Substrate processing method and substrate processing apparatus

Abstract

The substrate processing method of the present invention includes: a processing liquid supply step, which supplies processing liquid to the substrate; and a dissolved gas supply step, which dissolves dissolved gas separated by entering the plurality of passages of the separator in the processing liquid while the surface of the separator, which includes a plurality of passages with surface openings, is in contact with at least one of the processing liquid that contacts the substrate and the processing liquid that contacts the substrate.

Description

Technical Field

[0001] This invention relates to a substrate processing method and a substrate processing apparatus for processing substrates. Substrates include, for example, substrates for FPD (Flat Panel Display) devices such as semiconductor wafers, liquid crystal display devices, or organic EL (electroluminescence) display devices, substrates for optical discs, substrates for magnetic discs, substrates for magneto-optical discs, substrates for photomasks, ceramic substrates, and substrates for solar cells. Prior Technology

[0002] JP 2023-34828A discloses a substrate disposed in a processing chamber filled with ozone gas, and the substrate being heated while a liquid film of sulfuric acid is formed on the main surface of the substrate.

[0003] At least one embodiment of the present invention provides a substrate processing method and a substrate processing apparatus that can efficiently dissolve dissolved gases in a processing liquid. Summary of the Invention

[0004] One embodiment of the present invention provides a substrate processing method, comprising: a processing liquid supply step, which supplies processing liquid to a substrate; and a dissolved gas supply step, which involves dissolving dissolved gas separated by entering the plurality of passages of the separator into the processing liquid while the surface of a splitter including a plurality of passages with surface openings is in contact with at least one of the processing liquid contacting the substrate and the processing liquid before contacting the substrate.

[0005] In the above embodiments, at least one of the following features may also be added to the above substrate processing method.

[0006] The dissolved gas supply process includes the following steps: with the contact portion of the surface of the separator in contact with at least one of the processing liquid that contacts the substrate and the processing liquid that comes into contact with the substrate, and with the non-contact portion of the surface of the separator away from the processing liquid, the dissolved gas separated by flowing from the non-contact portion into the plurality of passages is released from the contact portion into the processing liquid.

[0007] The above-mentioned dissolved gas supply process includes the following steps: filling the gas region, which is the area opposite to the above-mentioned separator and the above-mentioned processing liquid, with the above-mentioned dissolved gas.

[0008] The aforementioned substrate processing method further includes: a cleaning liquid supply step, which involves supplying the cleaning liquid to the substrate after supplying the processing liquid to the substrate; and a separator cleaning step, which involves bringing the contact portion of the surface of the separator into contact with the cleaning liquid that contacts the substrate.

[0009] The separator cleaning process includes the following steps: bringing the contact portion of the surface of the separator into contact with the cleaning liquid that contacts the substrate, while releasing the cleaning gas separated by flowing the cleaning gas from the non-contact portion of the surface of the separator into the cleaning liquid from the contact portion.

[0010] The aforementioned substrate processing method further includes a separator drying step, which is performed after the aforementioned separator cleaning step. In this step, the cleaning gas separated by allowing the cleaning gas to flow from the non-contact portion of the aforementioned surface of the separator into the plurality of passages is released from the contact portion while the contact portion of the aforementioned surface of the separator is removed from the cleaning liquid that was in contact with the aforementioned substrate.

[0011] The dissolved gas supply process includes the following steps: in a state where the surface of the separator is in contact with the processing liquid in the tank, the dissolved gas separated by entering the plurality of passages of the separator is dissolved in the processing liquid; and the processing liquid supply process includes the following steps: supplying the processing liquid supplied from the tank to the substrate.

[0012] The above-mentioned processing liquid supply process includes the following steps: after the dissolved gas is dissolved in the processing liquid in the above-mentioned tank, an inert gas is supplied to the above-mentioned tank, thereby increasing the gas pressure in the above-mentioned tank to the value at which the above-mentioned processing liquid in the above-mentioned tank is discharged from the above-mentioned tank to the above-mentioned substrate.

[0013] The aforementioned separator is a porous material.

[0014] Another embodiment of the present invention provides a substrate processing apparatus comprising: a processing liquid nozzle for supplying processing liquid to a substrate; a separator including a plurality of passages with surface openings; a dissolved gas pipe for ejecting dissolved gas into the plurality of passages of the separator; and a dissolved gas supply unit for supplying the dissolved gas to the dissolved gas pipe; wherein the dissolved gas supply unit supplies the dissolved gas to the dissolved gas pipe while the surface of the separator is in contact with at least one of the processing liquid contacting the substrate and the processing liquid before contacting the substrate. The dissolved gas supply unit may be a dissolved gas generator for generating the dissolved gas to be supplied to the dissolved gas pipe or a fluid device in contact with the dissolved gas to be supplied to the dissolved gas pipe, or may include at least one of a dissolved gas generator and a fluid device. The fluid device may include at least one of piping, valves, connectors, and tanks, or may include other devices besides these. At least one of the above-mentioned features related to the substrate processing method may also be added to the substrate processing apparatus. Simple Explanation of the Diagram

[0015] Figure 1A is a schematic top view showing the layout of a substrate processing apparatus according to one embodiment of the present invention. Figure 1B shows a schematic side view of the substrate processing apparatus. Figure 2 is a schematic diagram of the interior of the horizontal observation and processing unit. Figure 3 is a schematic diagram of the internal structure of the horizontal observation and processing unit. Figure 4 is a schematic diagram obtained by enlarging a portion of the processing unit. Figure 5 is a schematic diagram of the first example of a separator arranged inside a tank. Figure 6 is a schematic diagram of a second example of a separator installed inside a tank. Figure 7 is a schematic diagram showing the state of supplying sulfuric acid from the tank to the substrate. Figure 8 is a schematic diagram illustrating the expected phenomena when dissolved gas is supplied to the separator while it is in contact with the processing liquid. Figure 9 is a flowchart illustrating one example of substrate processing performed by a substrate processing apparatus. Figures 10A, 10B, and 10C are schematic diagrams illustrating an example of substrate processing performed by a substrate processing apparatus. Figures 10D, 10E, and 10F are schematic diagrams illustrating an example of substrate processing performed by a substrate processing apparatus. Figures 10G, 10H and 10I are schematic diagrams illustrating an example of substrate processing performed by a substrate processing apparatus. Figures 10J, 10K and 10L are schematic diagrams illustrating an example of substrate processing performed by a substrate processing apparatus. Figures 10M and 10N are schematic diagrams illustrating an example of substrate processing performed by a substrate processing apparatus. Figure 11 is a schematic diagram showing another example of a blocking component. Figure 12 is a schematic diagram showing another example of a cavity. Figure 13 is a schematic diagram showing another example of a cavity. Implementation

[0016] Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

[0017] Figure 1A is a schematic top view showing the layout of a substrate processing apparatus 1 according to one embodiment of the present invention. Figure 1B is a schematic side view of the substrate processing apparatus 1.

[0018] As shown in Figure 1A, the substrate processing apparatus 1 is a monolithic device that processes wafer-shaped substrates W, such as semiconductor wafers, one by one. The substrate processing apparatus 1 includes: a loading port LP, which holds a carrier CA, such as a FOUP (Front-Opening Unified Pod), that holds multiple substrates W; multiple processing units 2, which process the substrates W transported from the carrier CA on the loading port LP using processing fluids such as processing liquid or processing gas; a transport system TS, which transports the substrates W between the carrier CA on the loading port LP and the multiple processing units 2; an outer wall 1a, which forms a sealed space that accommodates the multiple processing units 2 and the transport system TS; and a control device 3, which controls the substrate processing apparatus 1.

[0019] A plurality of processing units 2 form a plurality of towers TW. Figure 1A shows an example with 4 towers TW. As shown in Figure 1B, a plurality of processing units 2 contained in one tower TW are stacked vertically. As shown in Figure 1A, the plurality of towers TW form two rows extending in the depth direction of the substrate processing apparatus 1 (left-right direction of the paper in Figure 1A) when viewed from above. When viewed from above, these two rows are opposite each other across the transport path TP.

[0020] The transport system TS includes a transfer robot IR and a central robot CR. The transfer robot IR transports substrate W between the carrier CA on the loading port LP and the central robot CR. The central robot CR transports substrate W between multiple processing units 2. The transfer robot IR is positioned between the loading port LP and the central robot CR when viewed from above. The central robot CR is positioned in the transport path TP.

[0021] The transfer robot IR includes one or more hands Hi that horizontally support the substrate W. Hands Hi can move parallel in either the horizontal or vertical direction. Hands Hi can rotate about a vertical line. Hands Hi can load and unload the substrate W relative to the carrier CA on any loading port LP, and can exchange substrate W with the central robot CR.

[0022] The central robot CR includes one or more hands Hc that horizontally support the substrate W. The hands Hc can move parallel in either the horizontal or vertical direction. The hands Hc can rotate around a vertical line. The hands Hc can transfer the substrate W to the transfer robot IR and can move the substrate W in and out relative to any processing unit 2.

[0023] The control device 3 controls the electrical and electronic equipment installed in the substrate processing apparatus 1. The control device 3 includes at least one computer capable of communicating with it. The computer includes: a CPU (central processing unit) 3c, which performs information processing such as program execution; and memory 3m, which stores information such as the program to be executed by the CPU 3c. The control device 3 performs the following tasks, such as transporting and processing the substrate W, by controlling the substrate processing apparatus 1. In other words, the control device 3 is programmed to perform the following tasks, such as transporting and processing the substrate W.

