Substrate processing apparatus and substrate processing method

Abstract

The substrate processing apparatus (100) includes: a substrate holding section (20) for holding and rotating a substrate (W); and a mixture supply section (50) for supplying a sulfuric acid-hydrogen peroxide mixture to the substrate (W) rotating through the substrate holding section (20). The mixture supply section (50) supplies the sulfuric acid-hydrogen peroxide mixture to the substrate at a first flow rate during a first period, and at a second flow rate lower than the first flow rate during a second period following the first period. During the second period, the proportion of sulfuric acid in the sulfuric acid-hydrogen peroxide mixture is lower than the proportion of sulfuric acid in the sulfuric acid-hydrogen peroxide mixture during the first period.

Description

TECHNICAL FIELD

[0001] The present application relates to a substrate processing apparatus and a substrate processing method. BACKGROUND

[0002] Conventionally, in a manufacturing process of a device including a substrate such as a semiconductor device and a liquid crystal display device, a substrate processing apparatus that processes a substrate is used. The substrate is, for example, a semiconductor wafer or a glass substrate for a liquid crystal display device.

[0003] As a treatment for peeling off an object adhering to the surface of a substrate, an SPM (sulfuric acid hydrogen peroxide mixture) treatment is known. In the SPM treatment, a sulfuric acid hydrogen peroxide mixture in which sulfuric acid and hydrogen peroxide are mixed is supplied to the substrate, thereby peeling off the object adhering to the surface of the substrate.

[0004] In Patent Literature 1, an SPM treatment in which a substrate is treated with high-temperature SPM is described. In the substrate processing apparatus of Patent Literature 1, the ejection position of an SPM nozzle is moved from the center to the outer side of the substrate in accordance with the resist residue in the SPM photographed by a camera, thereby efficiently peeling off the object adhering to the surface of the substrate. Further, in Patent Literature 1, it is described that the substrate is treated with a first SPM containing abundant hydrogen peroxide and then treated with a second SPM containing abundant sulfuric acid. According to the method of Patent Literature 1, the remaining object can be removed well by the second SPM.

[0005] PRIOR ART DOCUMENTS

[0006] PATENT LITERATURE

[0007] Patent Literature 1: Japanese Patent Application Publication No. 2020-107779 SUMMARY

[0008] PROBLEMS TO BE SOLVED BY THE INVENTION

[0009] In the substrate processing apparatus of Patent Literature 1, the substrate is treated with high-temperature SPM, thereby the substrate can be efficiently treated with SPM. However, in the case where the substrate is treated with a high-temperature sulfuric acid hydrogen peroxide mixture, the droplets of the sulfuric acid hydrogen peroxide mixture on the substrate can splash to the surroundings. In this case, when the droplets of the sulfuric acid hydrogen peroxide mixture splash from the substrate and adhere to a certain member, the substrate can be contaminated by the adhering matter in the subsequent process. On the other hand, in the case where the substrate is treated with low-temperature SPM, the efficiency of the SPM treatment can be reduced.

[0010] The present application has been made in view of the above problems, and an object thereof is to provide a substrate processing apparatus and a substrate processing method in which the droplets of a sulfuric acid hydrogen peroxide mixture can be suppressed from splashing from a substrate and the substrate can be efficiently treated with SPM.

[0011] Means for solving the problem

[0012] A substrate processing apparatus according to an embodiment of the present application includes a substrate holding section that holds a substrate and rotates the substrate, and a mixed solution supply section that supplies a sulfuric acid-hydrogen peroxide mixed solution, in which sulfuric acid and hydrogen peroxide are mixed, to the substrate rotated by the substrate holding section. The mixed solution supply section supplies the sulfuric acid-hydrogen peroxide mixed solution to the substrate at a first flow rate during a first period, and supplies the sulfuric acid-hydrogen peroxide mixed solution to the substrate at a second flow rate smaller than the first flow rate during a second period after the first period. The proportion of the sulfuric acid in the sulfuric acid-hydrogen peroxide mixed solution during the second period is smaller than the proportion of the sulfuric acid in the sulfuric acid-hydrogen peroxide mixed solution during the first period.

[0013] In one embodiment, the substrate processing apparatus further includes an etching solution supply section that supplies an etching solution to the substrate before the mixed solution supply section supplies the sulfuric acid-hydrogen peroxide mixed solution to the substrate.

[0014] In one embodiment, the etching solution supply section supplies hydrofluoric acid or diluted hydrofluoric acid as the etching solution to the substrate.

[0015] In one embodiment, the mixed solution supply section supplies the sulfuric acid-hydrogen peroxide mixed solution, which is generated by mixing the sulfuric acid at 130°C or higher and 200°C or lower with the hydrogen peroxide at room temperature, to the substrate.

[0016] In one embodiment, the mixed solution supply section supplies the sulfuric acid-hydrogen peroxide mixed solution, in which the sulfuric acid and the hydrogen peroxide are mixed at a ratio of 4:1 to 9:1, to the substrate during the first period, and supplies the sulfuric acid-hydrogen peroxide mixed solution, in which the sulfuric acid and the hydrogen peroxide are mixed at a ratio of 2:1 to 3:1, to the substrate during the second period.

[0017] In one embodiment, the second period is longer than the first period.

[0018] In one embodiment, the substrate holding section rotates the substrate at a first rotation speed during the first period, and rotates the substrate at a second rotation speed during the second period after the substrate is rotated at the first rotation speed during the first period. The second rotation speed is smaller than the first rotation speed.

[0019] In one embodiment, the mixed solution supply section supplies the hydrogen peroxide to the substrate after the second period.

[0020] In one embodiment, the substrate processing apparatus further includes a flying inhibition member that inhibits droplets of the sulfuric acid-hydrogen peroxide mixed solution from flying from the substrate.

[0021] Another embodiment of the substrate processing method of the present invention includes an SPM (sulfuric acid-hydrogen peroxide) process in which a sulfuric acid-hydrogen peroxide mixture is supplied to a substrate held and rotated by a substrate holding portion, thereby treating the substrate with the sulfuric acid-hydrogen peroxide mixture. The SPM process includes: a first processing step in which the sulfuric acid-hydrogen peroxide mixture is supplied to the substrate at a first flow rate during a first period to treat the substrate; and a second processing step in which the sulfuric acid-hydrogen peroxide mixture is supplied to the substrate at a second flow rate lower than the first flow rate during a second period following the first period to treat the substrate; wherein the proportion of sulfuric acid in the sulfuric acid-hydrogen peroxide mixture during the second period is smaller than the proportion of sulfuric acid in the sulfuric acid-hydrogen peroxide mixture during the first period.

[0022] In one embodiment, the substrate processing method further includes an etching step, wherein the substrate is treated with an etching solution prior to the SPM processing step.

[0023] In one embodiment, during the etching process, hydrofluoric acid or diluted hydrofluoric acid is supplied to the substrate as the etching solution.

[0024] In one embodiment, during the SPM processing step, a sulfuric acid-hydrogen peroxide mixture, prepared by mixing sulfuric acid at a temperature above 130°C and below 220°C with hydrogen peroxide at room temperature, is supplied to the substrate.

[0025] In one embodiment, the first processing step supplies the substrate with a sulfuric acid-hydrogen peroxide mixture, which is formed by mixing the sulfuric acid and the hydrogen peroxide in a ratio of 4:1 to 9:1, during the first period; and the second processing step supplies the substrate with the sulfuric acid-hydrogen peroxide mixture, which is formed by mixing the sulfuric acid and the hydrogen peroxide in a ratio of 2:1 to 3:1, during the second period.

[0026] In one implementation, the second period is longer than the first period.

[0027] In one embodiment, during the SPM processing step, after the substrate is rotated at a first rotational speed during the first period, the substrate is rotated at a second rotational speed during the second period; the second rotational speed is smaller than the first rotational speed.

[0028] In one embodiment, the substrate processing method further includes a step of supplying hydrogen peroxide to the substrate after the second period, thereby treating the substrate with the hydrogen peroxide.

[0029] In one embodiment, during the SPM processing step, droplet scattering of the sulfuric acid-hydrogen peroxide mixture is suppressed by a scattering suppression member that is opposite to the position where the sulfuric acid-hydrogen peroxide mixture reaches the substrate.

[0030] Invention Effects

[0031] According to the present invention, a substrate processing apparatus and a substrate processing method are provided, which can suppress the splashing of sulfuric acid and hydrogen peroxide mixture droplets from the substrate and can efficiently perform SPM treatment on the substrate. Attached Figure Description

[0032] Figure 1 This is a schematic top view of the substrate processing apparatus of this embodiment.

[0033] Figure 2 This is a schematic diagram of the substrate processing unit in the substrate processing apparatus of this embodiment.

[0034] Figure 3 This is a block diagram of the substrate processing apparatus according to this embodiment.

[0035] Figure 4 A graph showing the number of droplets of sulfuric acid-hydrogen peroxide mixture splashed from the substrate in relation to the temperature of the mixture.

[0036] Figure 5 A graph showing the number of droplets of sulfuric acid-hydrogen peroxide mixture splashed from the substrate, corresponding to the sulfuric acid ratio and flow rate of the mixture.

[0037] Figure 6 A table showing the flow rate and sulfuric acid ratio of the sulfuric acid-hydrogen peroxide mixture in the first and second processes included in the SPM process of the substrate processing method of this embodiment.

[0038] Figure 7 (a) to (c) in the figure are schematic diagrams of the substrate processing method of this embodiment.

[0039] Figure 8 This is a flowchart of the substrate processing method according to this embodiment.

[0040] Figure 9 (a) to (e) in the figure are schematic diagrams of the substrate processing method of this embodiment.

[0041] Figure 10 (a) to (c) in the figure are schematic diagrams of the substrate processing method of this embodiment.

[0042] Figure 11 This is a flowchart of the substrate processing method according to this embodiment.

[0043] Figure 12 This is a schematic diagram of the substrate processing unit in the substrate processing apparatus of this embodiment.

[0044] Figure 13 This is a schematic top view of the substrate processing unit in the substrate processing apparatus of this embodiment.

[0045] Figure 14 This is a flowchart of the substrate processing method according to this embodiment. Detailed Implementation

[0046] Hereinafter, embodiments of the substrate processing apparatus and substrate processing method of the present invention will be described with reference to the accompanying drawings. Furthermore, the same reference numerals are used for the same or equivalent parts in the drawings, and descriptions will not be repeated. In addition, for ease of understanding of the present invention, the X-axis, Y-axis, and Z-axis will be described as orthogonal to each other in this specification. Typically, the X-axis and Y-axis are parallel to the horizontal direction, and the Z-axis is parallel to the vertical direction.

[0047] First, refer to Figure 1 An embodiment of the substrate processing apparatus 100 of the present invention will be described. Figure 1 This is a schematic top view of the substrate processing apparatus 100 of this embodiment.

[0048] The substrate processing apparatus 100 processes the substrate W. The substrate processing apparatus 100 processes the substrate W by means of at least one of etching, surface treatment, property imparting, processing film formation, removal of at least a portion of the film, and cleaning.

[0049] The substrate W is used as a semiconductor substrate. The substrate W includes a semiconductor wafer. For example, the substrate W is generally circular. Here, the substrate processing apparatus 100 processes the substrate W one wafer at a time.

[0050] like Figure 1 As shown, the substrate processing apparatus 100 includes a plurality of substrate processing units 10, a processing liquid tank 110, a processing liquid reservoir 120, a plurality of load ports LP, an indexer robot IR, a central robot CR, and a control device 101. The control device 101 controls the load ports LP, the indexer robot IR, and the central robot CR. The control device 101 includes a control unit 102 and a storage unit 104. In this specification, the indexer robot IR and the central robot CR may be collectively referred to as a handling unit.

[0051] Loading ports LP respectively accommodate multiple substrates W stacked together. A sorting robot IR moves substrates W between loading ports LP and a central robot CR. The central robot CR moves substrates W between the sorting robot IR and the substrate processing unit 10. The substrate processing unit 10 sprays processing liquid onto the substrates W to process them. The processing liquid includes chemical solutions, rinsing solutions, removal solutions, and / or water-repellent agents. A processing liquid tank 110 contains the processing liquid. Additionally, the processing liquid tank 110 can also contain gas.

[0052] Specifically, a plurality of substrate processing units 10 form a plurality of towers TW (in) Figure 1 There are four towers (TWs) in the center, and the plurality of towers (TWs) are arranged in a manner that surrounds the central robot arm (CR) when viewed from above. Each tower (TW) includes a plurality of substrate processing units 10 stacked vertically. Figure 1 There are three substrate processing units 10 in the middle. Processing liquid tanks 120 correspond to a plurality of towers TW. Liquid in the processing liquid tank 110 is supplied via any one of the processing liquid tanks 120 to all the substrate processing units 10 included in the tower TW corresponding to that processing liquid tank 120. Furthermore, gas in the processing liquid tank 110 is supplied via any one of the processing liquid tanks 120 to all the substrate processing units 10 included in the tower TW corresponding to that processing liquid tank 120.

[0053] Typically, the processing fluid tank 110 has a storage tank (reservoir) for preparing the processing fluid. The processing fluid tank 110 may also have a storage tank for one type of processing fluid, or it may have a storage tank for several types of processing fluid. In addition, the processing fluid tank 110 may also have pumps, valves and / or filters for circulating the processing fluid.

[0054] The control device 101 controls various operations of the substrate processing device 100. The substrate processing unit 10 processes the substrate W through the control device 101.

[0055] The control device 101 includes a control unit 102 and a storage unit 104. The control unit 102 has a processor. The control unit 102 has, for example, a central processing unit (CPU). Alternatively, the control unit 102 may also have a general-purpose arithmetic unit.

[0056] Storage unit 104 stores data and computer programs. The data includes recipe data. The recipe data includes information representing a plurality of recipes. The plurality of recipes respectively specify the processing content and processing order of the substrate W.

[0057] The storage unit 104 includes a main storage device and an auxiliary storage device. The main storage device is, for example, a semiconductor memory. The auxiliary storage device is, for example, a semiconductor memory and / or a hard disk drive. The storage unit 104 may also include removable media. The control unit 102 executes the computer program stored in the storage unit 104 to perform board processing operations.

[0058] Next, refer to Figure 2 This section describes the substrate processing unit 10 in the substrate processing apparatus 100 of this embodiment. Figure 2 This is a schematic diagram of the substrate processing unit 10 in the substrate processing apparatus 100.

[0059] The substrate processing unit 10 includes a chamber 11, an air supply unit 12, a substrate holding section 20, an etching solution supply section 30, a rinsing solution supply section 40, an SPM supply section 50, and a rinsing solution supply section 60.

[0060] The chamber 11 is generally box-shaped with an internal space. The chamber 11 houses the substrate W. Here, the substrate processing apparatus 100 is a monolithic type for processing substrates W one by one, and the substrates W are housed one by one in the chamber 11. The substrate W is housed in the chamber 11 and processed in the chamber 11. At least a portion of each of the substrate holding section 20, the etching solution supply section 30, the rinsing solution supply section 40, the SPM supply section 50, and the rinsing solution supply section 60 is housed in the chamber 11.

[0061] An air supply unit 12 is disposed above the chamber 11. For example, the air supply unit 12 is disposed on the top surface of the chamber 11. The air supply unit 12 delivers air into the chamber 11. The air supply unit 12 includes, for example, a fan filter unit (FFU). A downflow is formed within the chamber 11 through the air supply unit 12 and an exhaust device (not shown).

[0062] The substrate holding portion 20 holds the substrate W. The substrate holding portion 20 holds the substrate W horizontally with its upper surface (surface) Wa facing upwards and its back surface (lower surface) Wb facing vertically downwards. Furthermore, the substrate holding portion 20 rotates the substrate W while holding it. For example, a laminated structure with recesses is provided on the upper surface Wa of the substrate W. The substrate holding portion 20 rotates the substrate W while holding it.

[0063] For example, the substrate holding portion 20 may be a clamping type for holding the end of the substrate W. Alternatively, the substrate holding portion 20 may have any mechanism for holding the substrate W from the back surface Wb. For example, the substrate holding portion 20 may also be a vacuum type. In this case, the substrate holding portion 20 adsorbs the central portion of the non-device forming surface, i.e., the back surface Wb of the substrate W, onto the upper surface, thereby holding the substrate W horizontally. Alternatively, the substrate holding portion 20 may combine a clamping type and a vacuum type, in which a plurality of clamping pins contact the peripheral end face of the substrate W.

[0064] For example, the substrate holding part 20 includes a rotating base 21, a clamping member 22, a shaft 23, a rotary motor 24, and a housing 25. The clamping member 22 is disposed on the rotating base 21. The clamping member 22 clamps the substrate W. Typically, a plurality of clamping members 22 are disposed on the rotating base 21.

[0065] Shaft 23 extends vertically along the rotation axis Ax. A rotating base 21 is attached to the upper end of shaft 23. The substrate W is placed above the rotating base 21.

[0066] The rotating base 21 is circular. A clamping member 22 horizontally supports the substrate W. A shaft 23 extends downward from the center of the rotating base 21. A rotary motor 24 applies a rotational force to the shaft 23. The rotary motor 24 causes the shaft 23 to rotate in the rotational direction, thereby causing the substrate W and the rotating base 21 to rotate about the rotation axis Ax. The housing 25 houses the shaft 23 and the rotary motor 24.

[0067] The etching solution supply unit 30 supplies etching solution to the substrate W. Typically, the etching solution supply unit 30 supplies etching solution to the upper surface Wa of the substrate W. At least a portion of the etching solution supply unit 30 is housed within the chamber 11.

[0068] The etching solution supply unit 30 supplies etching solution to the upper surface Wa of the substrate W. The etching solution includes hydrofluoric acid or diluted hydrofluoric acid. For example, hydrofluoric acid can be heated to above 40°C and below 70°C, or to above 50°C and below 60°C. However, hydrofluoric acid may also be left unheated.

[0069] The etching solution supply unit 30 includes a pipe 32, a valve 34, and a nozzle 36. The nozzle 36 sprays etching solution onto the upper surface Wa of the substrate W. The nozzle 36 is connected to the pipe 32. Etching solution is supplied from a supply source to the pipe 32.

[0070] Valve 34 opens and closes the flow path within piping 32. Valve 34 adjusts the opening degree of piping 32 to regulate the flow rate of the etching solution supplied to piping 32. Specifically, valve 34 includes: a valve body (not shown) with a valve seat disposed therein; a valve body for opening and closing the valve seat; and an actuator (not shown) for moving the valve body between an open position and a closed position.

[0071] The nozzle 36 can also be configured to move relative to the substrate W. The etching solution supply unit 30 may also include a nozzle moving part 38. The nozzle moving part 38 can raise and lower the nozzle 36, and can also rotate the nozzle 36 horizontally about a rotation axis. The nozzle moving part 38 raises and lowers the nozzle 36. For example, the nozzle moving part 38 includes a ball screw mechanism and an electric motor that provides driving force to the ball screw mechanism. Furthermore, the nozzle moving part 38 rotates the nozzle 36 horizontally. For example, the nozzle moving part 38 includes an electric motor.

[0072] The rinsing fluid supply unit 40 supplies rinsing fluid to the substrate W. Typically, the rinsing fluid supply unit 40 supplies rinsing fluid to the upper surface Wa of the substrate W. At least a portion of the rinsing fluid supply unit 40 is housed within the chamber 11.

[0073] The rinsing fluid supply unit 40 supplies rinsing fluid to the upper surface Wa of the substrate W. Typically, the rinsing fluid includes carbonated water. Alternatively, the rinsing fluid may be a liquid other than carbonated water. For example, deionized water (DIW), electrolyzed water, ozone water, ammonia water, hydrochloric acid water with a dilution concentration (e.g., about 10 ppm to 100 ppm), and reduced water (hydrogen water) can be used as rinsing fluids.

[0074] The rinsing fluid supply unit 40 includes a pipe 42, a valve 44, and a nozzle 46. The nozzle 46 sprays rinsing fluid onto the upper surface Wa of the substrate W. The nozzle 46 is connected to the pipe 42. Rinsing fluid is supplied to the pipe 42 from a supply source. The valve 44 opens and closes the flow path within the pipe 42. The nozzle 46 may also be configured to be movable relative to the substrate W.

[0075] Valve 44 opens and closes the flow path within piping 42. Valve 44 adjusts the opening degree of piping 42 to regulate the flow rate of flushing fluid supplied to piping 42. Specifically, valve 44 includes: a valve body (not shown) with a valve seat disposed internally; a valve body for opening and closing the valve seat; and an actuator (not shown) for moving the valve body between an open position and a closed position.

[0076] The nozzle 46 can also be moved. The nozzle 46 can be moved in the horizontal and / or vertical directions by a moving mechanism controlled by the control unit 102.

[0077] The SPM supply unit 50 supplies a sulfuric acid-hydrogen peroxide mixture to the substrate W. Typically, the SPM supply unit 50 supplies the sulfuric acid-hydrogen peroxide mixture to the upper surface Wa of the substrate W. The sulfuric acid-hydrogen peroxide mixture can also be heated to 90°C or higher and 240°C or lower. At least a portion of the SPM supply unit 50 is housed within the chamber 11. In this specification, the SPM supply unit 50 may be referred to as a mixture supply unit 50.

[0078] The SPM supply unit (mixture supply unit) 50 includes piping 52a, valve 54a, piping 52b, valve 54b, heater 55a, pump 57a, and nozzle 56. Nozzle 56 sprays a sulfuric acid-hydrogen peroxide mixture onto the upper surface Wa of substrate W.

[0079] Here, nozzle 56 is connected to pipes 52a and 52b. Sulfuric acid is supplied from a supply source to pipe 52a. Valve 54a opens and closes the flow path within pipe 52a. Valve 54a adjusts the opening degree of pipe 52a to regulate the flow rate of sulfuric acid supplied to pipe 52a. Specifically, valve 54a includes: a valve body (not shown) with a valve seat disposed internally; a valve body for opening and closing the valve seat; and an actuator (not shown) for moving the valve body between an open position and a closed position.

[0080] Pump 57a allows sulfuric acid to flow through piping 52a. Heater 55a heats the sulfuric acid flowing in piping 52a. The temperature of the sulfuric acid can be adjusted by heater 55a. Heater 55a heats the sulfuric acid flowing in piping 52a and adjusts the temperature of the sulfuric acid (e.g., from about 70°C to 220°C). Heater 55a can also heat the sulfuric acid and measure its temperature.

[0081] Hydrogen peroxide is supplied from a supply source to pipe 52b. Valve 54b opens and closes the flow path within pipe 52b. Valve 54b adjusts the opening degree of pipe 52b to regulate the flow rate of hydrogen peroxide supplied to pipe 52b. Specifically, valve 54b includes: a valve body (not shown) with a valve seat disposed internally; a valve body for opening and closing the valve seat; and an actuator (not shown) for moving the valve body between an open position and a closed position.

[0082] Here, sulfuric acid flowing in pipe 52a and hydrogen peroxide flowing in pipe 52b are mixed in nozzle 56 to generate a sulfuric acid-hydrogen peroxide mixture. The temperature of the sulfuric acid-hydrogen peroxide mixture rises due to the mixing of the sulfuric acid and hydrogen peroxide.

[0083] The nozzle 56 can also be configured to move relative to the substrate W. The SPM supply unit 50 may also include a nozzle moving unit 58. The nozzle moving unit 58 can also raise or lower the nozzle 56, or rotate the nozzle 56 horizontally about a rotation axis. The nozzle moving unit 58 raises or lowers the nozzle 56. For example, the nozzle moving unit 58 includes a ball screw mechanism and an electric motor that provides driving force to the ball screw mechanism. In addition, the nozzle moving unit 58 rotates the nozzle 56 horizontally. For example, the nozzle moving unit 58 includes an electric motor.

[0084] Furthermore, when valve 54a is open, allowing sulfuric acid to flow in pipe 52a and valve 54b is open, allowing hydrogen peroxide to flow in pipe 52b, the SPM supply unit 50 supplies the sulfuric acid-hydrogen peroxide mixture to the substrate W through nozzle 56. Conversely, when valve 54a is closed, preventing sulfuric acid from flowing in pipe 52a, and valve 54b is open, allowing hydrogen peroxide to flow in pipe 52b, the SPM supply unit 50 supplies hydrogen peroxide to the substrate W through nozzle 56. Furthermore, when valve 54a is open, allowing sulfuric acid to flow in pipe 52a, and valve 54b is closed, preventing hydrogen peroxide from flowing in pipe 52b, the SPM supply unit 50 supplies sulfuric acid to the substrate W through nozzle 56.

[0085] The rinsing fluid supply unit 60 supplies rinsing fluid to the substrate W. Typically, the rinsing fluid supply unit 60 supplies rinsing fluid to the upper surface Wa of the substrate W. At least a portion of the rinsing fluid supply unit 60 is housed within the chamber 11.

[0086] The rinsing solution supply unit 60 supplies rinsing solution to the upper surface Wa of the substrate W. Examples of rinsing solutions include deionized water (DIW), carbonated water, electrolyzed water, ozone water, ammonia water, hydrochloric acid water with a dilution concentration (e.g., about 10 ppm to 100 ppm) and reduced water (hydrogen water).

[0087] The rinsing fluid supply unit 60 includes a pipe 62, a valve 64, and a nozzle 66. The nozzle 66 sprays rinsing fluid onto the upper surface Wa of the substrate W. The nozzle 66 is connected to the pipe 62. Rinsing fluid is supplied to the pipe 62 from a supply source. The valve 64 opens and closes the flow path within the pipe 62. The nozzle 66 may also be configured to be movable relative to the substrate W.

[0088] Valve 64 opens and closes the flow path within piping 62. Valve 64 adjusts the opening degree of piping 62 to regulate the flow rate of flushing fluid supplied to piping 62. Specifically, valve 64 includes: a valve body (not shown) with a valve seat disposed internally; a valve body for opening and closing the valve seat; and an actuator (not shown) for moving the valve body between an open position and a closed position.

[0089] The nozzle 66 can also be moved. The nozzle 66 can be moved in the horizontal and / or vertical directions by a moving mechanism controlled by the control unit 102.

[0090] The substrate processing unit 10 also includes a cup 90. The cup 90 collects processing liquid that spills from the substrate W. The cup 90 moves up and down. For example, during the supply of etching solution, rinsing solution, SPM and / or rinsing solution to the substrate W by the etching solution supply unit 30, rinsing solution supply unit 40, SPM supply unit 50 and / or rinsing solution supply unit 60, the cup 90 rises vertically upward to the side of the substrate W. In this case, the cup 90 collects the etching solution, rinsing solution, SPM and / or rinsing solution that spills from the substrate W due to the rotation of the substrate W. Furthermore, at the end of the supply of etching solution, rinsing solution, SPM and / or rinsing solution to the substrate W by the etching solution supply unit 30, rinsing solution supply unit 40, SPM supply unit 50 and / or rinsing solution supply unit 60, the cup 90 descends vertically downward from the side of the substrate W.

[0091] As described above, the control device 101 includes a control unit 102 and a storage unit 104. The control unit 102 controls the air supply unit 12, the substrate holding unit 20, the etching solution supply unit 30, the rinsing solution supply unit 40, the SPM supply unit 50, the rinsing solution supply unit 60, and / or the cup 90. In one example, the control unit 102 controls the air supply unit 12, the rotary motor 24, valves 34, 44, 54a, 54b, and 64, the nozzle moving units 38 and 58, the heater 55a, the pump 57a, and / or the cup 90.

[0092] The substrate processing apparatus 100 of this embodiment is suitable for manufacturing semiconductor devices in which semiconductors are disposed. Typically, in a semiconductor device, a conductive layer and an insulating layer are stacked on a substrate. The substrate processing apparatus 100 is suitable for cleaning and / or processing (e.g., etching, property modification, etc.) of the conductive layer and / or insulating layer during the manufacture of semiconductor devices.

[0093] Next, refer to Figures 1 to 3 The substrate processing apparatus 100 of this embodiment will be described. Figure 3 This is a block diagram of the substrate processing apparatus 100.

[0094] like Figure 3As shown, the control device 101 controls various operations of the substrate processing apparatus 100. The control device 101 controls the indexing robot IR, the central robot CR, the air supply unit 12, the substrate holding section 20, the etchant supply section 30, the rinsing fluid supply section 40, the SPM supply section 50, the rinsing fluid supply section 60, and the cup 90. Specifically, the control device 101 controls the indexing robot IR, the central robot CR, the air supply unit 12, the substrate holding section 20, the etchant supply section 30, the rinsing fluid supply section 40, the SPM supply section 50, the rinsing fluid supply section 60, and the cup 90 by sending control signals to them.

[0095] In addition, the storage unit 104 stores computer programs and data. The data includes procedure data. The procedure data includes information representing a plurality of procedures. The plurality of procedures respectively specify the processing content, processing order, and substrate processing conditions of the substrate W. The control unit 102 executes the computer program stored in the storage unit 104 to perform substrate processing operations.

[0096] The control unit 102 controls the indexing robot IR to transfer the substrate W through the indexing robot IR.

[0097] The control unit 102 controls the central robot CR, which handles the substrate W. For example, the central robot CR receives the unprocessed substrate W and moves it into any one of the plurality of chambers 11. Furthermore, the central robot CR receives the processed substrate W from the chamber 11 and moves it out.

[0098] The control unit 102 controls the air supply unit 12 to deliver air into the chamber 11. For example, the control unit 102 controls the air supply unit 12 and the exhaust device (not shown) to form a downflow within the chamber 11.

[0099] The control unit 102 controls the substrate holding unit 20, thereby controlling the loading and unloading of the substrate W, the start of the rotation of the substrate W, the change of the rotation speed of the substrate W, and the stop of the rotation of the substrate W. For example, the control unit 102 controls the substrate holding unit 20, thereby changing the rotation speed of the substrate holding unit 20. Specifically, the control unit 102 can change the rotation speed of the substrate W by changing the rotation speed of the rotary motor 24 of the substrate holding unit 20.

[0100] The control unit 102 controls the valve 34 of the etching solution supply unit 30, thereby switching the state of the valve 34 between an open state and a closed state. Specifically, the control unit 102 controls the valve 34 of the etching solution supply unit 30 to open the valve 34, thereby allowing the etching solution flowing toward the nozzle 36 and within the piping 32 to pass through. Conversely, the control unit 102 controls the valve 34 of the etching solution supply unit 30 to close the valve 34, thereby stopping the supply of etching solution flowing toward the nozzle 36 and within the piping 32.

[0101] The control unit 102 controls the valve 44 of the flushing fluid supply unit 40, thereby switching the state of the valve 44 between an open state and a closed state. Specifically, the control unit 102 controls the valve 44 of the flushing fluid supply unit 40 to open the valve 44, thereby allowing flushing fluid flowing toward the nozzle 46 within the piping 42 to pass through. