving the uniformity of the sulfuric acid-containing liquid thickness at various locations on the substrate. This, in turn, improves the uniformity of ozone concentration in the sulfuric acid-containing liquid at various locations on the substrate. Consequently, uneven removal of the organic film at various locations on the substrate can be reduced.

[0023] In one embodiment of the present invention, the processing space is disposed directly above the sulfuric acid bath. Furthermore, the transport process includes a step of placing multiple substrates in the processing space by lifting multiple substrates from the sulfuric acid bath.

[0024] According to this method, multiple substrates can be moved from the sulfuric acid bath into the processing space by moving them in one direction, such as lifting them from the sulfuric acid bath. Therefore, after the sulfuric acid-containing liquid adheres to the multiple substrates, they can be rapidly exposed to ozone-containing gas. Thus, the organic film can be rapidly removed from the substrates.

[0025] Another embodiment of the present invention provides a substrate processing apparatus, comprising a sulfuric acid tank for storing a sulfuric acid-containing liquid capable of impregnating multiple substrates, an ozone gas treatment unit for exposing multiple substrates to ozone gas, and a transport unit for transporting multiple substrates between the sulfuric acid tank and the ozone gas treatment unit.

[0026] According to the apparatus, an ozone gas treatment unit exposes multiple substrates, which have been immersed in a sulfuric acid-containing liquid in a single step, to ozone gas. This causes ozone from the ozone gas to dissolve in the sulfuric acid-containing liquid adhering to the multiple substrates after they have been removed from the sulfuric acid-containing liquid, thereby generating persulfate in the sulfuric acid-containing liquid adhering to the multiple substrates.

[0027] As a result, organic films such as resists can be removed quickly and thoroughly from the substrate.

[0028] In another embodiment of the present invention, the ozone gas treatment unit includes a gas treatment chamber having a processing space capable of accommodating multiple substrates, and exposing the multiple substrates contained in the processing space to ozone gas.

[0029] According to this device, multiple substrates can be exposed to ozone-containing gas almost simultaneously within the processing space. Therefore, organic films can be removed from the substrates more quickly and thoroughly.

[0030] In another embodiment of the present invention, the gas processing chamber has a wall portion that divides the processing space, a plurality of supply holes that open in the wall portion and supply ozone-containing gas to the processing space, and a plurality of exhaust holes that open in the wall portion and exhaust gas from the processing space.

[0031] According to this apparatus, ozone-containing gas is supplied to the processing space through multiple supply holes that open in the wall of the processing space, and the processing space is vented through multiple exhaust holes that open in the wall. Therefore, even if ozone in the atmosphere is consumed due to dissolution of the sulfuric acid-containing liquid in contact with the substrate, the ozone-containing gas supplied to the processing space can still be used to supply ozone to the atmosphere in contact with the sulfuric acid-containing liquid adhering to the substrate. Therefore, the concentration of ozone in the atmosphere in contact with the sulfuric acid-containing liquid on the substrate can be maintained at a sufficiently high level. Therefore, persulfate can be sufficiently generated in the sulfuric acid-containing liquid on the substrate.

[0032] In another embodiment of the present invention, the gas processing chamber has a plurality of supply hole rows, each composed of a plurality of supply holes, arranged in a predetermined arrangement direction. Furthermore, the transport unit supports a plurality of substrates arranged in the aforementioned arrangement direction and transports the plurality of substrates into the gas processing chamber such that each substrate is positioned between the supply hole rows.

[0033] According to this apparatus, a transport unit moves multiple substrates into a processing space with each substrate positioned between the rows of supply holes. Therefore, ozone-containing gas supplied from each row of supply holes can be supplied between the substrates. Consequently, ozone can be adequately supplied to the atmosphere in contact with the sulfuric acid-containing liquid on each substrate, allowing the ozone to fully dissolve in the sulfuric acid-containing liquid on each substrate. As a result, uneven removal of the organic film between the substrates can be reduced.

[0034] In another embodiment of the present invention, the sulfuric acid bath is capable of immersing multiple vertically oriented substrates in a sulfuric acid-containing liquid. The processing space is capable of accommodating multiple horizontally oriented substrates. Furthermore, the transport unit includes an orientation switching mechanism that switches the orientation of the multiple substrates between a vertical orientation and a horizontal orientation.

[0035] According to this apparatus, multiple substrates can be immersed in a sulfuric acid-containing liquid in a vertical orientation. Therefore, multiple substrates can be immersed in the sulfuric acid-containing liquid at approximately the same time. Furthermore, if the orientation of the multiple substrates is changed from vertical to horizontal using the orientation switching mechanism of the transport unit, and then the multiple substrates are transported to the gas treatment chamber, the horizontally oriented substrates can be exposed to ozone-containing gas. Therefore, uneven thickness of the sulfuric acid-containing liquid at different locations on the substrate can be suppressed due to the downward movement of the sulfuric acid-containing liquid adhering to the vertically oriented substrate due to its own weight. Therefore, uneven removal of the organic film at different locations on the substrate can be reduced.

[0036] In another embodiment of the invention, the transport unit includes a transport robot having a lifter that supports multiple substrates. The attitude switching mechanism switches the attitude of the multiple substrates between a vertical attitude and a horizontal attitude by deforming the lifter.

[0037] According to this device, after immersing multiple substrates in a sulfuric acid bath, the lifting mechanism of a transport robot can be deformed to change the orientation of the substrates from vertical to horizontal. Furthermore, the horizontally oriented substrates can be exposed to ozone gas in a gas treatment chamber. In this way, a single robot can be used to change the orientation of multiple substrates and transport them from the sulfuric acid bath to the gas treatment chamber. Since the transfer of substrates between robots can be eliminated, organic films can be quickly removed from the substrates.

[0038] In another embodiment of the invention, the processing space is positioned directly above the sulfuric acid tank. Furthermore, the transport unit moves up and down while supporting multiple substrates, thereby transporting the multiple substrates between the gas processing chamber and the sulfuric acid tank.

[0039] According to this apparatus, a transport unit supports multiple substrates while moving up and down, thereby transporting the substrates between a gas treatment chamber and a sulfuric acid tank. Therefore, by moving the substrates in one direction—lifting them from the sulfuric acid tank—the substrates can be moved from the sulfuric acid tank into the processing space. Thus, after the sulfuric acid-containing liquid adheres to the substrates, they can be rapidly exposed to ozone-containing gas. Therefore, organic films can be rapidly removed from the substrates.

[0040] In another embodiment of the present invention, the substrate processing apparatus further includes a cover member for separating the interior of the sulfuric acid tank from the processing space and for opening and closing the sulfuric acid tank. Therefore, the dissolution of ozone-containing gas in the sulfuric acid-containing liquid stored in the sulfuric acid tank can be suppressed. Therefore, in subsequent processing of multiple substrates, the removal of the organic film from the substrate before the supply of ozone-containing gas to the processing space can be suppressed. Therefore, deviations during the processing using persulfate can be suppressed.

[0041] In another embodiment of the present invention, the transport unit includes: a first transport robot that transports multiple substrates in a vertical orientation to the sulfuric acid tank; a second transport robot that transports multiple substrates in a horizontal orientation to the gas treatment chamber; and a main transport robot that transports multiple substrates between the first transport robot and the second transport robot. The orientation switching mechanism switches the orientation of the multiple substrates transported by the main transport robot between a horizontal orientation and a vertical orientation.

[0042] According to this device, different robots are used to transport multiple substrates to the sulfuric acid bath, transport multiple substrates to the gas treatment chamber, and change the posture of multiple substrates. Therefore, it is possible to suppress the complexity of the structure of each robot.

[0043] In another embodiment of the present invention, the second transport robot transports multiple substrates in a horizontal orientation to the gas treatment chamber and rotates the multiple substrates within the gas treatment chamber around a vertical axis passing through the center of the multiple substrates in a horizontal orientation.

[0044] According to this apparatus, multiple substrates can be rotated within a gas treatment chamber to remove excess sulfuric acid-containing liquid from the substrates. By utilizing the rotation of the substrates to remove the sulfuric acid-containing liquid, the uniformity of the sulfuric acid-containing liquid thickness at various locations on the substrates can be improved. This, in turn, improves the uniformity of ozone concentration in the sulfuric acid-containing liquid at various locations on the substrates. Consequently, uneven removal of organic films at various locations on the substrates can be reduced.

[0045] In another embodiment of the invention, a heat treatment chamber for heating multiple substrates is also included. The aforementioned transport unit further includes a third transport robot that transports the multiple horizontally oriented substrates to the heat treatment chamber, causing the multiple substrates to rotate within the heat treatment chamber about a vertical axis passing through the center of the horizontally oriented substrates. Furthermore, the main transport robot transports the multiple substrates between the sulfuric acid tank, the gas treatment chamber, and the heat treatment chamber.

[0046] According to this apparatus, multiple substrates can be rotated within a heat treatment chamber to remove excess sulfuric acid-containing liquid from the substrates. By utilizing the rotation of the substrates to remove the sulfuric acid-containing liquid, the uniformity of the thickness of the sulfuric acid-containing liquid at various locations on the substrates can be improved.

[0047] Excess sulfuric acid-containing liquid is removed from the substrates in a heating chamber, allowing multiple substrates to be heated simultaneously. The heated substrates are then transported to a gas treatment chamber via a main transport robot and a second transport robot, further removing excess sulfuric acid-containing liquid and exposing them to ozone gas. This improves the uniformity of ozone concentration in the sulfuric acid-containing liquid at various locations on the substrates and enhances the activity of persulfate. Consequently, uneven removal of the organic film at different locations on the substrates is further reduced.

[0048] The above-mentioned or other objects, features and effects of the present invention will become clear from the following description of the embodiments with reference to the accompanying drawings. Attached Figure Description

[0049] Figure 1 This is a schematic plan view showing the layout of a substrate processing apparatus according to an embodiment of the present invention.

[0050] Figure 2 This is a schematic front view showing a structural example of the main parts of the aforementioned substrate processing apparatus.

[0051] Figure 3 This is a cross-sectional view illustrating an example of the structure of the auxiliary handling robot included in the aforementioned substrate processing apparatus.

[0052] Figure 4 This is a block diagram illustrating an example of the electrical structure of the aforementioned substrate processing apparatus.

[0053] Figure 5 This is a flowchart illustrating an example of substrate processing performed by the aforementioned substrate processing apparatus.

[0054] Figures 6A to 6C This is a schematic diagram illustrating the situation of the substrate processing apparatus during the execution of the above-described substrate processing.

[0055] Figure 7 This is a diagram showing the side wall of the gas processing chamber as viewed from the processing space of the gas processing chamber when the elevator is in the gas processing position.

[0056] Figure 8 This is a flowchart illustrating another example of the above-described substrate processing.

[0057] Figure 9This is a front view of the main part of the substrate processing apparatus according to the first variation of the first embodiment.

[0058] Figures 10A to 10C This is a schematic diagram illustrating the substrate processing apparatus described in the first modified example above during the execution of substrate processing.

[0059] Figure 11 This is a front view of the main part of the substrate processing apparatus according to the second variation of the first embodiment.

[0060] Figure 12A as well as Figure 12B This is a schematic diagram illustrating a structural example of the first transport robot included in the substrate processing apparatus according to the second embodiment, showing a state in which the lifter supports a batch of substrates in a vertical posture and a state in which the lifter supports a batch of substrates in a horizontal posture.

[0061] Figures 13A-13C This is a schematic diagram illustrating a substrate processing apparatus according to a second embodiment during substrate processing.

[0062] Figure 14 This is a view of the side wall of the gas processing chamber as seen from the processing space of the gas processing chamber during the substrate processing in the second embodiment, when the lifter is in the gas processing position.

[0063] Figure 15 This is a schematic diagram illustrating a substrate processing apparatus related to a variation of the second embodiment.

[0064] Figure 16 This is a front view showing a structural example of the main parts of the substrate processing apparatus according to the third embodiment.

[0065] Figure 17A This is a schematic diagram illustrating an example of the structure of the main transport robot included in the substrate processing apparatus of the third embodiment. Figure 17B It is along Figure 17A A cross-sectional view of line XVIIB-XVIIB.

[0066] Figures 18A-18E This is a schematic diagram illustrating a substrate processing apparatus according to a third embodiment during substrate processing.