[0024] Next, processing unit 2 will be described.

[0025] Figures 2 and 3 are schematic diagrams of the interior of the horizontally viewed processing unit 2. Figure 2 shows the state where the blocking member 41 is positioned at the lower position and the substrate W is supported by a plurality of chuck pins 11. Figure 3 shows the state where the blocking member 41 is positioned at the upper position and the substrate W is supported by a plurality of chuck pins 11. As shown in Figure 2, the processing unit 2 includes: a chamber 4 that houses the substrate W; and a rotating chuck 10 that horizontally supports a substrate W within the chamber 4 and rotates it about a vertical axis of rotation A1 passing through the center of the substrate W.

[0026] The chamber 4 includes a box-shaped partition wall 5 with an opening for the substrate W to pass through, and a door 6 for opening and closing the opening. An FFU7 (fan filter unit) is positioned above an air outlet located on the upper part of the partition wall 5. The FFU7 continuously supplies clean air (air filtered by the filter) into the chamber 4 from the air outlet. The gas inside the chamber 4 is discharged from the chamber 4 through an exhaust pipe 8 connected to the bottom of the processing cup 31. This continuously creates a downward flow of clean air within the chamber 4. The flow rate of the exhaust gas discharged to the exhaust pipe 8 varies depending on the opening degree of the exhaust valve 9 located within the exhaust pipe 8.

[0027] The rotary chuck 10 includes: a circular rotating base 12, which is held horizontally; a plurality of chuck pins 11, which hold the substrate W horizontally above the rotating base 12; and a rotary motor 13, which rotates the rotating base 12 and the plurality of chuck pins 11 about a rotation axis A1. The rotary chuck 10 is not limited to a clamping chuck that contacts the end faces of the substrate W with the plurality of chuck pins 11, but can also be a vacuum chuck that holds the substrate W horizontally by adsorbing the back surface (lower surface) of the substrate W (which is a non-device forming surface) onto the upper surface 12u of the rotating base 12. When the rotary chuck 10 is a clamping chuck, the plurality of chuck pins 11 function as substrate holders. When the rotary chuck 10 is a vacuum chuck, the rotating base 12 function as a substrate holder.

[0028] The processing unit 2 includes a cylindrical processing cup 31 for catching processing liquid splashed from the substrate W. The processing cup 31 includes: a plurality of shields 34 for catching processing liquid discharged from the substrate W held by the rotating chuck 10 to the outside; a plurality of cups 33 for catching processing liquid guided downwards by the plurality of shields 34; and a cylindrical outer wall 32 surrounding the plurality of shields 34 and the plurality of cups 33. Figure 2 shows an example with two shields 34 and two cups 33, where the outer cup 33 and the inner shield 34 are integrally formed.

[0029] The protective cover 34 includes: a cylindrical portion 35 surrounding the rotating chuck 10; and an annular top wall 36 extending obliquely upward from the upper end of the cylindrical portion 35 toward the rotation axis A1. A plurality of top walls 36 overlap vertically, and a plurality of cylindrical portions 35 are arranged in a concentric circle. The annular upper end of the top wall 36 corresponds to the upper end of the protective cover 34 surrounding the substrate W and the rotating base 12 when viewed from above. A plurality of cups 33 are respectively disposed below the plurality of cylindrical portions 35. The cups 33 form annular grooves to receive the processing liquid guided downward from the protective cover 34.

[0030] Processing unit 2 includes a lifting actuator 34a that individually raises and lowers a plurality of protective covers 34. The lifting actuator 34a keeps the protective covers 34 stationary at any position within the range of an upper position to a lower position. Figure 2 shows a state in which the outer protective cover 34 is positioned in the upper position and the inner protective cover 34 is positioned in the lower position. The upper position is a position where the upper end of the protective cover 34 is positioned above the holding position of the base plate W held by the rotating chuck 10. The lower position is a position where the upper end of the protective cover 34 is positioned below the holding position.

[0031] An actuator is a device that converts driving energy, representing electrical, fluid, magnetic, thermal, or chemical energy, into mechanical work, i.e., the motion of a tangible object. Actuators include electric motors (rotary motors), linear motors, cylinders, and other devices. When the motion of the actuator differs from the motion of the object, a motion converter can be provided to convert the actuator's motion into linear or rotary motion. For example, when the actuator is an electric motor and causes the object to move linearly, a motion converter such as a ball screw or ball nut can convert the rotation of the electric motor into linear motion.

[0032] The processing unit 2 includes a plurality of nozzles that spray processing fluids such as processing liquids or processing gases toward the substrate W located above the rotary chuck 10. The plurality of nozzles includes: a first liquid nozzle 21 that sprays a first liquid toward the upper surface of the substrate W located above the rotary chuck 10; a second liquid nozzle 22 that sprays a second liquid toward the upper surface of the substrate W located above the rotary chuck 10; and a rinsing liquid nozzle 23 that sprays rinsing liquid toward the upper surface of the substrate W located above the rotary chuck 10. Figure 2 shows an example where the first liquid is sulfuric acid (H2SO4), the second liquid is SC1, and the rinsing liquid is pure water (DIW).

[0033] The first liquid nozzle 21 is connected to the first liquid pipe 21p that guides the first liquid. When the first liquid valve 21v installed on the first liquid pipe 21p is opened, the first liquid continuously sprays downward from the nozzle outlet of the first liquid nozzle 21. Similarly, the second liquid nozzle 22 is connected to the second liquid pipe 22p that guides the second liquid. When the second liquid valve 22v installed on the second liquid pipe 22p is opened, the second liquid nozzle 22 continuously sprays downward from the nozzle outlet of the second liquid nozzle 22.

[0034] The first solution may be a liquid containing at least one of sulfuric acid, nitric acid, hydrochloric acid, hydrofluoric acid, phosphoric acid, acetic acid, ammonia, hydrogen peroxide, organic acids (e.g., citric acid, oxalic acid, etc.), organic bases (e.g., TMAH: tetramethylammonium hydroxide, etc.), surfactants, and preservatives, or it may be a liquid other than those listed above. The same applies to the second solution. The first solution may also be a solution with the same composition as the second solution, but differing from the second solution in at least one of its concentration and temperature.

[0035] Although not illustrated, the first liquid valve 21v includes: a valve body having an annular valve seat for the passage of liquid medicine; a valve body movable relative to the valve seat; and an actuator that moves the valve body between a closed position where the valve body is in contact with the valve seat and an open position where the valve body is away from the valve seat. The same applies to other valves. The actuator can be a pneumatic actuator, an electric actuator, or any other type of actuator. The control device 3 opens and closes the first liquid valve 21v, etc., by controlling the actuator.

[0036] The flushing fluid nozzle 23 is connected to the flushing fluid piping 23p that guides the flushing fluid. When the flushing fluid valve 23v installed on the flushing fluid piping 23p is opened, the flushing fluid nozzle 23 continuously sprays flushing fluid downwards from its nozzle outlet. The flushing fluid can be any of the following: pure water (deionized water, DIW), carbonated water, electrolyzed ionized water, hydrogen water, ozone water, and hydrochloric acid water diluted to a concentration of, for example, around 10 to 100 ppm, or any other liquid.

[0037] The first drug nozzle 21 can be a scanning nozzle that moves the collision position of the drug relative to the substrate W within the upper surface of the substrate W, or it can be a fixed nozzle that cannot move the collision position of the drug relative to the substrate W. The same applies to other nozzles. Figure 3 shows an example where the first drug nozzle 21, the second drug nozzle 22, and the rinsing nozzle 23 are scanning nozzles.

[0038] As shown in Figure 3, the first liquid nozzle 21 is connected to a first nozzle actuator 21a that moves the first liquid nozzle 21 in at least one of the vertical and horizontal directions. The second liquid nozzle 22 is connected to a second nozzle actuator 22a that moves the second liquid nozzle 22 in at least one of the vertical and horizontal directions. The flushing fluid nozzle 23 is connected to a third nozzle actuator 23a that moves the flushing fluid nozzle 23 in at least one of the vertical and horizontal directions.

[0039] The first nozzle actuator 21a causes the first liquid nozzle 21 to move horizontally between a processing position where the liquid ejected from the first liquid nozzle 21 is supplied to the upper surface of the substrate W, and a standby position where the first liquid nozzle 21 is located around the processing cup 31 when viewed from above. The same applies to the second nozzle actuator 22a and the third nozzle actuator 23a. Figure 3 shows the state in which the first liquid nozzle 21 is positioned in the processing position.

[0040] Processing unit 2 includes a heating plate 14, which is an example of a heater used to heat the substrate W located above the rotating chuck 10. The heating plate 14 is disposed between the substrate W and the rotating base 12. The heating plate 14 includes a heating element (not shown) that generates Joule heat by energizing it, and a housing that contains the heating element. The heating element and housing are disposed below the substrate W. The heating element is connected to a wiring (not shown) that supplies power to it. The temperature of the heating element is changed by a control device 3. When the control device 3 heats the heating element, the entire substrate W is heated uniformly.

[0041] The outer casing of the heating plate 14 includes: a circular base portion disposed below the substrate W; and a plurality of hemispherical protrusions protruding upward from the upper surface of the base portion. The upper surface of the base portion is parallel to the lower surface of the substrate W and has an outer diameter smaller than the diameter of the substrate W. The plurality of protrusions contact the lower surface of the substrate W at positions that move upward away from the upper surface of the base portion. The plurality of protrusions are disposed at a plurality of positions within the upper surface of the base portion to horizontally support the substrate W. The substrate W is horizontally supported with its lower surface moving upward away from the upper surface of the base portion.

[0042] The heating plate 14 is horizontally supported by a support shaft 14s extending downward from the center of the heating plate 14. A plurality of chuck pins 11 are arranged around the heating plate 14. The center line of the heating plate 14 is arranged on the rotation axis A1 of the substrate W. Even if the rotating chuck 10 rotates, the heating plate 14 does not rotate. The outer diameter of the heating plate 14 is smaller than the diameter of the substrate W.

[0043] The heating plate 14 is capable of vertical parallel movement relative to the rotating base 12. The heating plate 14 is connected to the lifting actuator 14a via a support shaft 14s. The lifting actuator 14a causes the heating plate 14 to move vertically between an upper position (the position shown in FIG. 4) and a lower position (the positions shown in FIG. 2 and FIG. 3). The upper position is the contact position where the heating plate 14 contacts the lower surface of the substrate W. The lower position is the position where the heating plate 14 is positioned close to the lower surface of the substrate W and the upper surface of the rotating base 12, with the heating plate 14 in a state away from the substrate W.

[0044] The heating plate 14 is an example of a substrate holder. The lifting actuator 14a keeps the heating plate 14 stationary at any position within the range of an upper position to a lower position. When the substrate W is supported by the plurality of clamping pins 11 and the substrate W is released from its holding position, when the heating plate 14 rises to the upper position, the substrate W is lifted by the heating plate 14 and moves upward away from the plurality of clamping pins 11. In this state, when the heating plate 14 descends to the lower position, the substrate W on the heating plate 14 is placed on the plurality of clamping pins 11, and the heating plate 14 moves downward away from the substrate W.

[0045] The processing unit 2 includes a blocking member 41 disposed above the rotating chuck 10. The blocking member 41 is disposed inside the chamber 4. The blocking member 41 includes a circular plate portion 41p held horizontally and a cylindrical portion 41t extending downward from the outer periphery of the circular plate portion 41p. The circular plate portion 41p is also referred to as a blocking plate. The lower surface of the circular plate portion 41p corresponds to the lower surface of the blocking member 41. The center of the circular plate portion 41p is disposed on the rotation axis A1 of the base plate W. The inner diameter of the cylindrical portion 41t is smaller than the outer diameter of the rotating base 12. The outer diameter of the cylindrical portion 41t is smaller than the inner diameter of the upper end of the protective cover 34.

[0046] The blocking member 41 is connected to a lifting actuator 41a that allows the blocking member 41 to move vertically in parallel. The lifting actuator 41a keeps the blocking member 41 stationary at any position within the range of an upper position (the position shown in FIG. 3) to a lower position (the position shown in FIG. 2). The lower position is a position where the lower surface of the blocking member 41 is close to the upper surface of the substrate W, such that the scanning nozzle, such as the first liquid nozzle 21, cannot enter the space between the substrate W and the blocking member 41. The upper position is a standby position where the blocking member 41 is retracted to a height where the scanning nozzle can enter the space between the blocking member 41 and the substrate W.

[0047] As shown in Figure 2, when the lifting actuator 41a positions the blocking member 41 in the lower position, the lower end of the cylindrical portion 41t of the blocking member 41 is positioned lower than the substrate W held by the rotating chuck 10, and the substrate W is surrounded by the cylindrical portion 41t. This is also true even when the substrate W is supported by the heating plate 14 instead of the rotating chuck 10. A plurality of chuck pins 11 are disposed inside the cylindrical portion 41t.

[0048] When the lifting actuator 41a positions the blocking member 41 in the lower position, the gap between the cylindrical portion 41t and the rotating base 12 may or may not be sealed. In the former case, the cylindrical portion 41t may directly press against the rotating base 12, or it may press against the rotating base 12 through a rubber or resin sealing ring. Figure 2 shows an example of the cylindrical portion 41t directly pressing against the rotating base 12. When the blocking member 41 is positioned in the lower position, the space inside the blocking member 41 is sealed.

[0049] Next, the separator 51 disposed above the substrate W will be described.

[0050] Figure 4 is a schematic diagram of a portion of the processing unit 2, enlarged from previous views. Figure 4 shows the state where the blocking member 41 is positioned below and the substrate W is supported by the heating plate 14. The processing unit 2 includes: a separator 51 for separating gases such as dissolved gases; a dissolved gas pipe 44p for guiding the dissolved gas to be supplied to the separator 51; and an inert gas pipe 45p for guiding the inert gas to be supplied to the separator 51. Figure 4 shows an example where the dissolved gas is ozone gas (O3) and the inert gas is nitrogen gas (N2). When the dissolved gas is ozone gas, the processing unit 2 includes an ozone generator 44g for generating ozone gas to be supplied to the dissolved gas pipe 44p. The ozone generator 44g is an example of a dissolved gas supply unit and a dissolved gas supply source.

[0051] Dissolved gas valve 44V is installed on dissolved gas piping 44p. Inert gas valve 45V is installed on inert gas piping 45p. Opening dissolved gas valve 44V means it is switched to the open state. Closing dissolved gas valve 44V means it is switched to the closed state. The same applies to inert gas valve 45V.

[0052] The dissolved gas valve 44V being open indicates that dissolved gas in dissolved gas pipe 44p is supplied to separator 51. The dissolved gas valve 44V being closed indicates that dissolved gas in dissolved gas pipe 44p is not supplied to separator 51. Similarly, the inert gas valve being open indicates that inert gas in inert gas pipe 45p is supplied to separator 51. The inert gas valve being closed indicates that inert gas in inert gas pipe 45p is not supplied to separator 51.

[0053] As described below, ozone gas is supplied to sulfuric acid via separator 51. This is an example of a sulfuric acid-based processing solution. The first solution nozzle 21 (see Figure 3) is an example of a processing solution nozzle that sprays the processing solution toward the substrate W. When ozone gas dissolves in sulfuric acid, it forms ozone-containing sulfuric acid, i.e., SOM (Sulfuric acid and Ozone Mixture). Unless otherwise specified, SOM refers to a liquid. The sulfuric acid used in the production of SOM is concentrated sulfuric acid (an aqueous solution of sulfuric acid with a concentration of 90% or higher). If it does not affect the etching of the object being etched, an aqueous solution of sulfuric acid with a lower concentration than concentrated sulfuric acid can also be used to produce SOM.

[0054] The combination of the treatment liquid and dissolved gas can also be any combination other than sulfuric acid and ozone gas. For example, the combination of the treatment liquid and dissolved gas can be any one of water and ammonia, water and fluorine, or hydrogen peroxide water and ammonia, or any other combination. When ammonia dissolves in water, ammonia water is formed. When fluorine dissolves in water, hydrofluoric acid is formed. When ammonia dissolves in hydrogen peroxide water, a mixture of ammonia, hydrogen peroxide, and water, i.e., SC1, is formed.

[0055] The separator 51 is a tangible object comprising a plurality of passages opening on its surface. The separator 51 can be a tangible object that can be considered a rigid body, or it can be a flexible tangible object. The separator 51 can be a tangible object (such as a porous material or sponge) with a plurality of irregularly shaped passages opening at both ends on its surface, or it can be a tangible object (such as a honeycomb structure or a perforated plate) with a plurality of passages penetrating the separator 51 in the same direction. As long as both ends of the passages open on the surface of the separator 51, the passages can be long passages where the length of the passage's centerline is longer than the passage's width or diameter (length in the direction orthogonal to the passage's centerline), or short passages where the length of the passage's centerline is less than the passage's width or diameter. The cross-section of the passage orthogonal to the passage's centerline can be any of a polygon, a circle, or an ellipse, or any other shape. When the cross-section of the passage is circular, the diameter of the passage may be less than 1 mm.

[0056] Figure 4 shows an example where the separator 51 is disposed inside and fixed to the blocking member 41. The separator 51 moves together with the blocking member 41. In this example, the separator 51 is a horizontal circular plate with an outer diameter equal to the inner diameter of the cylindrical portion 41t. The separator 51 divides the space inside the blocking member 41, i.e., the space inside the cylindrical portion 41t, into an upper space SP1 on the upper side of the separator 51 and a lower space SP2 on the lower side of the separator 51. The upper space SP1 is the space between the circular plate portion 41p and the separator 51.

[0057] In the example shown in Figure 4, a plurality of gas supply ports 42 for ejecting gas are provided on the lower surface of the circular plate portion 41p of the blocking member 41, and a plurality of exhaust ports 43 for drawing gas are provided on the inner circumferential surface of the cylindrical portion 41t of the blocking member 41. The plurality of gas supply ports 42 are arranged at a plurality of positions on the circular plate portion 41p at different distances from the center. The plurality of exhaust ports 43 are arranged at a plurality of positions on the blocking member 41 that are separated in the circumferential direction. The plurality of exhaust ports 43 are arranged lower than the separator 51. The plurality of exhaust ports 43 can be arranged at the same height as the base plate W supported by the plurality of chuck pins 11 or heating plates 14, or they can be arranged higher or lower than the base plate W.

[0058] The dissolved gas piping 44p and inert gas piping 45p are connected to a plurality of gas supply ports 42. When the dissolved gas valve 44v is opened, ozone gas is ejected from the plurality of gas supply ports 42. Similarly, when the inert gas valve 45v is opened, nitrogen gas is ejected from the plurality of gas supply ports 42. A plurality of exhaust ports 43 are connected to an exhaust pipe 46p that transmits suction force. When the exhaust valve 46v installed on the exhaust pipe 46p is opened, gas is discharged from the space inside the blocking member 41 to the plurality of exhaust ports 43.

[0059] When dissolved gases such as ozone are ejected from the plurality of gas supply ports 42, the dissolved gases diffuse within the space SP1 above the blocking member 41 and flow from the upper space SP1 to the lower space SP2 via the separator 51. The same applies when nitrogen is ejected from the plurality of gas supply ports 42. The space SP1 above the blocking member 41 is an example of a gas region filled with gas.

[0060] With the blocking member 41 positioned in the lower position and the space inside the blocking member 41 sealed, the gas pressure in the upper space SP1 and the lower space SP2 increases when dissolved gas is ejected from the plurality of gas supply ports 42. The same occurs when nitrogen is ejected from the plurality of gas supply ports 42. The plurality of exhaust ports 43 draw gas from the lower space SP2. As a result, the gas pressure in the upper space SP1 and the lower space SP2 decreases.

[0061] Next, the separator 51 configured inside the tank 52 will be described.

[0062] Figure 5 is a schematic diagram of a first example of a separator 51 disposed in tank 52. Figure 6 is a schematic diagram of a second example of a separator 51 disposed in tank 52. Figure 7 is a schematic diagram of the state in which sulfuric acid in tank 52 is supplied to substrate W.

[0063] As shown in Figures 5 and 6, the substrate processing apparatus 1 includes: a tank 52 storing sulfuric acid, which is an example of a first liquid to be supplied to a first liquid nozzle 21; and a separator 51 disposed within the tank 52. The separator 51 shown in Figures 5 and 6 is identical in construction and material to the separators 51 shown in Figures 2 to 4, except for size and shape. Figure 5 shows an example of the separator 51 dividing the interior of the tank 52 into two regions: a gas region filled with gas and a liquid region filled with sulfuric acid. Figure 6 shows an example of the separator 51 disposed entirely within the sulfuric acid in the tank 52.

[0064] In the example shown in Figure 5, the upper region of separator 51 corresponds to the gas region, and the lower region of separator 51 corresponds to the liquid region. Separator 51 is positioned at the boundary between the gas and liquid regions. The upper surface of separator 51 is in contact with the gas inside tank 52, and the lower surface of separator 51 is in contact with the sulfuric acid inside tank 52. Separator 51 floats on the surface of the sulfuric acid inside tank 52. As the surface of the sulfuric acid moves up and down inside tank 52, separator 51 also moves up and down accordingly. This maintains the contact between separator 51 and the surface of the sulfuric acid inside tank 52. Separator 51 can also be fixed to tank 52. In this case, the contact between separator 51 and the surface of the sulfuric acid inside tank 52 can also be maintained by adding sulfuric acid to tank 52.

[0065] In the example shown in Figure 6, the area above the surface of the sulfuric acid is the gas region, and the area below the surface of the sulfuric acid is the liquid region. The separator 51 is positioned below the surface of the sulfuric acid within the tank 52. Therefore, the entire surface area of ​​the separator 51 is in contact with the sulfuric acid. The separator 51 is supported by a dissolved gas pipe 54p. Even if the surface of the sulfuric acid moves up and down within the tank 52, at least a portion of the surface of the separator 51 remains in contact with the sulfuric acid. The downstream end of the dissolved gas pipe 54p is located inside the separator 51. Ozone gas exits through an opening at the downstream end of the dissolved gas pipe 54p to the outside of the dissolved gas pipe 54p. Thus, ozone gas is released from the surface of the separator 51 into the sulfuric acid through the interior of the separator 51.

[0066] As shown in Figures 5 and 6, the substrate processing apparatus 1 includes: a dissolved gas pipe 54p, which supplies ozone gas, one example of a dissolved gas, into a tank 52; and an inert gas pipe 55p, which supplies nitrogen gas, one example of an inert gas, into a tank 52. When the dissolved gas valve 54v is opened, ozone gas generated by the ozone generator 54g is supplied into the tank 52 via the dissolved gas pipe 54p. When the inert gas valve 55v is opened, nitrogen gas is supplied into the tank 52 via the inert gas pipe 55p. The dissolved gas valve 54v switches between an open state and a closed state. The same applies to the inert gas valve 55v. In the example shown in either Figure 5 or Figure 6, the downstream end of the inert gas pipe 55p is positioned above the surface of the sulfuric acid in the tank 52.

[0067] The substrate processing apparatus 1 includes a pressure control valve 53. When the air pressure inside the tank 52 reaches a set value higher than atmospheric pressure, the pressure control valve 53 reduces the air pressure inside the tank 52, thereby maintaining the air pressure inside the tank 52 at a value below the set value. Although not shown, the pressure control valve 53 includes: an annular valve seat through which gas discharged from the tank 52 passes; a valve body movable relative to the valve seat; and an electric actuator that changes the cross-sectional area of ​​the flow path between the valve seat and the valve body by moving the valve body relative to the valve seat. The pressure control valve 53 further includes: a pressure sensor that detects air pressure upstream of the valve seat; and a valve controller that maintains the detected value of the pressure sensor at a value below the set value by moving the valve body with the electric actuator based on the detected value of the pressure sensor. The valve controller maintains the air pressure inside the tank 52 at a value below the set value specified by the control device 3.

[0068] In the example shown in Figure 5, when the dissolved gas valve 54v is opened, ozone gas is supplied to the gas region of tank 52, causing the gas pressure inside tank 52 to rise to a value below the set threshold. The ozone gas in the gas region is then supplied to the sulfuric acid inside tank 52 via separator 51. Thereby, the ozone gas comes into contact with the sulfuric acid in tank 52 and dissolves in it. Furthermore, the ozone gas forms numerous bubbles in the sulfuric acid within tank 52. This further dissolves the ozone gas in the sulfuric acid within tank 52.

[0069] In the example shown in Figure 6, when the dissolved gas valve 54v is opened, ozone gas is released from the surface of separator 51 into the sulfuric acid without passing through the gas zone. Here, the ozone gas comes into contact with the sulfuric acid in tank 52 and dissolves in it. Subsequently, the ozone gas forms a large number of bubbles in the sulfuric acid in tank 52. Here, the ozone gas further dissolves in the sulfuric acid in tank 52. The ozone gas bubbles are released from the surface of the sulfuric acid in tank 52 into the gas zone. Here, the gas pressure in tank 52 rises to a value that has not yet reached the set value.

[0070] The tank 52 is sealed. The upstream end of the first liquid pipe 21p is positioned below the surface of the sulfuric acid in the tank 52. The sulfuric acid in the tank 52 is supplied to the first liquid nozzle 21 via the first liquid pipe 21p. The control device 3 can also supply the sulfuric acid in the tank 52 to the first liquid nozzle 21 by increasing the gas pressure inside the tank 52. In this case, the control device 3 can increase the gas pressure inside the tank 52 by supplying ozone gas or nitrogen gas, or by supplying both ozone gas and nitrogen gas to the tank 52.

[0071] Figure 7 illustrates an example of supplying sulfuric acid from tank 52 to the first liquid nozzle 21 by supplying nitrogen gas into tank 52. In this case, control device 3 supplies ozone gas into tank 52 with the first liquid valve 21v closed. Here, the ozone gas dissolves in the sulfuric acid. Subsequently, control device 3 closes the dissolved gas valve 54v and opens the inert gas valve 55v. Here, nitrogen gas is supplied to tank 52 from the inert gas valve 55v.

[0072] When nitrogen is supplied after ozone gas, and the pressure inside tank 52 is maintained at a value higher than atmospheric pressure but lower than a set value, the ozone gas in the gas area of ​​tank 52 is replaced by nitrogen gas. Control device 3 opens the first liquid valve 21v when the pressure inside tank 52 is high. Thereby, sulfuric acid inside tank 52 is transported to the first liquid pipe 21p by the pressure of nitrogen gas and sprayed out from the first liquid nozzle 21. Therefore, the amount of ozone gas sprayed from the first liquid nozzle 21 can be reduced, while sulfuric acid dissolved in ozone gas is supplied from the first liquid nozzle 21 to the substrate W.

[0073] Next, the phenomena expected to occur when dissolved gas is supplied to separator 51 while it is in contact with the processing liquid will be explained.

[0074] Figure 8 is a schematic diagram used to illustrate this phenomenon. Figure 8 shows an example where the upper surface of the pattern formed on the upper surface of the substrate W is covered by a resist film RF, which is one example of the object to be etched. In this example, the separator 51 is a porous material. In the example shown in Figure 8, the upper surface of the separator 51 is a non-contact portion 51n that does not contact the processing liquid, and the lower surface of the separator 51 is a contact portion 51c that contacts the processing liquid. The upper and lower surfaces of the separator 51 are part of the surface of the separator 51. The contact portion 51c is away from the upper surface of the substrate W.

[0075] The separator 51 has multiple passages 51h that open at the contact portion 51c and the non-contact portion 51n. Therefore, when dissolved gas is supplied to the separator 51, the dissolved gas passes through the interior of the separator 51 and exits from the surface of the separator 51 to the exterior. The dissolved gas is separated into multiple separate dissolved gas clusters by entering the multiple passages 51h. A cluster of dissolved gas may be spherical, linear, or other shapes.

[0076] The pressure of the dissolved gas applied to separator 51 directs multiple dissolved gas clusters from multiple passages 51h to the processing liquid in contact with the surface of separator 51. When dissolved gas is supplied to separator 51 while its surface is in contact with the processing liquid, multiple dissolved gas clusters are released from multiple passages 51h into the processing liquid. This generates a large number of dissolved gas bubbles in the processing liquid.

[0077] A plurality of dissolved gas clusters contact the processing liquid on the surface of separator 51. When the processing liquid enters the plurality of passages 51h from the surface of separator 51, the plurality of dissolved gas clusters contact the processing liquid inside separator 51. Gas bubbles of dissolved gas generated in the processing liquid also contact the processing liquid. At least one of these contacts dissolves the dissolved gas in the processing liquid. When the dissolved gas contains substances that react with the processing liquid, the dissolved gas reacts with the processing liquid.

[0078] If the volume of dissolved gas is the same, the surface area of ​​the dissolved gas increases during separation compared to the case where the dissolved gas is not separated. When no dissolved gas is supplied to separator 51, that is, when the gas pressure in the plurality of passages 51h does not rise, as enlarged within the frame of the two-point chain in Figure 8, a hemispherical surface of the processing liquid forms at the ends or inside of the plurality of passages 51h due to the surface tension of the processing liquid. This increases the contact area between the processing liquid and the dissolved gas. The increased contact area between the processing liquid and the dissolved gas promotes the dissolution of the dissolved gas into the processing liquid. When the dissolved gas contains substances that react with the processing liquid, this increase further promotes the reaction between the dissolved gas and the processing liquid.

[0079] When the processing liquid and dissolved gas combination is sulfuric acid and ozone gas, ozone gas dissolves in sulfuric acid to form sulfuric acid containing ozone, i.e., SOM. The sulfuric acid in SOM dissociates into hydrogen ions and bisulfate ions. SOM contains not only sulfuric acid but also ozone molecules. The bisulfate ions in SOM react with the ozone molecules to generate water and persulfate ions. When SOM is heated, heat energy is applied to the persulfate ions in SOM. As a result, the persulfate ions become sulfate ion free radicals, which are also called sulfate free radicals. When sulfuric acid is heated while ozone gas is brought into contact with sulfuric acid through separator 51, the concentration of active species such as sulfate ion free radicals in SOM increases. This allows for the efficient removal of etched objects such as resist films (RF) by SOM.

[0080] Next, an example of the processing of substrate W will be described.

[0081] Figure 9 is a flowchart illustrating an example of substrate W processing performed by substrate processing apparatus 1. Figures 10A to 10N are schematic diagrams for illustrating this example. Hereinafter, the etching process for removing the resist film RF from the upper surface of the substrate W shown in Figure 8 will be described. The resist film RF is an example of the object to be etched. Hereinafter, refer to Figures 9 and 3. Refer appropriately to Figures 10A to 10N.

[0082] When the substrate W is processed by the substrate processing apparatus 1, a transfer process is performed to move the substrate W into the chamber 4 (step S1 in Figure 9).

[0083] Specifically, with all shields 34 in the lower position, all scanning nozzles in the standby position, the blocking member 41 in the upper position, the heating plate 14 in the lower position, and the plurality of chuck pins 11 open, the central robot CR (see Figure 1A) supports the substrate W with its hand Hc while simultaneously entering the chamber 4. With the plurality of chuck pins 11 open, the central robot CR places the substrate W from the hand Hc onto the plurality of chuck pins 11 with the substrate W facing upwards. Subsequently, the central robot CR retracts the hand Hc from inside the chamber 4. After the substrate W is placed onto the plurality of chuck pins 11, the lifting actuator 14a moves the heating plate 14 from the lower position to the upper position. Thus, as shown in Figure 10A, the substrate W is lifted by the heating plate 14 and moves upwards away from the plurality of chuck pins 11.

[0084] After the substrate W is supported by the heating plate 14, a first liquid supply process is performed, in which SOM, as an example of the first liquid, is supplied to the upper surface of the substrate W.

[0085] The first liquid supply process includes: a first liquid film formation process (step S2 in Figure 9), which forms a liquid film of sulfuric acid on the upper surface of the substrate W; and a first gas supply process (step S3 in Figure 9), which heats the sulfuric acid on the substrate W on one side and supplies ozone gas to the separator 51 that is in contact with the sulfuric acid on the substrate W on the other side.

[0086] During the first liquid film formation process, with the blocking member 41 in the upper position, the first nozzle actuator 21a moves the first liquid nozzle 21 from the standby position to the processing position. Then, the first liquid valve 21v is opened. As shown in FIG10B, the first liquid nozzle 21 begins to spray sulfuric acid. Before the sulfuric acid spraying begins, the lifting actuator 34a raises at least one protective cover 34 from the lower position to the upper position.

[0087] Sulfuric acid ejected from the first liquid nozzle 21 collides with the upper surface of the substrate W supported by the heating plate 14 and then spreads along the upper surface of the substrate W. Thus, the entire area of ​​the upper surface of the substrate W supported by the heating plate 14 is covered with a liquid film of sulfuric acid. Subsequently, the first liquid valve 21v is closed, causing the first liquid nozzle 21 to stop ejecting sulfuric acid. While the first liquid nozzle 21 is not ejecting sulfuric acid, the first nozzle actuator 21a moves the first liquid nozzle 21 from the processing position to the standby position.

[0088] During the first gas supply process, with the entire upper surface of the substrate W covered by a liquid film of sulfuric acid, the lifting actuator 41a moves the blocking member 41 from the upper position to the lower position. This closes the gap between the cylindrical portion 41t of the blocking member 41 and the rotating base 12 of the rotating chuck 10, thereby sealing the space inside the blocking member 41 (the space inside the cylindrical portion 41t). When the blocking member 41 is positioned in the lower position, the distance from the lower surface of the separator 51 to the upper surface of the substrate W decreases from a value greater than the thickness of the sulfuric acid liquid film to a value less than that thickness. This brings the lower surface of the separator 51, fixed to the blocking member 41, into contact with the liquid film of sulfuric acid on the substrate W.

[0089] A heating plate 14 supports the substrate W on one side and heats the substrate W on the other. This heats the sulfuric acid in contact with the substrate W. When the heating plate 14 heats the substrate W, the temperature of the sulfuric acid on the substrate W rises to a value higher than room temperature (e.g., 20-30°C) but lower than the boiling point of sulfuric acid. The temperature of the sulfuric acid when the heating plate 14 heats the substrate W can be 100°C or 200°C or higher, or it can be lower than 100°C or 200°C. The heating plate 14 can begin heating simultaneously with the supply of sulfuric acid to the substrate W, or it can begin heating before or after the supply of sulfuric acid to the substrate W.

[0090] As shown in Figure 10C, with the space inside the blocking member 41 sealed, the lower surface of the separator 51 in contact with the liquid film of sulfuric acid on the substrate W, and the heating plate 14 heating the substrate W, the dissolved gas valve 44V is opened. This causes ozone gas to be ejected from the plurality of gas supply ports 42 of the blocking member 41. The ozone gas ejected from the plurality of gas supply ports 42 fills the space SP1 above the blocking member 41 and moves from the space SP1 above the blocking member 41 to the space SP2 below the blocking member 41 via the separator 51. This causes the ozone gas to dissolve into the liquid film of sulfuric acid on the substrate W, transforming the liquid film of sulfuric acid on the substrate W into a liquid film of SOM. The SOM reacts with the resist film RF (see Figure 8) formed on the upper surface of the substrate W. This removes the resist film RF from the substrate W.

[0091] After supplying SOM to the entire area of ​​the upper surface of the substrate W, a purging process is performed to fill the space inside the shielding member 41 with inert gas (step S4 in Figure 9).

[0092] Specifically, after a predetermined time has elapsed since ozone gas began to be emitted from the plurality of gas supply ports 42 of the blocking member 41, the dissolved gas valve 44v is closed, stopping the emission of ozone gas from the plurality of gas supply ports 42 of the blocking member 41. Then, as shown in FIG10D, the inert gas valve 45v is opened with the blocking member 41 in the lower position. With the exhaust valve 46v closed, the exhaust valve 46v is opened simultaneously with or after the opening of the inert gas valve 45v. In this way, the ozone gas remaining in the space inside the blocking member 41 is replaced by inert gas.

[0093] After the space inside the blocking member 41 is filled with inert gas, a first rinsing fluid supply process is performed, in which pure water, as one example of rinsing fluid, is supplied to the upper surface of the substrate W (step S5 in Figure 9).

[0094] Specifically, the lifting actuator 41a moves the blocking member 41 from the lower position to the upper position. This causes the lower surface of the separator 51 to move upward away from the SOM on the substrate W. Then, with the substrate W supported by the heating plate 14 and the blocking member 41 in the upper position, the third nozzle actuator 23a moves the rinsing fluid nozzle 23 from the standby position to the processing position. Then, the rinsing fluid valve 23v is opened. Thus, as shown in FIG10E, the rinsing fluid nozzle 23 begins to spray pure water. The lifting actuator 34a can also move at least one shield 34 vertically before the pure water spray begins, thereby switching the shield 34 used to catch the liquid discharged from the substrate W. This is also true for the second drug supply process, the second rinsing fluid supply process, and the third rinsing fluid supply process described below.

[0095] The pure water ejected from the rinsing nozzle 23 collides with the upper surface of the substrate W supported by the heating plate 14 and then diffuses along the upper surface of the substrate W. In this way, the SOM on the substrate W is replaced by pure water, thereby covering the entire area of ​​the upper surface of the substrate W supported by the heating plate 14 with a film of pure water. Afterwards, the rinsing valve 23v is closed, causing the rinsing nozzle 23 to stop ejecting pure water. The third nozzle actuator 23a moves the rinsing nozzle 23 from the processing position to the standby position while the rinsing nozzle 23 is not ejecting pure water.

[0096] The heating plate 14 stops heating before the SOM on the substrate W is replaced by pure water. The heating plate 14 can stop heating simultaneously with the cessation of ozone gas emission from the plurality of gas supply ports 42 of the blocking member 41, or it can stop heating before or after the cessation of ozone gas emission from the plurality of gas supply ports 42 of the blocking member 41. The heating plate 14 can also stop heating after the SOM on the substrate W is replaced by pure water. As described below, the substrate W is transferred from the heating plate 14 to the plurality of chuck pins 11. The heating plate 14 can stop heating simultaneously with the transfer of the substrate W to the plurality of chuck pins 11, or it can stop heating before or after the transfer of the substrate W to the plurality of chuck pins 11.

[0097] After replacing the SOM on the substrate W with pure water, a second solution supply process is performed, in which SC1, as one example of the second solution, is supplied to the upper surface of the substrate W (step S6 in Figure 9).

[0098] Specifically, with the substrate W supported by the heating plate 14 and the blocking member 41 in the upper position, the second nozzle actuator 22a moves the second liquid nozzle 22 from the standby position to the processing position. Then, the second liquid valve 22v is opened. As shown in FIG10F, the second liquid nozzle 22 begins to spray SC1. The SC1 sprayed from the second liquid nozzle 22 collides with the upper surface of the substrate W supported by the heating plate 14 and spreads along the upper surface of the substrate W. This displaces the pure water on the substrate W with SC1, thereby covering the entire area of ​​the upper surface of the substrate W supported by the heating plate 14 with a liquid film of SC1. Then, the second liquid valve 22v is closed, stopping the second liquid nozzle 22 from spraying SC1. The second nozzle actuator 22a moves the second liquid nozzle 22 from the processing position to the standby position while the second liquid nozzle 22 is not spraying SC1.

[0099] After replacing the pure water on the substrate W with SC1, a first separator cleaning process (step S7 in Figure 9) is performed to clean the separator 51 using SC1 as a cleaning liquid and nitrogen as a cleaning gas.

[0100] Specifically, with the entire surface of the substrate W covered by the liquid film of SC1, the lifting actuator 41a moves the blocking member 41 from the upper position to the lower position. As shown in FIG10G, this seals the space inside the blocking member 41, and the lower surface of the separator 51 comes into contact with the liquid film of SC1 on the substrate W. When the lower surface of the separator 51 contacts the liquid film of SC1 on the substrate W, particles or SOM residues adhering to the lower surface of the separator 51 are removed by SC1.

[0101] After the shut-off member 41 moves to the lower position, the inert gas valve 45v is opened, causing nitrogen gas to be ejected from the plurality of gas supply ports 42 of the shut-off member 41. This fills the upper space SP1 of the shut-off member 41 with nitrogen gas, and the nitrogen gas flows from the upper space SP1 to the lower space SP2 via the separator 51. If any residue remains inside the separator 51, the nitrogen gas flowing from the lower surface of the separator 51 discharges the residue to the outside of the separator 51. This removes the residue from the separator 51.

[0102] After nitrogen gas is ejected from the plurality of gas supply ports 42 of the blocking member 41, the first separator drying process (step S8 in Figure 9) is carried out to remove liquid from the separator 51.

[0103] Specifically, with the entire surface of the substrate W covered by a liquid film of SC1, the blocking member 41 is in the lower position, and nitrogen gas is being ejected from the plurality of gas supply ports 42 of the blocking member 41. The lifting actuator 41a then moves the blocking member 41 from the lower position to the upper position. As shown in FIG10H, the lower surface of the separator 51 moves upward away from the liquid film of SC1 on the substrate W. The nitrogen gas flowing out from the lower surface of the separator 51 causes the SC1 adhering to the lower surface of the separator 51 to fall onto the SC1 on the substrate W. If SC1 remains inside the separator 51, the nitrogen gas discharges the SC1 to the outside of the separator 51, causing it to fall onto the SC1. This removes the liquid, including SC1, from the separator 51. After the liquid is removed from the separator 51, the separator 51 can be in a dry state, or it can be in a wet state as long as the liquid does not fall from the separator 51.

[0104] SC1 is one example of a cleaning fluid used to clean the substrate W and the separator 51. The cleaning fluid can be any liquid other than SC1, or a rinsing solution such as pure water. Nitrogen is one example of a cleaning gas used to clean the separator 51. The cleaning gas can be any inert gas other than nitrogen, or a gas other than an inert gas such as clean air.

[0105] Next, a second rinsing fluid supply process is performed, in which pure water, as one example of rinsing fluid, is supplied to the upper surface of the substrate W (step S9 in Figure 9).

[0106] Specifically, with the substrate W supported by the heating plate 14 and the blocking member 41 in the upper position, the third nozzle actuator 23a moves the rinsing fluid nozzle 23 from the standby position to the processing position. Then, the rinsing fluid valve 23v is opened. As shown in FIG10I, the rinsing fluid nozzle 23 begins to spray rinsing fluid. The rinsing fluid sprayed from the rinsing fluid nozzle 23 collides with the upper surface of the substrate W supported by the heating plate 14 and spreads along the upper surface of the substrate W. This displaces SC1 on the substrate W with pure water, thereby covering the entire area of ​​the upper surface of the substrate W supported by the heating plate 14 with a film of pure water. Then, the rinsing fluid valve 23v is closed, stopping the rinsing fluid nozzle 23 from spraying pure water. With the rinsing fluid nozzle 23 no longer spraying pure water, the third nozzle actuator 23a moves the rinsing fluid nozzle 23 from the processing position to the standby position.

[0107] Next, a second separator cleaning process is carried out, in which pure water, another example of a cleaning liquid, and nitrogen, another example of a cleaning gas, are used to clean the separator 51 (step S10 in Figure 9).

[0108] Specifically, with the entire surface of the substrate W covered by a film of pure water, the lifting actuator 41a moves the blocking member 41 from the upper position to the lower position. As shown in FIG10J, the space inside the blocking member 41 is sealed, and the lower surface of the separator 51 comes into contact with the film of pure water on the substrate W.

[0109] After the blocking member 41 moves to the lower position, the inert gas valve 45v is opened, causing nitrogen to be ejected from the plurality of gas supply ports 42 of the blocking member 41. As a result, the space SP1 above the blocking member 41 is filled with nitrogen, and the nitrogen flows from the upper space SP1 to the lower space SP2 through the separator 51.

[0110] After nitrogen gas is ejected from the plurality of gas supply ports 42 of the blocking member 41, a second separator drying process (step S11 in Figure 9) is carried out to remove liquid from the separator 51.

[0111] Specifically, with the entire surface of the substrate W covered by a film of pure water, the blocking member 41 is in the lower position, and nitrogen gas is being ejected from the plurality of gas supply ports 42 of the blocking member 41. The lifting actuator 41a then moves the blocking member 41 from the lower position to the upper position. As shown in FIG10K, the lower surface of the separator 51 moves upward away from the film of pure water on the substrate W. The nitrogen gas flowing out from the lower surface of the separator 51 causes the pure water adhering to the lower surface of the separator 51 to fall onto the pure water on the substrate W. If pure water remains inside the separator 51, the nitrogen gas discharges the pure water to the outside of the separator 51, causing it to fall onto the pure water. This removes liquids such as pure water from the separator 51. After removing liquid from the separator 51, the separator 51 can be in a dry state, or it can be in a wet state as long as no liquid falls from the separator 51.

[0112] After the blocking member 41 is moved to the upper position, a substrate transfer process is performed to move the substrate W from the heating plate 14 to a plurality of chuck pins 11 (step S12 in Figure 9).

[0113] Specifically, with the blocking member 41 in the upper position and the plurality of chuck pins 11 open, the lifting actuator 14a moves the heating plate 14 from the upper position to the lower position. Thereby, as shown in FIG10L, the substrate W is placed on the plurality of chuck pins 11, and the heating plate 14 moves downward away from the substrate W. Then, the plurality of chuck pins 11 are closed, and the rotary motor 13 is rotated. Thereby, the substrate W held by the plurality of chuck pins 11 begins to rotate.

[0114] After placing the substrate W on a plurality of chuck pins 11, a third rinsing solution supply process is performed, in which pure water, as one example of rinsing solution, is supplied to the upper surface of the substrate W (step S13 in Figure 9).

[0115] Specifically, with the blocking member 41 in the upper position, the third nozzle actuator 23a moves the rinsing fluid nozzle 23 from the standby position to the processing position and opens the rinsing fluid valve 23v. As shown in FIG10M, the pure water on the substrate W is replaced with fresh pure water, and the entire area of ​​the upper surface of the substrate W, held by the plurality of clamp pins 11, is covered by a film of pure water. Subsequently, the rinsing fluid valve 23v is closed, and the third nozzle actuator 23a moves the rinsing fluid nozzle 23 from the processing position to the standby position.

[0116] After replacing the pure water on the substrate W with new pure water, a drying process is carried out by rotating the substrate W at high speed to dry the substrate W (step S14 in Figure 9).

[0117] Specifically, with the rinsing fluid stopped being ejected from the rinsing fluid nozzle 23, the rotary motor 13 accelerates the substrate W in the rotational direction. This causes the substrate W to rotate at a drying speed greater than the rotational speed of the substrate W when the rinsing fluid is supplied to it (i.e., the rinsing fluid supply speed). As shown in FIG10N, by rotating the substrate W at the drying speed, liquid is removed from the substrate W, thereby drying the substrate W. Afterwards, the rotary motor 13 stops rotating. This stops the rotation of the substrate W while it is held by the plurality of chuck pins 11.

[0118] After the rotation of the substrate W stops, the substrate W is removed from the chamber 4 in a removal process (step S15 in Figure 9).

[0119] Specifically, the plurality of chuck pins 11 switch from a closed state to an open state. This releases the chuck pins 11 from holding the substrate W while it is supported by the chuck pins 11. Simultaneously or before / after releasing the substrate W, the lifting actuator 34a lowers all the protective covers 34 to the lower position. Then, the central robot CR (see Figure 1A) inserts its hand Hc into the chamber 4. The central robot CR receives the substrate W from the plurality of chuck pins 11 and supports it using the hand Hc. Subsequently, while supporting the substrate W with the hand Hc, the central robot CR moves the hand Hc to the outside of the chamber 4. This removes the processed substrate W from the chamber 4.

[0120] Next, the effects of this implementation method will be explained.

[0121] In this embodiment, the surface of the separator 51 is brought into contact with at least one of the processing liquid on the contact substrate W and the processing liquid in front of the contact substrate W. In this state, dissolved gas flows into a plurality of passages of the separator 51. The dissolved gas is separated into a plurality of separate dissolved gas clusters by entering the plurality of passages of the separator 51. Since the plurality of passages are open on the surface of the separator 51, the plurality of dissolved gas clusters leave the surface of the separator 51 to the outside of the separator 51. Thereby, the plurality of dissolved gas clusters come into contact with the processing liquid and dissolve. Because the dissolved gas is separated, the contact area between the processing liquid and the dissolved gas is increased compared to the case where the dissolved gas does not separate but comes into contact with the processing liquid. Therefore, the dissolved gas can be efficiently dissolved in the processing liquid, and the processing liquid containing the dissolved gas can be supplied to the substrate W.

[0122] In this embodiment, dissolved gas is supplied to the non-contact portion 51n of the separator 51 when the contact portion 51c (see FIG. 8) of the separator 51's surface is in contact with the processing liquid and the non-contact portion 51n (see FIG. 8) of the separator 51's surface is away from the processing liquid. The dissolved gas enters the interior of the separator 51 from the non-contact portion 51n and exits into the processing liquid from the contact portion 51c. Compared to the case where the entire surface area of ​​the separator 51 is in contact with the processing liquid, the area on which dissolved gas can be supplied to the separator 51 is larger. This allows for the supply of dissolved gas to the separator 51 at a high flow rate.

[0123] In this embodiment, the gas region, which is the area opposite to the treatment liquid in the separator 51, is filled with dissolved gas. The non-contact portion 51n of the separator 51 is part of the boundary of the gas region. Therefore, compared with the case where the gas region is not filled with dissolved gas, the contact area between the dissolved gas and the non-contact portion 51n can be increased, thereby increasing the flow rate of dissolved gas entering the interior of the separator 51 from the non-contact portion 51n.

[0124] In this embodiment, after the processing liquid is supplied to the substrate W, a cleaning liquid such as SC1 is supplied to the substrate W. Then, the contact portion 51c of the separator 51 comes into contact with the cleaning liquid on the substrate W. When the processing liquid adheres to the contact portion 51c of the separator 51, the processing liquid moves into the cleaning liquid. This removes the processing liquid from the contact portion 51c of the separator 51. Since the substrate W and the separator 51 are cleaned using the same cleaning liquid, the amount of cleaning liquid used can be reduced. Furthermore, since the substrate W and the separator 51 are cleaned simultaneously, the time required for cleaning the substrate W and the separator 51 can be shortened.

[0125] In this embodiment, while the contact portion 51c of the separator 51 is brought into contact with the cleaning liquid on the contact substrate W, a cleaning gas such as nitrogen is introduced into the plurality of passages of the separator 51 from the non-contact portion 51n of the separator 51. Thereby, the separated cleaning gas is released from the contact portion 51c into the cleaning liquid. If there are residues such as processing liquid or particles in the plurality of passages of the separator 51, the cleaning gas removes these residues from the separator 51. This allows for cleaning not only the contact portion 51c of the separator 51 but also the interior of the separator 51.

[0126] In this embodiment, after cleaning the separator 51, with the contact portion 51c of the separator 51 removed from the cleaning liquid that was in contact with the substrate W, cleaning gas flows from the non-contact portion 51n of the separator 51 into a plurality of passages of the separator 51. When a liquid such as a processing liquid adheres to the contact portion 51c of the separator 51, the cleaning gas flowing out of the contact portion 51c removes the liquid from the contact portion 51c. When liquid remains inside the separator 51, the cleaning gas flowing out of the contact portion 51c discharges the liquid to the outside of the separator 51. This reduces the amount of liquid adhering to the separator 51.

[0127] In this embodiment, the surface of the separator 51 is brought into contact with the processing liquid inside the tank 52. In this state, dissolved gas flows into a plurality of passages of the separator 51. The dissolved gas entering the plurality of passages of the separator 51 exits from the surface of the separator 51 to the outside of the separator 51 and dissolves in the processing liquid inside the tank 52. This processing liquid is then supplied to the substrate W. Because the dissolved gas is dissolved in the processing liquid inside the tank 52, the diffusion range of the dissolved gas can be limited within the tank 52, thereby reducing the amount of dissolved gas used. If the gas pressure inside the tank 52 is increased by supplying dissolved gas, the dissolved gas can be dissolved in the processing liquid more efficiently.

[0128] In this embodiment, after the dissolved gas dissolves in the processing liquid within tank 52, an inert gas is supplied to tank 52. This raises the pressure within tank 52 to a level at which the processing liquid is discharged from tank 52 to the substrate W. Therefore, compared to pressurizing the processing liquid within tank 52 by supplying dissolved gas, the amount of dissolved gas used can be reduced, thereby reducing the amount of dissolved gas exiting tank 52. When the dissolved gas is a reactive gas such as ozone, it is possible to suppress or prevent the dissolved gas exiting tank 52 from reacting with the components within the chamber 4 housing the substrate W. Furthermore, the processing liquid can be transported from tank 52 to the substrate W without using a pump, thus preventing the pump from being corroded by dissolved gases such as ozone.

[0129] In this embodiment, the surface of a porous body, exemplified by separator 51, is brought into contact with the processing liquid. Dissolved gas is supplied to the porous body in this state. The porous body has a plurality of irregularly shaped passages forming inside, opening onto its surface. When dissolved gas is supplied to the porous body, the separated dissolved gas flows out from the surface of the porous body. The surface of the porous body is uneven. If the shape and size of the contours are the same, the surface area of ​​an uneven surface is larger than that of a flat surface. Therefore, the contact area between the processing liquid and the porous body can be increased, thereby increasing the contact area between the processing liquid and the dissolved gas.

[0130] Next, other implementation methods will be described.

[0131] When the blocking member 41 with cylindrical portion 41t is positioned in the lower position, a plurality of collet pins 11 may also be positioned on the outer side of cylindrical portion 41t.

[0132] Alternatively, the substrate W can be rotated and heated while its upper surface is covered by a liquid film of the processing liquid. Specifically, the substrate W can be rotated while the heating plate 14 is moving downward away from the substrate W, and the heating plate 14 can heat the substrate W.

[0133] Alternatively, the separator 51 can supply dissolved gas to only one of the processing liquids in contact with the substrate W and the processing liquids in front of the substrate W. That is, the separator 51 can also be installed only above the substrate W or inside the tank 52.

[0134] When the separator 51 is only installed in the tank 52, in addition to heating the substrate W and the processing liquid using the heating plate 14, or alternatively, the substrate W and the processing liquid can be heated by irradiating the processing liquid on the substrate W with light from a lamp, which is an example of a heater. The processing liquid in the circulation path that circulates the processing liquid in the tank 52 can also be heated by a circulating heater, which is an example of a heater. If heating the processing liquid is not required, at least one of the heating plate 14, the lamp, and the circulating heater can be omitted.

[0135] As shown in Figure 11, when dissolved gas is supplied to the treatment liquid via separator 51, the gap between the blocking member 41 and the rotating base 12 may not need to be sealed. Specifically, the cylindrical portion 41t of the blocking member 41 may be omitted (see Figure 3). In this case, the exhaust pipe 8 may also draw in dissolved gases such as ozone. Alternatively, regardless of whether the blocking member 41 has the cylindrical portion 41t, the separator 51 may be able to move vertically parallel to the circular plate portion 41p of the blocking member 41.

[0136] Figure 11 shows an example of the lifting actuator 51a causing the separator 51 to move horizontally between an upper position (shown by the solid line) and a lower position (shown by the two-point chain line). The upper position is the position where the separator 51 moves upward away from the processing liquid on the substrate W. The lower position is the position where the separator 51 contacts the processing liquid on the substrate W. When the blocking member 41 is positioned in the upper position, the separator 51 can contact or move away from the circular plate portion 41p. When the separator 51 is positioned in the lower position, a space is formed between the separator 51 and the circular plate portion 41p for the dissolved gas to diffuse, thus enabling the dissolved gas to be uniformly supplied to the separator 51.

[0137] As shown in Figures 12 and 13, chamber 4 can also be a sealed chamber without FFU7 (see Figure 2). Figures 12 and 13 show an example of chamber 4 including an upper wall 4u and a lower wall 4L disposed above and below the substrate W, and a cylindrical peripheral wall 4p surrounding the substrate W along a vertical line. In this example, the peripheral wall 4p is fixed to the lower wall 4L, and the upper wall 4u can move vertically parallel to the peripheral wall 4p and the lower wall 4L. The opening and closing actuator 4a causes the upper wall 4u to move vertically parallel between the lower position (the position shown in Figure 12) where the gap between the upper wall 4u and the peripheral wall 4p is closed, and the substrate W to move vertically parallel to the upper position (the position shown in Figure 13) where the upper wall 4u can move between the upper wall 4u and the peripheral wall 4p.

[0138] Heating plate 14 holds substrate W horizontally within chamber 4 while simultaneously heating it. As shown in FIG13, substrate W is relayed between central robot CR (see FIG1A) and heating plate 14 by a plurality of horizontally supporting pins 15. Lifting actuator 15a causes the plurality of supporting pins 15 to move horizontally and parallel between an upper position (shown in FIG13) where the upper ends of the plurality of supporting pins 15 are above the upper ends of the peripheral wall 4p and a lower position (shown in FIG12) where the upper ends of the plurality of supporting pins 15 are below the heating plate 14.

[0139] The first liquid nozzle 21, the second liquid nozzle 22, and the rinsing liquid nozzle 23 are disposed within the chamber 4. Figures 12 and 13 show an example of the first liquid nozzle 21, the second liquid nozzle 22, and the rinsing liquid nozzle 23 being fixed nozzles that spray the treatment liquid onto the upper surface of the substrate W on the heating plate 14. As shown in Figure 12, the separator 51 can move horizontally relative to the upper wall 4u between the upper position (the position shown by the solid line) where the separator 51 is above the treatment liquid on the substrate W and the lower position (the position shown by the two-point chain line) where the separator 51 is in contact with the treatment liquid on the substrate W.

[0140] The substrate processing apparatus 1 is not limited to an apparatus for processing a circular substrate W, but may also be an apparatus for processing a polygonal substrate W.

[0141] Two or more of the above components can also be combined. Two or more of the above processes can also be combined.

[0142] 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 interpreted as limited to these specific examples, and the spirit and scope of the present invention are defined only by the appended patent claims.

[0143] 1: Substrate processing device 1a:Outer wall 2: Processing Unit 3: Control device 3c: CPU 3m: Memory 4: Chamber 4L: Lower wall 4a: Opening / closing actuator 4p: Zhou Bi 4u: Upper wall 5: Spacer 6: Door 7:FFU 8: Exhaust pipe 9: Exhaust valve 10: Rotary Chuck 11: Chuck pin 12: Rotating base 12u: Upper surface 13: Rotary motor 14: Heating plate 14a: Lifting actuator 14s: Support shaft 15: Top-lifting pin 15a: Lifting Actuator 21: First liquid nozzle 21a: Nozzle Actuator No. 1 21p: First drug solution piping 21v: First liquid valve 22: Second liquid nozzle 22a: Second nozzle actuator 22p: Second drug solution piping 22V: Second liquid valve 23: Flushing fluid nozzle 23a: Third nozzle actuator 23p: Flushing fluid piping 23V: Flushing fluid valve 31: Handling the cup 32:Tubular outer wall 33: Cup 34: Protective shield 34a: Lifting actuator 35: Cylindrical section 36: Top Wall 41: Blocking component 41a: Lifting actuator 41p: Circular plate section 41t: Cylindrical section 42: Gas supply port 43: Exhaust port 44g: Ozone generator 44p: Dissolved gas piping 44V: Dissolved gas valve 45p: Inert gas piping 45V: Inert gas valve 46p: Exhaust pipe 46V: Exhaust valve 51: Separator 51a: Lifting Actuator 51c: Contact part 51h: Pathway 51n: Non-contact part 52: Can 53: Pressure control valve 54g: Ozone generator 54p: Dissolved gas piping 54V: Dissolved gas valve 55p: Inert gas piping 55V: Inert gas valve A1: Axis of rotation CA: Vehicle CR: Central Robot Hc: Hand Hi: Hands IR: Transport Robot LP: Loading Port RF: Anti-corrosion film S1: Steps S2: Steps S3: Steps S4: Steps S5: Steps S6: Steps S7: Steps S8: Steps S9: Steps S10: Steps S11: Steps S12: Steps S13: Steps S14: Steps S15: Steps SP1: Upper Space SP2: Lower Space TP: Transport Path TS: Transport System TW: Tower W: substrate

Claims

1. A substrate processing method, comprising: a processing liquid supply step, wherein processing liquid is supplied to a substrate; and a dissolved gas supply step, wherein, with the surface of a separator comprising a plurality of passages with surface openings in contact with the processing liquid contacting the substrate, dissolved gas separated by entering the plurality of passages of the separator is dissolved in the processing liquid.

2. The substrate processing method of claim 1, wherein the dissolved gas supply step comprises the following step: with the contact portion of the surface of the separator in contact with the processing liquid that contacts the substrate, and with the non-contact portion of the surface of the separator away from the processing liquid, the dissolved gas separated by flowing from the non-contact portion into the plurality of passages is released from the contact portion into the processing liquid.

3. The substrate processing method of claim 2, wherein the dissolved gas supply step includes the following step: filling the gas region, which is opposite to the separator and the processing liquid, with the dissolved gas.

4. The substrate processing method according to any one of claims 1 to 3, further comprising: a cleaning liquid supply step, wherein the cleaning liquid is supplied to the substrate after the processing liquid is supplied to the substrate; and a separator cleaning step, wherein the contact portion of the surface of the separator is brought into contact with the cleaning liquid that is in contact with the substrate.

5. The substrate processing method of claim 4, wherein the separator cleaning process includes the following steps: contacting the contact portion of the surface of the separator with the cleaning liquid that contacts the substrate, and simultaneously releasing the cleaning gas separated by allowing the cleaning gas to flow from the non-contact portion of the surface of the separator into the cleaning liquid from the contact portion.

6. The substrate processing method of claim 5 further includes a separator drying step, which is performed after the separator cleaning step, wherein the separator drying step is performed after the separator cleaning step, wherein the separator is separated from the cleaning liquid that was in contact with the substrate by the contact portion of the contact portion, and the cleaning gas separated by the cleaning gas flowing from the non-contact portion of the separator's surface into the plurality of passages is released from the contact portion.

7. The substrate processing method of any one of claims 1 to 3, wherein the separator is a porous material.

8. The substrate processing method according to any one of claims 1 to 3, wherein in the dissolved gas supply process, the separator faces the entire surface of the substrate.

9. A substrate processing method, comprising: a processing liquid supply step, wherein processing liquid is supplied to a substrate; and a dissolved gas supply step, wherein dissolved gas separated by entering the plurality of passages of a separator having a plurality of passages with surface openings is dissolved in the processing liquid before contacting the substrate; the dissolved gas supply step comprises the step of dissolving the dissolved gas separated by entering the plurality of passages of the separator in the processing liquid while the separator, formed of a porous material, is completely immersed in the processing liquid in a tank; and the processing liquid supply step comprises the step of supplying the processing liquid supplied from the tank to the substrate.

10. The substrate processing method of claim 9, wherein the processing liquid supply step includes the following step: after the dissolved gas is dissolved in the processing liquid in the tank, an inert gas is supplied to the tank, thereby increasing the gas pressure in the tank to a value at which the processing liquid in the tank is discharged from the tank to the substrate.

11. A substrate processing apparatus comprising: a processing liquid nozzle for supplying processing liquid to a substrate; a separator including a plurality of passages with surface openings; a dissolving gas pipe for ejecting dissolving gas into the plurality of passages of the separator; and a dissolving gas supply unit for supplying the dissolving gas to the dissolving gas pipe; wherein the dissolving gas supply unit supplies the dissolving gas to the dissolving gas pipe while the surface of the separator is in contact with the processing liquid contacting the substrate.

12. The substrate processing apparatus of claim 11, wherein the separator faces the entire surface of the substrate.

13. A substrate processing apparatus comprising: a processing liquid nozzle for supplying processing liquid to a substrate; a dissolving gas pipe for spraying dissolving gas into a plurality of passages of a separator; and a dissolving gas supply unit for supplying the dissolving gas into the dissolving gas pipe; wherein the dissolving gas supply unit dissolves the dissolving gas separated by entering the plurality of passages of the separator in the processing liquid within a container, while the separator formed of a porous material is fully immersed in the processing liquid.

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