[0067] Figure 19 This is a front view of the main part of the substrate processing apparatus according to the first variation of the third embodiment.

[0068] Figure 20A and Figure 20B This is a schematic diagram illustrating a substrate processing apparatus according to a first variation of a third embodiment during substrate processing.

[0069] Figure 21 This is a flowchart illustrating an example of substrate processing performed by a substrate processing apparatus according to a first variation of the third embodiment.

[0070] Figure 22 This is a front view of the main part of the substrate processing apparatus according to the second variation of the third embodiment.

[0071] Figure 23 This is a schematic diagram illustrating an example of the structure of a monolithic processing unit in a substrate processing apparatus. Detailed Implementation

[0072] <Structure of the substrate processing apparatus according to the first embodiment>

[0073] Figure 1 This is a schematic plan view showing the layout of a substrate processing apparatus 1 according to an embodiment of the present invention.

[0074] The substrate processing apparatus 1 is a batch processing apparatus that processes multiple substrates W simultaneously. The substrate processing apparatus 1 includes: a loading port LP for transporting a carrier C for accommodating a wafer-shaped substrate W, such as a semiconductor wafer; multiple processing units 2 for processing the substrates W transported from the loading port LP using a processing fluid; a transport unit 3 for transporting the substrates W between the loading port LP and the multiple processing units 2; and a controller 4 for controlling the substrate processing apparatus 1.

[0075] The treatment fluids include treatment liquids and treatment gases, as detailed below. Treatment liquids include chemical solutions, rinsing solutions, sulfuric acid-containing liquids, hydrophilic liquids, etc. Treatment gases include ozone-containing gases, displacement gases, heating gases, etc.

[0076] The multiple processing units 2 include: multiple batch liquid processing units that process multiple substrates W using a processing liquid and multiple batch gas processing units that process multiple substrates W using a processing gas.

[0077] The multiple liquid processing units include: a sulfuric acid processing unit 5 for treating multiple substrates W with a sulfuric acid-containing liquid; a first rinsing processing unit 7 for rinsing the multiple substrates W with a rinsing solution; a chemical solution processing unit 8 for treating the multiple substrates W with a chemical solution; and a second rinsing processing unit 9 for rinsing the multiple substrates W with a rinsing solution. The gas processing unit includes an ozone gas processing unit 6 for treating the multiple substrates W with ozone gas.

[0078] Sulfuric acid-containing liquids are, for example, aqueous solutions of sulfuric acid. These solutions contain sulfuric acid (H₂SO₄) and water (H₂O). Examples of aqueous solutions of sulfuric acid include dilute or concentrated sulfuric acid. Sulfuric acid-containing liquids may also contain substances other than sulfuric acid and water. Sulfuric acid-containing liquids can also be formed by mixing sulfuric acid with water such as DIW (deionized water).

[0079] Ozone-containing gas can be ozone gas itself, or a mixture of ozone gas and other gases. Gases other than ozone gas are, for example, inert gases. Inert gases contained in ozone-containing gas can be, for example, nitrogen, inert gases, or mixtures thereof. An inert gas is, for example, argon. The displacing gas is, for example, an inert gas, air, or a mixture thereof.

[0080] The rinsing solution is not limited to DIW, but can also be DIW, carbonated water, electrolyzed ionized water, hydrochloric acid with a dilution concentration (e.g., 1 ppm or more and 100 ppm or less), ammonia with a dilution concentration (e.g., 1 ppm or more and 100 ppm or less), or reduced water (hydrogen water). The rinsing solution used in the first rinsing treatment unit 7 and the rinsing solution used in the second rinsing treatment unit 9 can also be different from each other.

[0081] The solutions include, for example, ammonia-hydrogen-peroxide mixture (APM solution), hydrofluoric acid, etc.

[0082] The substrate W, which is the object of processing by the substrate processing apparatus 1, is, for example, a substrate from which an organic film such as a resist is exposed on the main surface.

[0083] The handling unit 3 includes a carrier handling device 15 and a posture switching robot 16; the carrier handling device 15 handles carriers C between the loading port LP and the processing unit 2 and accommodates multiple carriers C; the posture switching robot 16 moves multiple substrates W into and out of the carriers C held in the carrier handling device 15, and switches the posture of the substrates W between horizontal and vertical postures.

[0084] "Switching the orientation of multiple substrates W between vertical and horizontal orientations" means being able to switch the orientation of each substrate W from vertical to horizontal, and also being able to switch the orientation of each substrate W from horizontal to vertical.

[0085] "Horizontal orientation" refers to the orientation in which the main surface of substrate W is horizontal. "Vertical orientation" refers to the orientation in which the main surface of substrate W is vertical. Vertical orientation is also called upright orientation.

[0086] In addition to performing attitude switching actions, the attitude switching robot 16 also performs batch assembly actions, which involve forming a batch of multiple (e.g., 50) substrates W taken from multiple carriers C, and batch release actions, which involve accommodating the multiple substrates W contained in a batch within multiple carriers C.

[0087] The handling unit 3 also includes: a main handling robot 17 that handles a batch of substrates W between the attitude switching robot 16 and the multiple processing units 2, and multiple auxiliary handling robots 18 that handle a batch of substrates W between the main handling robot 17 and the multiple processing units 2.

[0088] The multiple auxiliary handling robots 18 include: a first auxiliary handling robot 18A that handles one batch of substrates W between the sulfuric acid treatment unit 5, the ozone gas treatment unit 6 and the first rinsing treatment unit 7, and a second auxiliary handling robot 18B that handles multiple substrates W between the chemical solution treatment unit 8 and the second rinsing treatment unit 9.

[0089] The main transport robot 17 receives a batch of substrates W from the attitude switching robot 16. The main transport robot 17 then hands over the batch of substrates W received from the attitude switching robot 16 to the first auxiliary transport robot 18A and the second auxiliary transport robot 18B, receiving the batch of substrates W supported by the first auxiliary transport robot 18A and the second auxiliary transport robot 18B.

[0090] The multiple processing units 2 also include a drying processing unit 10 for drying multiple substrates W and a cleaning processing unit 11 for cleaning the main transport robot 17. The main transport robot 17 is also capable of transporting a batch of substrates W to the drying processing unit 10.

[0091] The first auxiliary transport robot 18A transports a batch of substrates W received from the main transport robot 17 between the sulfuric acid treatment unit 5, the ozone gas treatment unit 6, and the first rinsing treatment unit 7. Similarly, the second auxiliary transport robot 18B transports a batch of substrates W received from the main transport robot 17 between the chemical solution treatment unit 8 and the second rinsing treatment unit 9.

[0092] Figure 2 This is a schematic front view illustrating a structural example of the main parts of the substrate processing apparatus 1.

[0093] The sulfuric acid treatment unit 5 includes: a sulfuric acid tank 20 for storing sulfuric acid-containing liquid for impregnating one batch of substrates W, and a sulfuric acid treatment chamber 21 for housing the sulfuric acid tank 20. The sulfuric acid tank 20 is open upwards, and the sulfuric acid treatment chamber 21 has an upper end 21a that can be opened and closed.

[0094] The first rinsing processing unit 7 includes: a rinsing liquid tank 30 for storing rinsing liquid for impregnating one batch of substrates W, and a rinsing processing chamber 31 for housing the rinsing liquid tank 30. The rinsing liquid tank 30 is open upwards, and the rinsing processing chamber 31 has an upper end 31a that can be opened and closed.

[0095] The ozone gas treatment unit 6 includes a gas treatment chamber 40 that exposes a batch of substrates W to ozone gas. The gas treatment chamber 40 has a treatment space 40a capable of accommodating a batch of substrates W, and the batch of substrates W contained in the treatment space 40a is exposed to ozone gas.

[0096] The ozone gas treatment unit 6 includes: an ozone supply path 41 for supplying ozone-containing gas to the gas treatment chamber 40; an ozone gas valve 42 for opening and closing the ozone supply path 41; a replacement gas supply path 43 for supplying replacement gas to the gas treatment chamber 40; a replacement gas valve 44 for opening and closing the replacement gas supply path 43; an exhaust path 45 for discharging the atmosphere from the gas treatment chamber 40; and an exhaust valve 46 for opening and closing the exhaust path 45.

[0097] Although not illustrated, ozone gas valve 42 includes a valve body with an internal valve seat, a valve core for opening and closing the valve seat, and an actuator for moving the valve core between an open position and a closed position. Other valves have the same structure.

[0098] Ozone supply path 41 is, for example, constructed by piping. Displacement gas supply path 43 is, for example, constructed by piping. Exhaust path 45 is, for example, constructed by piping.

[0099] The ozone gas treatment unit 6 includes an ozone flow path heater 47 for heating the ozone-containing gas within the ozone supply flow path 41. The ozone gas treatment unit 6 may also include an ozone treatment chamber heater (not shown) for heating the gas treatment chamber 40. The ozone flow path heater 47 and the ozone treatment chamber heater are examples of ozone heating units that heat at least one of the ozone-containing gas within the ozone supply flow path 41 and the ozone-containing gas within the gas treatment chamber 40.

[0100] The gas processing chamber 40 has a wall 48 that divides the processing space 40a. The wall 48 has an upper wall 48u, a bottom wall 48b, and a side wall 48s that connect the upper wall 48u and the bottom wall 48b. The upper wall 48u is openable and closable. The side wall 48s is polygonal or arc-shaped in plan view.

[0101] The gas processing chamber 40 has a plurality of supply holes 49A that open in the side wall portion 48s and supply ozone-containing gas supplied from the ozone supply flow path 41 to the processing space 40a, and a plurality of exhaust holes 49B that open in the side wall portion 48s and exhaust the atmosphere in the processing space 40a. The plurality of supply holes 49A are positioned opposite to the plurality of exhaust holes 49B in the side wall portion 48s. The plurality of supply holes 49A can also supply replacement gas supplied from the replacement gas supply flow path 43 to the processing space 40a. The number of supply holes 49A is the same as the number of exhaust holes 49B. Both the supply holes 49A and the exhaust holes 49B are, for example, circular holes (see below). Figure 7 ).

[0102] The first transport robot 18A transports a batch of substrates W in a vertical orientation. The first transport robot 18A can transport the batch of substrates W to the sulfuric acid tank 20 of the sulfuric acid treatment unit 5, immersing the batch of substrates W vertically in the sulfuric acid-containing liquid within the sulfuric acid tank 20. The first transport robot 18A can also transport the batch of substrates W to the gas treatment chamber 40 of the ozone gas treatment unit 6, positioning the batch of substrates W vertically within the treatment space 40a of the gas treatment chamber 40. The first transport robot 18A can also transport the batch of substrates W to the rinsing liquid tank 30 of the first rinsing treatment unit 7, immersing the batch of substrates W vertically in the rinsing liquid within the rinsing liquid tank 30.

[0103] <Structure of the First Transport Robot>

[0104] Figure 3 This is a cross-sectional view illustrating a structural example of the first transport robot 18A included in the substrate processing apparatus 1.

[0105] The first transport robot 18A includes a lifter 50 supporting a batch of substrates W, a lifter mechanism 51 for lifting the lifter 50, and a sliding mechanism 52 for moving (sliding) the lifter 50 horizontally.

[0106] The lifting mechanism 51 includes a lifting actuator (not shown) that generates a driving force to raise and lower the lifting device 50. The lifting actuator is, for example, an electric motor or a cylinder. The lifting mechanism 51 may also include a power transmission mechanism (not shown) that transmits the driving force of the lifting actuator to the lifting device 50. The power transmission mechanism includes, for example, at least one of a ball screw mechanism and a rack and pinion mechanism.

[0107] The sliding mechanism 52 includes a sliding actuator (not shown) that generates a driving force to move the lift 50 in a horizontal direction. The sliding actuator is, for example, an electric motor or a cylinder. The sliding mechanism 52 may also include a power transmission mechanism (not shown) that transmits the driving force of the sliding actuator to the lift 50.

[0108] The lifter 50 is not particularly limited, but may have a structure as shown below. The lifter 50 includes multiple (e.g., three) support portions 53 (see also) that support one batch of substrates W from below. Figure 2 ), and a connecting part 54 connected to one end of a plurality of support parts 53.

[0109] Each support portion 53 has the same number of support grooves 55 as the substrate W. Figure 3 The diagram only shows the support groove 55 of the central support 53 out of the three support sections 53. In each support section 53, multiple support grooves 55 are provided at equal intervals along the arrangement direction (horizontal direction) of a batch of substrates W. The periphery of each substrate W is accommodated in multiple support grooves 55 located at the same position in the arrangement direction. Therefore, the lifter 50 can lift and lower a batch of substrates W while maintaining the posture of a batch of substrates W in a vertical position.

[0110] Reference Figure 2 The lifting device 50 of the first transport robot 18A is capable of moving horizontally above the gas processing chamber 40, the sulfuric acid processing chamber 21, and the rinsing processing chamber 31. The lifting device 50 of the first transport robot 18A is capable of moving horizontally between a first upper position directly above the sulfuric acid processing chamber 21, a second upper position directly above the gas processing chamber 40, and a third upper position directly above the rinsing processing chamber 31 via a sliding mechanism 52.

[0111] The lifting device 50 of the first transport robot 18A can move up and down between the sulfuric acid treatment position (where a batch of substrates W is immersed in sulfuric acid liquid in the sulfuric acid tank 20) ​​and the first upper position via the lifting device 51. The lifting device 50 of the first transport robot 18A can also move up and down between the gas treatment position (where a batch of substrates W is housed in the processing space 40a) and the second upper position via the lifting device 51. Furthermore, the lifting device 50 of the first transport robot 18A can move up and down between the rinsing treatment position (where a batch of substrates W is immersed in rinsing liquid in the rinsing liquid tank 30) and the third upper position via the lifting device 51.

[0112] The sulfuric acid treatment position is such that the upper end of the vertically positioned substrate W is located below the surface of the sulfuric acid-containing liquid in the sulfuric acid tank 20. The rinsing treatment position is such that the upper end of the vertically positioned substrate W is located below the surface of the rinsing liquid in the rinsing liquid tank 30.

[0113] <Electrical Structure of the Substrate Processing Device>

[0114] Figure 4 This is a block diagram illustrating an example of the electrical structure of the substrate processing apparatus 1.

[0115] The controller 4 is equipped with a microcomputer and controls the controlled objects of the board processing device 1 according to a predetermined program. More specifically, the controller 4 includes a processor (CPU) 4A and a memory 4B storing the program, and is configured to execute various control processes for board processing by executing the program through the processor 4A.

[0116] Specifically, controller 4 controls the movements of the carrier transport device 15, the attitude switching robot 16, the main transport robot 17, multiple auxiliary transport robots 18, and multiple processing units 2. The valves and heaters of each processing unit 2 are controlled by controller 4.

[0117] <An example of substrate processing>

[0118] Figure 5 This is a flowchart illustrating an example of substrate processing performed by substrate processing apparatus 1. Figures 6A to 6C This is a schematic diagram illustrating the situation of substrate processing apparatus 1 during substrate processing.

[0119] In the substrate processing performed by the substrate processing apparatus 1, for example, Figure 5 As shown, the process includes sulfuric acid impregnation (step S1), ozone exposure (step S2), rinsing (step S3), and drying (step S4). The following mainly refers to... Figure 1 , Figure 2 as well as Figure 5 This section provides a detailed explanation of the substrate processing. (Refer to relevant sources.) Figures 6A to 6C .

[0120] The main transport robot 17 receives a batch of substrates W, consisting of multiple substrates W, from the attitude switching robot 16. The main transport robot 17 then hands over the batch of substrates W received from the attitude switching robot 16 to the first auxiliary transport robot 18A. The batch of substrates W is supported by the lift 50 of the first auxiliary transport robot 18A.

[0121] After the first auxiliary transport robot 18A receives a batch of substrates W from the main transport robot 17, the elevator 50 moves to the first upper position. Figure 6A (The position is indicated by the double-dotted line). The elevator 50 can also receive a batch of substrates W from the main handling robot 17 when it is in the first upper position.

[0122] The lifter 50, in a state supporting a batch of substrates W in a vertical orientation, moves from the first upper position ( Figure 6A The position indicated by the double-dotted line is facing the sulfuric acid treatment position. Figure 6A (The position shown by the solid line) decreases. Therefore, as... Figure 6AAs shown, one batch of substrates W is immersed vertically in sulfuric acid bath 20 in sulfuric acid liquid (sulfuric acid immersion process: step S1).

[0123] Then, the elevator 50 rises towards the first upper position, thereby removing one batch of substrates W from the sulfuric acid-containing liquid in the sulfuric acid tank 20. The elevator 50 then moves from the first upper position to the second upper position (…). Figure 6B The position indicated by the double-dotted line is moved. Then, the elevator 50 descends from the second upper position to the gas processing position. Figure 6B (The position is shown by the solid line in the middle). Thus, the first handling process (handling process) is performed, in which one batch of substrates W is removed from the sulfuric acid bath 20 and transported to the gas treatment chamber 40.

[0124] With the lift 50 in the gas processing position, the ozone gas valve 42 and the exhaust valve 46 are opened. As a result, the atmosphere in the processing space 40a of the gas processing chamber 40 is exhausted, and ozone-containing gas is supplied to the processing space 40a. By supplying ozone-containing gas to the processing space 40a, a batch of substrates W with sulfuric acid liquid attached is exposed to ozone-containing gas (ozone exposure process: step S2, vertical exposure process).

[0125] By exposing a substrate W coated with a sulfuric acid-containing liquid to an ozone-containing gas, the ozone in the ozone gas dissolves in the sulfuric acid-containing liquid, generating persulfate. Persulfate can then be used to dissolve the organic film exposed from the substrate W in the sulfuric acid-containing liquid. Sometimes, the organic film does not completely dissolve in the sulfuric acid-containing liquid and peels off from the upper surface of the substrate W.

[0126] Preferably, ozone-containing gas is supplied to the processing space 40a, thereby replacing the atmosphere within the processing space 40a with ozone-containing gas, and the processing space 40a is filled with ozone-containing gas (ozone-containing gas filling process). If the processing space 40a is filled with ozone-containing gas, persulfate can be rapidly and sufficiently generated in the sulfuric acid-containing liquid.

[0127] The temperature of the ozone-containing gas is preferably in the range of 50°C or higher and 270°C or lower. More preferably, it is in the range of 80°C or higher and 170°C or lower. This improves the activity of persulfate and rapidly removes organic films.

[0128] like Figure 7As shown, in the gas processing chamber 40, multiple supply hole rows 49AL, each consisting of multiple supply holes 49A, are arranged in a first arrangement direction D1 (horizontal direction). More specifically, each supply hole row 49AL consists of multiple supply holes 49A arranged in a predetermined column direction (vertical direction in this example). The first arrangement direction D1 intersects (orthogonally) this column direction. A batch of substrates W supported by the lift 50 is arranged in the horizontal direction. The arrangement spacing P1 of the batch of substrates W is consistent with the arrangement spacing P2 of the multiple supply hole rows 49AL. When the lift 50 is in the gas processing position supporting a batch of substrates W in a vertical posture, when viewed from a horizontal direction parallel to the main surface of the substrate W, one substrate W is located between adjacent supply hole rows 49AL.

[0129] exist Figure 7 For ease of explanation, the reference numeral "49A" for the supply holes and the reference numeral "49B" for the exhaust holes are also shown. The multiple exhaust holes 49B are configured in the same way as the multiple supply holes 49A. In the gas processing chamber 40, multiple exhaust hole rows 49BL, each composed of multiple exhaust holes 49B, are arranged in the first arrangement direction D1 (horizontal direction) with the same arrangement spacing P2 as the multiple supply hole rows 49AL. Each exhaust hole row 49BL is composed of multiple exhaust holes 49B arranged in a predetermined column direction (vertical direction in this example). The first arrangement direction D1 intersects (orthogonally in this example) the column direction. When the lift 50 is in the gas processing position with one batch of substrates W in a vertically supported state, when viewed from a horizontal direction parallel to the main surface of the substrate W, one substrate W is located between adjacent exhaust hole rows 49BL.

[0130] Then, the elevator 50 rises towards the second upper position, thereby removing one batch of substrates W from the gas processing chamber 40. The elevator 50 then moves from the second upper position to the third upper position (…). Figure 6C The elevator 50 moves from the third upper position towards the rinsing treatment position (as indicated by the double-dotted line). Figure 6C (The position shown by the solid line) decreases. Therefore, as... Figure 6C As shown, one batch of substrates W is immersed in the rinsing liquid in the rinsing liquid tank 30 (rinsing process: step S3). Thus, the second handling step of removing one batch of substrates W from the gas treatment chamber 40 and transferring it to the rinsing liquid tank 30 is performed.

[0131] One batch of substrates W is rinsed by immersing them in rinsing solution in rinsing tank 30. Specifically, sulfuric acid-containing liquid containing dissolved organic film and organic film peeled off from substrates W are removed from substrates W.

[0132] After removing one batch of substrates W from the gas processing chamber 40, the ozone gas valve 42 is closed, and in its place, the replacement gas valve 44 is opened. This supplies replacement gas to the processing space 40a of the gas processing chamber 40, replacing the atmosphere within the processing space 40a. As a result, ozone-containing gas is removed from the processing space 40a (ozone removal process).

[0133] Then, the elevator 50 rises to the third upper position. This removes one batch of substrates W from the rinsing liquid in the rinsing liquid tank 30. With the elevator 50 in the third upper position, the first auxiliary transport robot 18A delivers one batch of substrates W to the main transport robot 17. The main transport robot 17 then transports the batch of substrates W received from the first auxiliary transport robot 18A to the drying unit 10.

[0134] In the drying unit 10, a batch of substrates W is dried using methods such as reduced pressure drying (drying process: step S4). Afterwards, the main transport robot 17 hands over the batch of substrates W to the attitude switching robot 16. The attitude switching robot 16 changes the attitude of the batch of substrates W received from the main transport robot 17 from a vertical orientation to a horizontal orientation, and then accommodates the batch of substrates W in multiple carriers C held in the carrier transport device 15. By repeating this series of actions, multiple substrates W transported to the substrate processing device 1 are processed.

[0135] According to the first embodiment, a batch of substrates W can be immersed in a sulfuric acid-containing liquid in a vertical position. Therefore, multiple substrates W can be immersed in the sulfuric acid-containing liquid at approximately the same time. The ozone gas treatment unit 6 exposes the batch of substrates W immersed in the sulfuric acid-containing liquid at one time to ozone gas. This allows the ozone in the ozone gas to dissolve in the sulfuric acid-containing liquid adhering to the batch of substrates W after removal from the sulfuric acid-containing liquid, generating persulfate in the sulfuric acid-containing liquid. As a result, the organic film can be rapidly and thoroughly removed from the main surface of the batch of substrates W.

[0136] Furthermore, according to the first embodiment, a batch of substrates W taken from the sulfuric acid bath 20 is placed in the processing space 40a of the gas treatment chamber 40. Therefore, a batch of substrates W can be exposed to ozone-containing gas almost simultaneously. Therefore, the organic film can be removed more quickly and thoroughly from the main surface of a batch of substrates W.

[0137] According to the first embodiment, ozone-containing gas is supplied to the processing space 40a through multiple supply holes 49A, and the processing space 40a is vented through multiple exhaust holes 49B, thereby exposing one batch of substrates W to the ozone-containing gas. Therefore, even if the ozone in the atmosphere in contact with the sulfuric acid-containing liquid on the substrate W is consumed due to the ozone dissolving in the sulfuric acid-containing liquid, the ozone-containing gas supplied to the processing space 40a can still be used to supply ozone to the atmosphere in contact with the sulfuric acid-containing liquid adhering to the substrate W. Therefore, the concentration of ozone in the atmosphere in contact with the sulfuric acid-containing liquid on the substrate W can be maintained at a sufficiently high level. Therefore, persulfate can be generated in the sulfuric acid-containing liquid on the substrate W.

[0138] In the gas processing chamber 40, multiple supply hole rows 49AL are arranged in a first arrangement direction D1. A batch of substrates W is supported by a lift 50 in this arrangement in the first arrangement direction D1. The batch of substrates W is arranged in the processing space 40a with each substrate W positioned between the supply hole rows 49AL. Therefore, ozone-containing gas from each supply hole row 49AL can be supplied to the substrates W. Thus, ozone can be adequately supplied to the atmosphere in contact with the sulfuric acid-containing liquid on each substrate W, allowing the ozone to fully dissolve in the sulfuric acid-containing liquid on each substrate W. As a result, uneven removal of organic films between the substrates W can be reduced.

[0139] If, before the sulfuric acid impregnation process (step S1), a batch of substrates W is introduced into the gas treatment chamber 40, exposing the batch of substrates W to ozone gas, then the batch of substrates W can be hydrophilized. That is, it is also possible to... Figure 8 As shown in the substrate processing, a hydrophilication process (step S5) is performed before the sulfuric acid impregnation process (step S1). In this substrate processing, a batch of substrates W is exposed to ozone gas before and after impregnation in a sulfuric acid-containing liquid. By performing... Figure 8 The substrate processing shown involves hydrophilizing one batch of substrates W before immersion in a sulfuric acid-containing liquid.

[0140] Therefore, the wettability of substrate W is improved, and sulfuric acid-containing liquids easily adhere to substrate W. Thus, sulfuric acid-containing liquids can be thinly diffused across the entire main surface of substrate W. Therefore, during the ozone exposure process, ozone can easily reach the main surface of substrate W, and the organic film can be quickly and thoroughly removed from the main surface of substrate W.

[0141] <First Variation of the First Embodiment>

[0142] Next, a first modified example of the substrate processing apparatus 1 will be described.

[0143] Figure 9This is a front view of the main part of the substrate processing apparatus 1 of the first modified example of the first embodiment.

[0144] In the first modified example, the sulfuric acid treatment chamber 21 is not provided, and the sulfuric acid tank 20 is arranged inside the gas treatment chamber 40. The treatment space 40a of the gas treatment chamber 40 is located directly above the sulfuric acid tank 20.

[0145] The first transport robot 18A supports multiple substrates W while moving up and down, thereby transporting the substrates W between the processing space 40a and the sulfuric acid tank 20. The sulfuric acid processing unit 5 does not have a sulfuric acid processing chamber 21, but includes a cover member 22 that separates the interior of the sulfuric acid tank 20 from the processing space 40a and opens and closes the sulfuric acid tank 20. In a first variation, the processing space 40a is divided by a side wall portion 48s, an upper wall portion 48u, and the cover member 22. The cover member 22 is driven by a cover drive mechanism (not shown) such as a motor to open and close the sulfuric acid tank 20.

[0146] The lifting device 50 of the first transport robot 18A is capable of horizontal movement above the gas processing chamber 40 and the flushing processing chamber 31. The lifting device 50 can move horizontally to a second upper position directly above the gas processing chamber 40 and a third upper position directly above the flushing processing chamber 31 via a sliding mechanism 52. The lifting device 50 can move up and down between the sulfuric acid processing position, the gas processing position, and the second upper position via the lifting device mechanism 51. The lifting device 50 can move up and down between the flushing processing position and the third upper position via the lifting device mechanism 51.

[0147] Figures 10A to 10C This is a schematic diagram illustrating the situation of the substrate processing apparatus 1 involved in the first modified example of substrate processing.

[0148] According to the substrate processing apparatus 1 of the first modified example, it is capable of performing... Figure 5 The substrate processing shown. Hereinafter, the substrate processing performed by the substrate processing apparatus 1 of the first modified example and... Figures 6A to 6C The differences in substrate processing shown will be explained in detail.

[0149] In the substrate processing of the first variation, after receiving a batch of substrates W from the main transport robot 17, the elevator 50 moves to the second upper position. Figure 10A The position indicated by the double-dotted line. The lift 50, while supporting one batch of substrates W, is oriented towards the sulfuric acid treatment position. Figure 10A (The position shown by the solid line) decreases. Therefore, as... Figure 10A As shown, one batch of substrates W is immersed in sulfuric acid liquid in sulfuric acid bath 20 (sulfuric acid immersion process: Figure 5 (Step S1 shown). Open the cover component 22 before the elevator 50 enters the sulfuric acid tank 20.

[0150] Subsequently, the lift 50 rises, thereby removing one batch of substrates W from the sulfuric acid-containing liquid in the sulfuric acid tank 20. The lift 50 moves from the sulfuric acid treatment position ( Figure 10B The position indicated by the double-dotted line rises and moves to the gas processing position. Figure 10B (The position is shown by the solid line in the middle). In this way, a batch of substrates W is placed in the processing space 40a (first handling step) by lifting a batch of substrates W from the sulfuric acid tank 20. After the lifter 50 retracts from the sulfuric acid tank 20, the cover member 22 is closed.

[0151] With the lift 50 in the gas processing position, the ozone gas valve 42 and the exhaust valve 46 are opened. As a result, the atmosphere within the processing space 40a of the gas processing chamber 40 is exhausted, and ozone-containing gas is supplied to the processing space 40a. Therefore, by supplying ozone-containing gas to the processing space 40a, a batch of substrates W with sulfuric acid-containing liquid adhering to them is exposed to ozone-containing gas (ozone exposure process: Figure 5 Step S2 is shown.

[0152] By exposing a substrate W coated with a sulfuric acid-containing liquid to an ozone-containing gas, the ozone in the ozone-containing gas dissolves in the sulfuric acid-containing liquid adhering to the substrate W. This allows the generation of persulfate in the sulfuric acid-containing liquid from a batch of substrates W. The persulfate can then be used to dissolve the organic film exposed from the substrate W in the sulfuric acid-containing liquid. Sometimes, the organic film does not completely dissolve in the sulfuric acid-containing liquid and peels off from the upper surface of the substrate W.

[0153] Preferably, the atmosphere within the processing space 40a is replaced with ozone-containing gas by supplying ozone-containing gas to the processing space 40a, thereby filling the processing space 40a with ozone-containing gas (ozone-containing gas filling process). In a first variation, when the elevator 50 is in the gas processing position, the substrate W is also located between the supply hole rows 49AL (see reference). Figure 7 ).

[0154] Then, the elevator 50 rises towards the second upper position, thereby removing one batch of substrates W from the gas processing chamber 40. The elevator 50 then moves from the second upper position to the third upper position (…). Figure 10C The elevator 50 moves from the third upper position towards the rinsing treatment position (as indicated by the double-dotted line). Figure 10C (The position shown by the solid line) decreases. Therefore, as... Figure 10C As shown, one batch of substrates W is immersed in the rinsing solution in the rinsing solution tank 30 (rinsing process: Figure 5 (See step S3). Thus, the second transport step of removing one batch of substrates W from the gas processing chamber 40 and transporting them to the rinsing liquid tank 30 is performed.

[0155] One batch of substrates W is rinsed by immersing them in rinsing solution in rinsing tank 30. Specifically, sulfuric acid-containing liquid containing dissolved organic film and organic film peeled off from substrates W are removed.

[0156] After removing one batch of substrates W from the gas processing chamber 40, the ozone gas valve 42 is closed, and in turn, the replacement gas valve 44 is opened. This supplies replacement gas to the processing space 40a of the gas processing chamber 40, replacing the atmosphere within the processing space 40a. Consequently, ozone-containing gas is removed from the processing space 40a.

[0157] After that, with Figures 6A to 6C The substrate processing shown also performs a drying process (step S4).

[0158] According to a first variation of the first embodiment, by moving a batch of substrates W in one direction, such as lifting them from the sulfuric acid bath 20, a batch of substrates W can be moved from the sulfuric acid bath 20 to the processing space 40a. Therefore, after the sulfuric acid-containing liquid adheres to a batch of substrates W, the batch of substrates W can be rapidly exposed to ozone-containing gas. Therefore, the organic film can be rapidly removed from the main surface of the batch of substrates W.

[0159] The interior of the sulfuric acid tank 20 and the processing space 40a are separated by a cover member 22 that opens and closes the sulfuric acid tank 20. Therefore, the dissolution of ozone-containing gas in the sulfuric acid-containing liquid stored in the sulfuric acid tank 20 can be suppressed. Therefore, in the processing of the next batch of substrate W, the removal of the organic film from the substrate W before the supply of ozone-containing gas to the processing space 40a can be suppressed. Therefore, deviations during the processing of each batch using persulfate can be suppressed.

[0160] <Second variation of the first embodiment>

[0161] Next, a second modification of the substrate processing apparatus 1 will be described.

[0162] Figure 11 This is a front view of the main part of the substrate processing apparatus 1 according to the second variation of the first embodiment.

[0163] In a second variation, the substrate processing apparatus 1 further includes a hydrophilic treatment unit 12 for treating a batch of substrates W using a hydrophilic solution. The hydrophilic solution is, for example, ozone water.

[0164] The hydrophilic treatment unit 12 includes: a hydrophilic liquid tank 60 for storing a hydrophilic liquid for impregnating one batch of substrates W, and a hydrophilic treatment chamber 61 for housing the hydrophilic liquid tank 60. The hydrophilic liquid tank 60 is open upwards, and the hydrophilic treatment chamber 61 has an upper end 61a that can be opened and closed.

[0165] The lifting device 50 of the first transport robot 18A can move horizontally above the gas processing chamber 40, sulfuric acid processing chamber 21, rinsing processing chamber 31, and hydrophilic processing chamber 61. The lifting device 50, via the sliding mechanism 52, can move to a fourth upper position directly above the hydrophilic processing chamber 61, in addition to the first, second, and third upper positions.

[0166] According to the substrate processing apparatus 1 of the second modification, it is capable of performing... Figure 5 The substrate processing shown. The substrate processing apparatus 1 according to the second modification example can also perform... Figure 8 The substrate processing shown.

[0167] In execution Figure 8 In the case of substrate processing shown, after the first auxiliary transport robot 18A receives a batch of substrates W from the main transport robot 17, the lift 50 moves to the fourth upper position. The lift 50 descends toward the hydrophilic treatment position while supporting a batch of substrates W. As a result, a batch of substrates W is immersed in the hydrophilic solution in the hydrophilic solution tank 60 (hydrophilicization process: step S5).

[0168] Then, one batch of substrate W was taken out from the hydrophilic liquid bath 60 and... Figures 6A to 6C Similarly, the substrate processing shown involves sulfuric acid impregnation (step S1) to drying (step S4).

[0169] According to a second variation of the first embodiment, a batch of substrates W can be hydrophilized before immersing in a sulfuric acid-containing liquid. Therefore, the wettability of substrate W is improved, and the sulfuric acid-containing liquid easily adheres to substrate W. Thus, the sulfuric acid-containing liquid can be thinly diffused across the entire main surface of substrate W. Therefore, during the ozone exposure process, ozone can easily reach the main surface of substrate W, and the organic film can be quickly and thoroughly removed from the substrate.

[0170] <Structure of the substrate processing apparatus in the second embodiment>

[0171] Next, a structural example of the substrate processing apparatus 1A according to the second embodiment will be described. Figure 12A as well as Figure 12B This is a schematic diagram illustrating a structural example of the first transport robot 18A included in the substrate processing apparatus 1A according to the second embodiment. Figure 12A as well as Figure 12B In the middle, regarding the above-mentioned Figures 1 to 11 The structure shown is the same as the one labeled with. Figure 1 Equivalent reference symbols are used, and their descriptions are omitted. For those discussed later... Figures 13A to 15 The same applies.

[0172] The main difference between the substrate processing apparatus 1A of the second embodiment and the substrate processing apparatus 1 of the first embodiment is that the elevator 50 of the first transport robot 18A can switch the posture of a batch of substrates W between a vertical posture and a horizontal posture by deformation.

[0173] The lifting device 50 of the first transport robot 18A in the second embodiment includes: a clamping part 56 that clamps and supports the periphery of a batch of substrates W, a rotating support shaft 57 that rotates the clamping part 56, and a connecting part 58 that is connected to the clamping part 56 via the rotating support shaft 57 and transmits power to the lifting device structure 51 and the sliding mechanism 52.

[0174] The first transport robot 18A includes a posture switching mechanism 70 that switches the posture of a batch of substrates W between a vertical posture and a horizontal posture. The posture switching mechanism 70 deforms the lifting device 50 by rotating the clamping part 56 about a horizontally oriented rotary support shaft 57. The rotary support shaft 57 and the clamping part 56 constitute a posture conversion structure that switches the posture of the held batch of substrates W between a vertical posture and a horizontal posture. This posture conversion structure is driven by the posture switching mechanism 70. Figure 12A This indicates the first support state of a batch of substrates W in a vertical orientation supported by the elevator 50. Figure 12B This indicates the second support state of a batch of substrates W in which the elevator 50 supports a horizontal posture.

[0175] The attitude switching mechanism 70 includes, for example, an actuator such as an electric motor that rotates the rotary support shaft 57 about its central axis A1.

[0176] <An example of substrate processing in the second embodiment>

[0177] Figures 13A-13C This is a schematic diagram illustrating the second embodiment of the substrate processing apparatus 1A used to explain the execution of substrate processing.

[0178] According to the substrate processing apparatus 1A of the second embodiment, it is capable of performing... Figure 5 The substrate processing shown. Hereinafter, the substrate processing performed by the substrate processing apparatus 1A and... Figures 6A to 6C The differences in substrate processing shown will be explained in detail.

[0179] After the first auxiliary transport robot 18A receives a batch of substrates W from the main transport robot 17, the elevator 50 moves to the first upper position. Figure 13A (The position is indicated by the double-dotted line). The first auxiliary handling robot 18A can also receive a batch of substrates W from the main handling robot 17 when the elevator 50 is in the first upper position.

[0180] The lifting device 50 moves from the first upper position toward the sulfuric acid treatment position in the first supported state. Figure 13A (The position shown by the solid line) decreases. Therefore, as... Figure 13A As shown, one batch of substrates W, in a vertical orientation, is immersed in a sulfuric acid bath 20 containing sulfuric acid (sulfuric acid immersion process: Figure 5 Step S1 is shown.

[0181] Then, the elevator 50 rises towards the first upper position, thereby removing one batch of substrates W from the sulfuric acid-containing liquid in the sulfuric acid tank 20. The elevator 50 then moves from the first upper position to the second upper position (…). Figure 13B The position indicated by the double-dotted line is moved. Furthermore, the attitude switching mechanism 70 changes the state of the lift 50 from the first support state to the second support state. Thus, the attitude of one batch of substrates W changes from a vertical attitude to a horizontal attitude (first attitude change process).

[0182] Furthermore, the elevator 50 moves from the second upper position toward the gas processing position ( Figure 13B The elevator 50 (as shown by the solid line) descends and is positioned in the gas processing position. With the elevator 50 in the gas processing position, the ozone gas valve 42 and the exhaust valve 46 are opened. As a result, the atmosphere within the processing space 40a of the gas processing chamber 40 is exhausted, and ozone-containing gas is supplied to the processing space 40a. By supplying ozone-containing gas to the processing space 40a, a batch of substrates W, in a horizontal position with sulfuric acid liquid adhering to them, is exposed to the ozone-containing gas (ozone exposure process: Figure 5 Step S2, horizontal exposure process (as shown).

[0183] It should be noted that the first attitude change procedure can also be performed after the elevator 50 is positioned in the gas processing position and before it begins to supply ozone-containing gas to the processing space 40a.

[0184] Preferably, ozone-containing gas is supplied to the processing space 40a, thereby replacing the atmosphere within the processing space 40a with ozone-containing gas, and the processing space 40a is filled with ozone-containing gas (ozone-containing gas filling process). If the processing space 40a is filled with ozone-containing gas, persulfate can be rapidly and sufficiently generated in the sulfuric acid-containing liquid.

[0185] like Figure 14As shown, in the gas processing chamber 40, multiple supply hole rows 49AL, each consisting of multiple supply holes 49A, are arranged in a second arrangement direction D2 (vertical direction). Each supply hole row 49AL consists of multiple supply holes 49A arranged in a predetermined column direction (horizontal direction in this example), and the second arrangement direction D2 intersects (orthogonally to) this column direction. A batch of substrates W supported by the lift 50 is arranged in the vertical direction. When the lift 50 is in the gas processing position supporting a batch of substrates W in a horizontal posture, when viewed from a horizontal direction parallel to the main surface of the substrate W, one substrate W is located between adjacent supply hole rows 49AL.

[0186] exist Figure 14 For ease of explanation, the reference numeral "49A" for the supply hole and the reference numeral "49B" for the exhaust hole are also shown. The multiple exhaust holes 49B are configured in the same way as the multiple supply holes 49A. In the gas processing chamber 40, multiple exhaust hole rows 49BL, each composed of multiple exhaust holes 49B, are arranged in the second arrangement direction D2 (vertical direction). Each exhaust hole row 49BL is composed of multiple exhaust holes 49B arranged in a predetermined column direction (horizontal direction in this example). The second arrangement direction D2 intersects (orthogonally) this column direction. When the lift 50 is in the gas processing position with one batch of substrates W in a horizontally supported posture, when viewed from a horizontal direction parallel to the main surface of the substrate W, one substrate W is located between adjacent exhaust hole rows 49BL.

[0187] Then, the elevator 50 rises towards the second upper position, thereby removing one batch of substrates W from the gas processing chamber 40. The elevator 50 then moves from the second upper position to the third upper position (…). Figure 13C The position indicated by the double-dotted line in the middle is moved. Moreover, the attitude switching mechanism 70 changes the state of the lift 50 from the second support state to the first support state. As a result, the attitude of one batch of substrates W is changed from a horizontal attitude to a vertical attitude (second attitude change process).

[0188] Then, the lift 50 moves from the third upper position toward the flushing treatment position ( Figure 13C (The position shown by the solid line) decreases. Therefore, as... Figure 13C As shown, a batch of substrates W in a vertical orientation is immersed in the rinsing liquid in the rinsing liquid tank 30 (rinsing process: step S3). Thus, a second handling step is performed to remove the batch of substrates W from the gas treatment chamber 40 and transfer it to the rinsing liquid tank 30.

[0189] One batch of substrates W is rinsed by immersing them in rinsing solution in rinsing tank 30. Specifically, sulfuric acid-containing liquid containing dissolved organic film and organic film peeled off from substrates W are removed from substrates W.

[0190] After removing one batch of substrates W from the gas processing chamber 40, the ozone gas valve 42 is closed, and in its place, the replacement gas valve 44 is opened. This supplies replacement gas to the processing space 40a of the gas processing chamber 40, replacing the atmosphere within the processing space 40a. As a result, ozone-containing gas is removed from the processing space 40a (ozone removal process).

[0191] Subsequently, the first transfer robot 18A delivers a batch of substrates W to the main transfer robot 17. The main transfer robot 17 then transports the batch of substrates W received from the first transfer robot 18A to the drying unit 10. Afterward, the batch of substrates W is dried and finally housed in multiple carriers C.

[0192] According to the second embodiment, a batch of substrates W can be immersed in a sulfuric acid-containing liquid in a vertical position. Therefore, a batch of substrates W can be immersed in the sulfuric acid-containing liquid at approximately the same time. By placing a batch of substrates W removed from the sulfuric acid bath 20 in the processing space 40a, a batch of substrates W can be simultaneously exposed to ozone-containing gas. Therefore, the organic film can be removed from the substrates W more quickly and thoroughly.

[0193] Furthermore, regarding the orientation of a batch of substrates, before exposure to ozone gas, the orientation of the substrate W in a batch is changed from a vertical orientation to a horizontal orientation. Therefore, it is possible to suppress uneven thickness of the sulfuric acid-containing liquid at various locations on the substrate W caused by the downward movement of the sulfuric acid-containing liquid due to its own weight. Thus, it is possible to reduce uneven removal of the organic film at various locations on the main surface of the substrate W.

[0194] According to the second embodiment, the attitude switching mechanism 70 switches the attitude of a batch of substrates W between a vertical attitude and a horizontal attitude by deforming the lifter 50. More specifically, the lifter 50 has an attitude conversion structure capable of switching the attitude of a batch of substrates W held between a vertical attitude and a horizontal attitude, and this attitude conversion structure is driven by the attitude switching mechanism 70.

[0195] Therefore, after immersing a batch of substrates W in a vertical position into the sulfuric acid bath 20, the lifting mechanism 50 of the first transport robot 18A (the transport robot) can be deformed to change the orientation of the batch of substrates W from vertical to horizontal. Furthermore, the horizontally positioned batch of substrates W can be exposed to ozone gas in the gas treatment chamber 40. In this way, a single robot (the first transport robot 18A) can be used to change the orientation of a batch of substrates W and transport the batch of substrates W from the sulfuric acid bath 20 to the gas treatment chamber 40. Since the handover of substrates W between robots can be eliminated, the organic film can be quickly removed from the substrates W.

[0196] Furthermore, according to the second embodiment, ozone-containing gas is supplied to the processing space 40a through multiple supply holes 49A, and the processing space 40a is vented through multiple exhaust holes 49B, thereby exposing one batch of substrates W to the ozone-containing gas. Therefore, even if the ozone in the atmosphere in contact with the sulfuric acid-containing liquid on the substrate W is consumed due to the ozone dissolving in the sulfuric acid-containing liquid, the ozone-containing gas supplied to the processing space 40a can still be used to supply ozone to the atmosphere in contact with the sulfuric acid-containing liquid adhering to the substrate W. Therefore, the concentration of ozone in the atmosphere in contact with the sulfuric acid-containing liquid on the substrate W can be maintained at a sufficiently high level. Therefore, persulfate can be generated in the sulfuric acid-containing liquid on the substrate W.

[0197] In the gas processing chamber 40, multiple supply hole rows 49AL are arranged in a second arrangement direction D2. A batch of substrates W is supported by a lift 50 in this arrangement in the second arrangement direction D2. The batch of substrates W is arranged in the processing space 40a with each substrate W positioned between the supply hole rows 49AL. Therefore, ozone-containing gas from each supply hole row 49AL can be supplied to the substrates W. Thus, ozone can be adequately supplied to the atmosphere in contact with the sulfuric acid-containing liquid on each substrate W, allowing the ozone to fully dissolve in the sulfuric acid-containing liquid on each substrate W. As a result, uneven removal of organic films between the substrates W can be reduced.

[0198] <Substrate processing apparatus of a modified embodiment of the second embodiment>

[0199] Figure 15 This is a schematic diagram of a substrate processing apparatus 1A used to illustrate a modified example of the second embodiment.

[0200] In the substrate processing apparatus 1A of the modified example of the second embodiment, the substrate processing apparatus 1A of the first modified example of the first embodiment (refer to...) Figure 9Similarly, instead of a sulfuric acid treatment chamber 21, a sulfuric acid tank 20 is provided within a gas treatment chamber 40. The treatment space 40a of the gas treatment chamber 40 is located directly above the sulfuric acid tank 20.

[0201] In the substrate processing apparatus 1A of the second embodiment, the same substrate processing as that of the substrate processing apparatus 1 of the first embodiment can be performed (see reference). Figures 10A to 10C That is, after immersing a batch of substrates W in sulfuric acid bath 20 in a vertical position, the batch of substrates W is lifted from sulfuric acid bath 20, thereby placing the batch of substrates W in processing space 40a (first handling step).

[0202] However, after removing one batch of substrates W from the sulfuric acid bath 20 and before exposing one batch of substrates W to ozone gas, the state of the lift 50 is changed from the first support state to the second support state by the attitude switching mechanism 70. As a result, the attitude of one batch of substrates W is changed from a vertical attitude to a horizontal attitude (first attitude change process).

[0203] The first attitude change process can also be performed during the period from when a batch of substrates W is removed from the sulfuric acid tank 20 until they are placed in the processing space 40a. Alternatively, the first attitude change process can be performed after the elevator 50 is placed in the gas processing position and before ozone-containing gas is supplied to the processing space 40a.

[0204] According to a variation of the second embodiment, by moving a batch of substrates W in one direction, such as lifting them from the sulfuric acid tank 20, a batch of substrates W can be moved from the sulfuric acid tank 20 to the processing space 40a. Therefore, after the sulfuric acid-containing liquid adheres to a batch of substrates W, the batch of substrates W can be rapidly exposed to ozone-containing gas. Thus, the organic film can be rapidly removed from the substrates W.

[0205] The interior of the sulfuric acid tank 20 and the processing space 40a are separated by a cover member 22 that opens and closes the sulfuric acid tank 20. Therefore, it is possible to suppress the dissolution of ozone-containing gas in the sulfuric acid-containing liquid stored in the sulfuric acid tank 20. Therefore, in the processing of the next batch of substrate W, it is possible to prevent the removal of the organic film from the substrate W from beginning before the supply of ozone-containing gas to the processing space 40a. Therefore, it is possible to suppress deviations during the processing of each batch using persulfate.

[0206] <Structure of the substrate processing apparatus according to the third embodiment>

[0207] Next, a structural example of the substrate processing apparatus 1B according to the third embodiment will be described. Figure 16 This is a front view of the main part of the substrate processing apparatus 1B according to the third embodiment. Figure 16 In the middle, regarding the above-mentioned Figures 1-15 The structure shown is the same as the one labeled with. Figure 1 The same reference numerals are used in the accompanying drawings, and their descriptions are omitted. For those described later... Figures 17A to 22 The same applies.

[0208] The main difference between the substrate processing apparatus 1B of the third embodiment and the substrate processing apparatus 1 of the first embodiment is that the orientation of a batch of substrates W can be switched between vertical and horizontal orientations by deforming the hand 80 of the main handling robot 17. In addition, instead of multiple auxiliary handling robots 18, multiple lifting handling robots 19 are provided, each corresponding to a multiple processing unit 2.

[0209] In detail, the plurality of lifting and transporting robots 19 include: a first lifting and transporting robot 19A that transports one batch of substrates W between the main transporting robot 17 and the sulfuric acid treatment unit 5; a second lifting and transporting robot 19B that transports one batch of substrates W between the main transporting robot 17 and the ozone gas treatment unit 6; and a third lifting and transporting robot 19C that transports one batch of substrates W between the main transporting robot 17 and the first rinsing treatment unit 7. The first lifting and transporting robot 19A is an example of the first transporting robot, and the second lifting and transporting robot 19B is an example of the second transporting robot.

[0210] Although not illustrated, the plurality of lifting and transporting robots 19 may also include other lifting and transporting robots that transport one batch of substrates W between the main transporting robot 17 and the liquid treatment unit 8, and other lifting and transporting robots that transport one batch of substrates W between the main transporting robot 17 and the second rinsing treatment unit 9.

[0211] The structure of each lifting and transporting robot 19, for example, is similar to... Figure 3 The first transport robot 18A shown is identical. However, the lifting transport robot 19 does not have a sliding mechanism 52 (see reference). Figure 3 ).

[0212] Furthermore, the lifter 50 of the second lifting and handling robot 19B is configured to support a batch of substrates W in a horizontal posture. The lifter 50 of the second lifting and handling robot 19B is not particularly limited, but may have, for example, the following structure. The lifter 50 includes, for example, a plurality of (e.g., the same number as the substrates W) peripheral support portions 88 that support each substrate W from below (also see below). Figure 18A (etc.) and connecting part 89 that connects multiple peripheral support parts 88.

[0213] Hereinafter, the lifter 50 of the first lifting and handling robot 19A will be referred to as the first lifter 50A, the lifter 50 of the second lifting and handling robot 19B will be referred to as the second lifter 50B, and the lifter 50 of the third lifting and handling robot 19C will be referred to as the third lifter 50C. The first lifter 50A and the third lifter 50C constitute a batch of base plates W that support a vertical posture.

[0214] The first lifter 50A can move up and down between the sulfuric acid treatment position and the first upper position via the lifter mechanism 51 of the first lifting and transporting robot 19A. The second lifter 50B can move up and down between the gas treatment position and the second upper position via the lifter mechanism 51 of the second lifting and transporting robot 19B. The third lifter 50C can move up and down between the rinsing treatment position and the third upper position via the lifter mechanism 51 of the third lifting and transporting robot 19C.

[0215] <Structure of the Main Transport Robot in the Third Embodiment>

[0216] Figure 17A This is a schematic diagram illustrating a structural example of the main transport robot 17 according to the third embodiment. Figure 17B It is along Figure 17A A cross-sectional view of line XVIIB-XVIIB.

[0217] The main transport robot 17 is not particularly limited, but may have a structure as follows.

[0218] The main handling robot 17 includes a hand 80 capable of holding (supporting) a batch of substrates W and a slide rail 83 that slidably supports the hand 80.

[0219] The main handling robot 17 also includes a hand drive mechanism 84 that causes the hand 80 to move (slide) horizontally along the slide rail 83. The hand 80 can move horizontally between the following positions: a first handover position (described later) where it can hand over one batch of substrates W to a first elevator 50A located in a first upper position. Figure 18A as well as Figure 18B The position shown by the solid line in the middle), the second handover position (described later) that allows one batch of substrates W to be handed over between the second elevator 50B located in the second upper position and the second handover position. Figure 18C as well as Figure 18D The position shown by the solid line), and the third handover position (described later) where a batch of substrates W can be handed over between the third elevator 50C located in the third upper position and the third handover position. Figure 18E (The position indicated by the solid line).

[0220] The hand 80 has a holding portion 85 for holding a batch of substrates W, a pair of holding portions 86 for holding the substrates W held by the holding portion 85, a first connecting shaft 81 connected to the holding portion 85 and extending in a horizontal direction, and a second connecting shaft 82 connected to the first connecting shaft 81 and extending in a vertical direction.

[0221] A pair of gripping portions 86 are positioned opposite each other. One gripping portion 86 contacts the periphery of the substrate W, while the other gripping portion 86 contacts the periphery from the opposite side of the first gripping portion 86, thereby gripping the substrate W. The pair of gripping portions 86 grip a batch of substrates W by moving toward each other and release the gripping of a batch of substrates W by moving apart from each other.

[0222] like Figure 17B As shown, the holding portion 85 is provided with a plurality of holding grooves 87 for holding substrates W, and the holding portion 85 is capable of holding the same number of substrates W as the holding grooves 87. In order to facilitate clamping the periphery of the substrates W, protrusions and recesses (not shown) may also be provided in each holding portion 86.

[0223] The main handling robot 17 includes a posture switching mechanism 71 that deforms the hand 80 to switch the posture of a batch of substrates W. The posture switching mechanism 71 includes a first rotation mechanism 72 that rotates a first connecting shaft 81 about its central axis A2, and a second rotation mechanism 73 that rotates a second connecting shaft 82 about its central axis A3.

[0224] By holding one batch of substrates W in the hand 80, the hand 80 is deformed using the first rotation mechanism 72 and the second rotation mechanism 73, thereby achieving a first holding state in which the hand 80 holds one batch of substrates W in a vertical posture (see below). Figure 18A The second holding state of one batch of substrates W, which maintains a horizontal orientation (see below). Figure 18D The orientation of a batch of substrates W can be switched between horizontal and vertical orientations.

[0225] <An example of substrate processing in the third embodiment>

[0226] Figures 18A-18E This is a schematic diagram illustrating the situation of the substrate processing apparatus 1B in the third embodiment for explaining the execution of substrate processing.

[0227] According to the substrate processing apparatus 1B of the third embodiment, it is capable of performing... Figure 5 The substrate processing shown. Hereinafter, the substrate processing of substrate processing apparatus 1B and... Figures 6A to 6C The differences in substrate processing shown will be explained in detail.

[0228] The main handling robot 17 receives a batch of substrates W, consisting of multiple substrates W, from the attitude switching robot 16 and moves them to the first handover position. In the first holding state, the main handling robot 17 hands over the batch of substrates W to the first lifting handling robot 19A. The substrates W handed over to the first lifting handling robot 19A are in a vertical orientation.

[0229] The first lifting device 50A of the first lifting and transporting robot 19A is located in the first upper position. Figure 18A The substrate W is received in a state where it is positioned as shown by the double-dotted line. The substrate W is supported by the first lifter 50A of the first lifting and handling robot 19A.

[0230] The first elevator 50A, while supporting one batch of substrates W, descends from the first upper position toward the sulfuric acid treatment position. Thus, as... Figure 18A As shown, one batch of substrates W is immersed vertically in sulfuric acid bath 20 in sulfuric acid liquid (sulfuric acid immersion process: step S1).

[0231] Then, the first elevator 50A rises towards the first upper position, thereby removing one batch of substrates W from the sulfuric acid-containing liquid in the sulfuric acid tank 20. For example... Figure 18B As shown, the hand 80 of the main handling robot 17 receives a batch of substrates W from the first elevator 50A located in the first upper position.

[0232] After receiving a batch of substrates W from the first elevator 50A, the hand 80 of the main handling robot 17 moves to the second handover position. (As...) Figure 18C As shown, the state of the hand 80 of the main handling robot 17 is changed to the second holding state through the posture switching mechanism 71, and the posture of a batch of substrates W held on the hand 80 changes from vertical posture to horizontal posture (first posture change process).

[0233] The orientation of a batch of substrates W can be changed either when the hand 80 is in the first handover position or when the hand 80 is in the second handover position. Alternatively, the orientation of a batch of substrates W can be changed at a predetermined time during the period when the hand 80 moves from the first handover position to the second handover position.

[0234] like Figure 18C As shown, the second elevator 50B, located in the second upper position, receives a batch of substrates W in a horizontal orientation from the main transport robot 17, located in the second handover position. Afterwards, the second elevator 50B moves from the second upper position (… Figure 18D The position indicated by the double-dotted line is oriented towards the gas processing position. Figure 18D The position indicated by the solid line is moved.

[0235] With the second lift 50B in the gas processing position, the ozone gas valve 42 and the exhaust valve 46 are opened. As a result, the atmosphere within the processing space 40a of the gas processing chamber 40 is exhausted, and ozone-containing gas is supplied to the processing space 40a. Figure 18D As shown, by supplying ozone-containing gas to the processing space 40a, a batch of substrates W in a horizontal orientation is exposed to ozone-containing gas (ozone exposure process: Figure 5 Step S2, horizontal exposure process (as shown).

[0236] By exposing a substrate W coated with a sulfuric acid-containing liquid to an ozone-containing gas, the ozone in the ozone gas dissolves in the sulfuric acid-containing liquid adhering to the substrate W, generating persulfate in the sulfuric acid-containing liquid of one batch of substrates W. Persulfate can be used to dissolve the organic film exposed from the substrate W in the sulfuric acid-containing liquid. Sometimes the organic film does not completely dissolve in the sulfuric acid-containing liquid and peels off from the upper surface of the substrate W.

[0237] Preferably, ozone-containing gas is supplied to the processing space 40a, thereby replacing the atmosphere within the processing space 40a with ozone-containing gas, and the processing space 40a is filled with ozone-containing gas (ozone-containing gas filling process). If the processing space 40a is filled with ozone-containing gas, persulfate can be rapidly and sufficiently generated in the sulfuric acid-containing liquid.

[0238] When the second elevator 50B supports the batch of substrates W in a horizontal position, the positional relationship between the batch of substrates W, the multiple supply hole rows 49AL, and the multiple exhaust hole rows 49BL in the gas processing position is the same as in the second embodiment (see reference). Figure 14 ).

[0239] Subsequently, the second elevator 50B rises towards the second upper position, thereby removing one batch of substrates W from the gas processing chamber 40. The hand 80 of the main handling robot 17 receives one batch of substrates W from the second elevator 50B located in the second upper position.

[0240] After receiving a batch of substrates W from the second elevator 50B, the hand 80 of the main handling robot 17 moves to the third handover position. (As...) Figure 18E As shown, the state of the hand 80 of the main handling robot 17 is changed to the first holding state through the posture switching mechanism 71, and the posture of a batch of substrates W held by the hand 80 is changed from the horizontal posture to the vertical posture (second posture change process).

[0241] The orientation of a batch of substrates W can be changed when the hand 80 is in the second handover position or when the hand 80 is in the third handover position. Alternatively, the orientation of a batch of substrates W can be changed at a predetermined time during the period when the hand 80 moves from the second handover position to the third handover position.

[0242] like Figure 18E As shown, the third lifter 50C, located at the third upper position, receives a batch of substrates W in a vertical orientation from the main handling robot 17, located at the third handover position. Then, the third lifter 50C descends from the third upper position toward the rinsing processing position. Thus, the batch of substrates W in a vertical orientation is immersed in the rinsing liquid in the rinsing liquid tank 30 (rinsing process: step S3).

[0243] One batch of substrates W is rinsed by immersing them in rinsing solution in rinsing tank 30. Specifically, sulfuric acid-containing liquid containing dissolved organic film and organic film peeled off from substrates W are removed.

[0244] After removing one batch of substrates W from the gas processing chamber 40, the ozone gas valve 42 is closed, and instead, the replacement gas valve 44 is opened. This supplies replacement gas to the processing space 40a of the gas processing chamber 40, causing the atmosphere within the processing space 40a to be replaced by the replacement gas. Consequently, ozone-containing gas is removed from the processing space 40a.

[0245] Subsequently, the third lifting and handling robot 19C delivers one batch of substrates W to the main handling robot 17. The main handling robot 17 then transports the batch of substrates W received from the third lifting and handling robot 19C to the drying processing unit 10.

[0246] According to the third embodiment, it achieves the same effect as the second embodiment.

[0247] According to the third embodiment, the handling unit 3 includes a first lifting handling robot 19A (first handling robot), a second lifting handling robot 19B (second handling robot), and a main handling robot 17 that handles one batch of substrates W between the first lifting handling robot 19A and the second lifting handling robot 19B. Furthermore, the attitude switching mechanism 71 switches the attitude of the batch of substrates W handled by the main handling robot 17 between a horizontal attitude and a vertical attitude.

[0248] Therefore, the transport of one batch of substrates W to the sulfuric acid tank 20, the transport of one batch of substrates W to the gas treatment chamber 40, and the attitude change of one batch of substrates W are all performed by different robots. Therefore, it is possible to suppress the complexity of the structure of each robot.

[0249] <The substrate processing apparatus of the first variation of the third embodiment>

[0250] Figure 19 This is a front view of the main part of the substrate processing apparatus 1B of the first variant of the third embodiment.

[0251] In a first variation of the third embodiment, the second lifting and transporting robot 19B transports a batch of substrates W in a horizontal orientation to the gas processing chamber 40, and within the gas processing chamber 40, multiple substrates W are rotated around a vertical axis A4 that passes through the center of the batch of substrates W in a horizontal orientation.

[0252] In detail, the second lifting and handling robot 19B includes: a substrate rotation mechanism 90 that rotates the second lifter 50B around the vertical axis A4; a lifting track 91 that supports the substrate rotation mechanism 90 and the second lifter 50B in a way that can lift and lower; and a lifting drive mechanism 92 that lifts and lowers the second lifter 50B and the substrate rotation mechanism 90 along the lifting track 91.

[0253] The second lifter 50B of the second lifting and transporting robot 19B in the first variation of the third embodiment is not particularly limited, and may have, for example, the following structure. The second lifter 50B includes, for example, a periphery holding portion 96 for holding the periphery of each substrate W and a connecting portion 97 for connecting the lifting track 91 and the periphery holding portion 96.

[0254] In addition, the ozone gas treatment unit 6 includes a replacement gas flow path heater 93 for heating the replacement gas in the replacement gas supply flow path 43.

[0255] The temperature of the displacement gas is preferably in the range of 50°C or higher and 270°C or lower. More preferably, it is in the range of 80°C or higher and 170°C or lower.

[0256] Figure 20A as well as Figure 20B This is a schematic diagram illustrating a first variation of the substrate processing apparatus 1B used to explain the execution of substrate processing in the third embodiment. Figure 21 This is a flowchart illustrating an example of substrate processing performed by the substrate processing apparatus 1B of the first variant of the third embodiment.

[0257] According to the substrate processing apparatus 1B of the first variant of the third embodiment, it is capable of performing with Figures 18A-18E The substrate processing shown in the third embodiment is the same as that used in the substrate processing. Hereinafter, it will be described in the same way as... Figures 18A-18E The differences in substrate processing shown will be explained in detail.

[0258] like Figure 21As shown, in the substrate processing apparatus 1B of the first variant of the third embodiment, a substrate rotation process (step S6) is performed after the sulfuric acid impregnation process (step S1) and before the ozone exposure process (step S2). More specifically, it is described below.

[0259] In the substrate processing of the first variation of the third embodiment, similarly to the substrate processing of the third embodiment, a batch of substrates W, after being immersed in a sulfuric acid-containing liquid, is transferred from the first elevator 50A to the main transport robot 17. Then, as in... Figure 20A As shown, the second elevator 50B, located in the second upper position, receives a batch of substrates W in a horizontal orientation from the main transport robot 17, located in the second holding state in the second handover position. Afterwards, the second elevator 50B moves from the second upper position (refer to...) Figure 20A ) Towards the gas processing location ( Figure 20B The position indicated by the solid line is moved.

[0260] With the second lifter 50B in the gas handling position, the second lifter 50B rotates around the vertical axis A4. As a result, one batch of substrates W rotates together with the second lifter 50B (substrate rotation process: Figure 21 (See step S6). As a result, the sulfuric acid-containing liquid is dispersed from the substrate W, and the liquid film of the sulfuric acid-containing liquid adhering to the main surface of each substrate W is thinned (sulfuric acid thinning process).

[0261] After at least one batch of substrates W begins to rotate, the ozone gas valve 42 and the exhaust valve 46 are opened. As a result, the atmosphere within the processing space 40a of the gas processing chamber 40 is exhausted, and ozone-containing gas is supplied to the processing space 40a. Figure 20B As shown, by supplying ozone-containing gas to the processing space 40a, a batch of substrates W in a horizontal orientation is exposed to ozone-containing gas (ozone exposure process: Figure 21 (See step S2 shown). It should be noted that during the supply of ozone gas, one batch of substrates W can be rotated, and the rotation of one batch of substrates W can also be stopped.

[0262] After a batch of substrates W is exposed to ozone gas, the second lift 50B moves to the second upper position while its rotation is stopped. Afterwards, the batch of substrates W is transferred to the main handling robot 17 for a rinsing process. Figure 21 Step S3 and drying process shown Figure 21 Step S4 is shown.

[0263] According to a first variation of the third embodiment, after the attitude change process and before one batch of substrates W is exposed to ozone-containing gas in the ozone exposure process, one batch of substrates W is rotated around the vertical axis A4.

[0264] Therefore, excess sulfuric acid-containing liquid can be removed from the substrate W, improving the uniformity of the sulfuric acid-containing liquid thickness at various locations on the substrate W. This, in turn, improves the uniformity of ozone concentration in the sulfuric acid-containing liquid at various locations on the substrate W. Consequently, uneven removal of the organic film at various locations on the substrate W can be reduced.

[0265] Alternatively, unlike the first variation, after the rotation of one batch of substrates W begins and before the ozone-containing gas is supplied to the processing space 40a, a displacement gas is supplied to heat one batch of substrates W. By heating the entire batch of substrates W with a displacement gas before the ozone-containing gas is supplied, the activity of persulfate can be easily and uniformly improved. This reduces uneven removal of the organic film between substrates W.

[0266] <The substrate processing apparatus of the second variation of the third embodiment>

[0267] Figure 22 This is a front view of the main part of the substrate processing apparatus 1B of the second variation of the third embodiment.

[0268] In the substrate processing apparatus 1B of the second variation of the third embodiment, with Figure 16 The substrate processing apparatus 1B shown is different, and also includes a heat processing unit 13 that heats a batch of substrates W while rotating them.

[0269] The heat treatment unit 13 includes a heat treatment chamber 100 having a heat treatment space 100a capable of accommodating one batch of substrates W. The heat treatment chamber 100 has an upper end portion 100b that can be opened and closed. The heat treatment unit 13 includes: a heat gas supply passage 101 for supplying heat gas to the heat treatment chamber 100, a heat gas valve 102 for opening and closing the heat gas supply passage 101, a heat gas discharge passage 103 for discharging the atmosphere inside the heat treatment chamber 100, and a heat gas discharge valve 104 for opening and closing the heat gas discharge passage 103.

[0270] The heating gas is, for example, an inert gas. The temperature of the heating gas is preferably in the range of 50°C or higher and 270°C or lower. More preferably, it is in the range of 80°C or higher and 170°C or lower.

[0271] The substrate processing apparatus 1B also includes a fourth lifting and transporting robot 19D that transports a batch of substrates W between the main transport robot 17 and the heat treatment unit 13. The fourth lifting and transporting robot 19D is an example of the third transporting robot. The structure of the fourth lifting and transporting robot 19D is, for example, similar to... Figure 3 The first transport robot 18A shown is identical.

[0272] However, the sliding mechanism 52 is not provided in the fourth lifting and handling robot 19D. In addition, the fourth lifting and handling robot 19D is configured as a batch of base plates W supporting a horizontal posture.

[0273] The fourth lifting and handling robot 19D includes: a fourth lifter 50D, a substrate rotation mechanism 105 that rotates the fourth lifter 50D around a vertical axis A5, a lifting track 106 that supports the substrate rotation mechanism 105 and the fourth lifter 50D in a way that allows them to be lifted and lowered, and a lifting drive mechanism 107 that allows the fourth lifter 50D and the substrate rotation mechanism 105 to be lifted and lowered along the lifting track 106.

[0274] The fourth lifter 50D of the fourth lifting and handling robot 19D is not particularly limited, but may have a structure such as the following. The fourth lifter 50D includes, for example, a periphery holding portion 108 for holding the periphery of each substrate W and a connecting portion 109 connecting the lifting track 106 and the periphery holding portion 108. The fourth lifter 50D of the fourth lifting and handling robot 19D can move up and down between a fifth upper position located directly above the heat treatment unit 13 and a heat treatment position where a batch of substrates W is housed in the heat treatment space 100a.

[0275] The fourth lifting and transporting robot 19D transports multiple substrates W in a horizontal orientation to the heat treatment chamber 100, and rotates the multiple substrates W around the vertical axis A5 passing through the center of the multiple substrates W in a horizontal orientation within the heat treatment chamber 100.

[0276] In a second variation of the third embodiment, the hand 80 of the main handling robot 17 is able to move to a fourth handover position where a batch of substrates W can be handed over to the fourth elevator 50D located in the fifth upper position.

[0277] In the second variation of the third embodiment, it is also possible to perform... Figure 21 The substrate processing shown. That is, in the substrate processing apparatus 1B of the second variation of the third embodiment, the substrate rotation process (step S6) is performed after the sulfuric acid impregnation process (step S1) and before the ozone exposure process (step S2). In detail, it is described below.

[0278] In the substrate processing of the second variation of the third embodiment, similarly to the substrate processing of the third embodiment, a batch of substrates W, after being immersed in a sulfuric acid-containing liquid, is transferred from the first elevator 50A to the main transport robot 17. Then, the fourth elevator 50D, located at the fifth upper position, receives the batch of substrates W in a horizontal orientation from the main transport robot 17, located at the fourth transfer position. Afterwards, the fourth elevator 50D moves from the fourth upper position toward the heat treatment position.

[0279] With the fourth lifter 50D in the heat treatment position, the fourth lifter 50D rotates around the vertical axis A5. As a result, one batch of substrates W rotates together with the fourth lifter 50D (substrate rotation process: step S6). As a result, sulfuric acid liquid is dispersed from the substrates W, and the liquid film of sulfuric acid liquid adhering to the main surface of each substrate W is thinned (sulfuric acid thinning process).

[0280] Simultaneously with or after the start of rotation of a batch of substrates W, the heating gas valve 102 and the heating gas discharge valve 104 are opened. This expels the atmosphere from the heating processing space 100a of the heating processing chamber 100 and supplies heating gas into the heating processing space 100a. By supplying heating gas to the heating processing space 100a, the batch of substrates W in a horizontal orientation is heated (heating rotation process).

[0281] Subsequently, one batch of substrates W is transferred from the fourth elevator 50D to the main transport robot 17 for ozone exposure. Figure 21 Step S2), rinsing process ( Figure 21 Step S3) and drying process ( Figure 21 Step S4).

[0282] According to a second variation of the third embodiment, a batch of substrates W can be rotated within the heat treatment chamber 100 to remove excess sulfuric acid-containing liquid from the substrates W. By removing the sulfuric acid-containing liquid through rotation of the substrates W, the uniformity of the thickness of the sulfuric acid-containing liquid at various locations on the substrates W can be improved.

[0283] Excess sulfuric acid-containing liquid is removed from substrate W in the heat treatment chamber 100, thus allowing for the simultaneous removal of sulfuric acid-containing liquid and heating of a batch of substrate W. After heating, the batch of substrate W is transported to the gas treatment chamber 40 via the main transport robot 17 and the second lifting transport robot 19B, where excess sulfuric acid-containing liquid is removed, and the heated batch of substrate W is exposed to ozone-containing gas. This improves the uniformity of ozone concentration in the sulfuric acid-containing liquid at various locations on substrate W and enhances the activity of persulfate. Consequently, uneven removal of the organic film at various locations on substrate W can be further reduced.

[0284] Alternatively, unlike the second variation, the heating gas valve 102 and the heating gas exhaust valve 104 can be opened before the substrate W of a batch begins to rotate, so as to fully heat the heating chamber 100.

[0285] <Other Implementation Methods>

[0286] The present invention is not limited to the embodiments described above, and can be implemented in other ways as illustrated below.

[0287] (1) For example, such as Figure 23 As shown, the multiple processing units 2 may also include a single processing unit 110 that processes the substrate W one by one. In detail, a single processing unit 110 includes a rotary chuck 111, a processing cover 112, a heater 113, an ozone-containing gas nozzle 114, a rinsing fluid nozzle 115, and a chamber 116.

[0288] A rotating chuck 111 holds the substrate W in a horizontal position while rotating the substrate W about a vertical axis A6 passing through the center of the substrate W. A processing shroud 112 surrounds the rotating chuck 111 and receives the processing liquid that splashes from the substrate W. A heater 113 heats the substrate W held on the rotating chuck 111. An ozone-containing gas nozzle 114 supplies ozone-containing gas toward the substrate W. A rinsing liquid nozzle 115 supplies rinsing liquid toward the substrate W.

[0289] After a batch of substrates W is immersed in sulfuric acid liquid in sulfuric acid bath 20, one substrate W from the batch is transferred to single-substrate processing unit 110 (transfer process). The substrate W transferred to single-substrate processing unit 110 is rotated by rotary chuck 111 and heated by heater 113 (substrate rotation process). Then, ozone-containing gas is sprayed from ozone-containing gas nozzle 114, thereby exposing the substrate W with the sulfuric acid liquid to ozone-containing gas (ozone exposure process). Single-substrate processing unit 110 is an example of an ozone gas treatment unit.

[0290] Next, the substrate W is rinsed by spraying rinsing fluid from the rinsing fluid nozzle 115. Then, the substrate W is rotated at high speed by rotating the chuck 111, thereby drying the substrate W (drying process).

[0291] If multiple single processing units 110 are provided, after a batch of substrates W is immersed in a sulfuric acid-containing liquid, all substrates W can be quickly exposed to ozone-containing gas.

[0292] (2) A heater 120 for heating the sulfuric acid-containing liquid stored in the sulfuric acid tank 20 may also be provided (see reference). Figure 2(The double-dotted line). For example, the temperature of the sulfuric acid-containing liquid is preferably 150°C or higher. By heating the sulfuric acid-containing liquid with heater 120, the activity of persulfate can be increased, and the organic film can be removed quickly. Alternatively, a heater can be installed to heat the sulfuric acid-containing liquid in the piping that supplies the sulfuric acid-containing liquid to the sulfuric acid tank 20, instead of heater 120. In addition, the sulfuric acid-containing liquid used in the sulfuric acid tank 20 can also be discharged from the sulfuric acid tank 20 and reused.

[0293] (3) In the first variation of the first embodiment and the second variation of the second embodiment, a sulfuric acid tank 20 is disposed in the gas treatment chamber 40. However, the sulfuric acid tank 20 may also be housed in the sulfuric acid treatment chamber 21, and the gas treatment chamber 40 may be disposed directly above the sulfuric acid treatment chamber 21.

[0294] (4) If the lifting device 50 and the hand 80 are not equipped with a mechanism for switching the posture of the substrate W, the posture of a batch of substrates W can be changed from a vertical posture to a horizontal posture by the posture switching robot 16 after the sulfuric acid impregnation process. Similarly, after the ozone exposure process, the posture of a batch of substrates W can also be changed from a horizontal posture to a vertical posture by the posture switching robot 16.

[0295] In addition, if the substrate processing apparatus 1A described above is used, it is also possible to maintain the orientation of a batch of substrates W in a horizontal position while performing the sulfuric acid impregnation process, the ozone exposure process, and the rinsing process.

[0296] (5) Alternatively, the processing space 40a can be filled with ozone-containing gas before a batch of substrates W is transported to the ozone gas processing unit 6. In this case, by transporting a batch of substrates W to the ozone gas processing unit 6, a batch of substrates W can be exposed to ozone-containing gas. In short, it is sufficient to expose a batch of substrates W transported to the ozone gas processing unit 6 to ozone-containing gas. That is, the supply of ozone-containing gas to the processing space 40a can begin before a batch of substrates W is placed in the processing space 40a, or it can begin after a batch of substrates W is placed in the processing space 40a.

[0297] (6) In the above embodiments, the controller 4 controls the entire substrate processing apparatus 1. However, the controllers for controlling each component of the substrate processing apparatus 1 may also be distributed in multiple locations. In addition, the controller 4 does not need to directly control each component, and the signals output from the controller 4 may be received by the sub-controllers controlling each component of the substrate processing apparatus 1.

[0298] (7) It should be noted that in the above embodiments, expressions such as "horizontal" and "vertical" are used, but they do not need to be strictly "horizontal" and "vertical". That is, these expressions allow for deviations in manufacturing precision, setting precision, etc.

[0299] (8) In addition, sometimes blocks are used to represent the structures schematically, but the shape, size and positional relationship of each block do not represent the shape, size and positional relationship of each structure.

[0300] The embodiments of the present invention have been described in detail, but these are merely specific examples used to clarify the technical content of the present invention. The present invention should not be construed as being limited to these specific examples, and the scope of the present invention is defined only by the appended claims.

Claims

1. A substrate processing method, comprising: The sulfuric acid impregnation process involves immersing multiple substrates in a sulfuric acid bath containing sulfuric acid liquid; The handling process involves removing multiple substrates from the sulfuric acid bath and transferring them to the ozone gas treatment unit; and The ozone exposure process involves exposing multiple substrates transported to the ozone gas treatment unit to ozone-containing gas. In the transport process, with the sulfuric acid-containing liquid adhering to the surfaces of the multiple substrates, the multiple substrates are transported from the sulfuric acid bath to the ozone gas treatment unit. In the ozone exposure process, the ozone-containing gas is dissolved in the sulfuric acid-containing liquid adhering to the surfaces of the plurality of substrates, and persulfate is generated in the sulfuric acid-containing liquid. The ozone gas treatment unit includes a gas treatment chamber that houses multiple of the substrates. The gas processing chamber has a pair of walls facing each other to divide the processing space within the chamber, a plurality of supply holes opening on one side of the pair of walls to supply ozone-containing gas into the processing space, and a plurality of exhaust holes opening on the other side of the pair of walls to exhaust gas from the processing space, wherein the plurality of supply holes and the plurality of exhaust holes are respectively facing each other. The ozone exposure process includes: exposing multiple substrates containing ozone gas by placing them in the processing space, thereby removing multiple substrates from the sulfuric acid bath. The ozone exposure process includes the following steps: supplying ozone-containing gas to the processing space from the plurality of supply holes, and venting the processing space through the plurality of exhaust holes, thereby exposing the plurality of substrates disposed in the processing space to the ozone-containing gas.

2. The substrate processing method according to claim 1, wherein, In the gas processing chamber, multiple supply holes, each consisting of a plurality of supply holes, are arranged in a predetermined arrangement direction. The ozone exposure process includes the following steps: arranging the multiple substrates in the processing space such that the multiple substrates are arranged in the arrangement direction and each substrate is located between the supply hole rows.

3. The substrate processing method according to claim 1, wherein, The sulfuric acid impregnation process includes a vertical impregnation process in which multiple substrates in a vertical orientation are immersed in a sulfuric acid bath containing sulfuric acid liquid. The substrate processing method further includes a posture change process, in which the posture of the multiple substrates removed from the sulfuric acid bath is changed from a vertical posture to a horizontal posture. The ozone exposure process includes a horizontal exposure process in which multiple substrates in a horizontal orientation are exposed to ozone-containing gas.

4. The substrate processing method according to claim 3, further comprising a substrate rotation step, wherein the plurality of substrates are rotated about a vertical axis passing through the center portion of the plurality of substrates in the horizontal orientation, after the orientation change step and before the plurality of substrates are exposed to ozone gas in the ozone exposure step.

5. The substrate processing method according to any one of claims 1 to 4, wherein, The processing space is located directly above the sulfuric acid tank. The handling process includes: a process of placing the multiple substrates in the processing space by lifting the multiple substrates from the sulfuric acid bath.

6. A substrate processing apparatus, comprising: A sulfuric acid bath for storing sulfuric acid-containing liquid capable of impregnating multiple substrates; Multiple substrates are exposed to an ozone gas treatment unit containing ozone gas; and A transport unit for moving multiple substrates between the sulfuric acid tank and the ozone gas treatment unit. With the sulfuric acid-containing liquid adhering to the surfaces of the multiple substrates, the transport unit transports the multiple substrates from the sulfuric acid bath to the ozone gas treatment unit. The ozone gas treatment unit dissolves the ozone-containing gas in the sulfuric acid-containing liquid attached to the surfaces of the plurality of substrates, generating persulfate in the sulfuric acid-containing liquid. The ozone gas treatment unit includes a gas treatment chamber having a processing space capable of accommodating multiple substrates, and exposing the multiple substrates housed in the processing space to ozone-containing gas. The gas processing chamber has a pair of walls facing each other in a manner that divides the processing space, a plurality of supply holes that open on one side of the pair of walls and supply ozone-containing gas to the processing space, and a plurality of exhaust holes that open on the other side of the pair of walls and exhaust gas from the processing space. The plurality of supply holes and the plurality of exhaust holes are respectively facing each other, and the plurality of supply holes spray ozone-containing gas into the plurality of exhaust holes.

7. The substrate processing apparatus according to claim 6, wherein, The gas processing chamber has multiple rows of supply holes, each row consisting of multiple supply holes arranged in a predetermined direction. The transport unit supports multiple substrates arranged in the arrangement direction and moves the multiple substrates into the gas processing chamber with each substrate positioned between the rows of supply holes.

8. The substrate processing apparatus according to claim 6, wherein, The sulfuric acid bath is capable of immersing multiple vertically oriented substrates in a sulfuric acid-containing liquid. The processing space can accommodate multiple substrates in a horizontal orientation. The handling unit includes a posture switching mechanism that switches the posture of multiple substrates between vertical and horizontal postures.

9. The substrate processing apparatus according to claim 8, wherein, The handling unit includes a handling robot, which has a lifter to support multiple substrates and handles the multiple substrates between the sulfuric acid tank and the gas treatment chamber. The attitude switching mechanism switches the attitude of multiple substrates between vertical and horizontal attitudes by deforming the elevator.

10. The substrate processing apparatus according to any one of claims 6 to 9, wherein, The processing space is located directly above the sulfuric acid tank. The transport unit supports multiple substrates while moving up and down, thereby transporting multiple substrates between the gas treatment chamber and the sulfuric acid tank.

11. The substrate processing apparatus according to claim 10, further comprising a cover member for separating the interior of the sulfuric acid tank from the processing space and for opening and closing the sulfuric acid tank.

12. The substrate processing apparatus according to claim 8, wherein, The transport unit includes: The first transport robot moves multiple substrates in a vertical orientation to the sulfuric acid tank. A second transport robot, and [other robots], move multiple horizontally oriented substrates to the gas treatment chamber. A main transport robot that transports multiple substrates between the first transport robot and the second transport robot; The attitude switching mechanism switches the attitude of the multiple substrates being handled by the main handling robot between a horizontal attitude and a vertical attitude.

13. The substrate processing apparatus according to claim 12, wherein, The second transport robot transports multiple horizontally oriented substrates into the gas treatment chamber and rotates the multiple substrates within the gas treatment chamber around a vertical axis passing through the center of the multiple horizontally oriented substrates.

14. The substrate processing apparatus according to claim 12, further comprising a heat treatment chamber for heating a plurality of substrates. The transport unit further includes a third transport robot that transports multiple horizontally oriented substrates to the heat treatment chamber and rotates the multiple substrates within the heat treatment chamber about a vertical axis passing through the center of the multiple horizontally oriented substrates. The main transport robot transports multiple substrates between the sulfuric acid tank, the gas treatment chamber, and the heat treatment chamber.

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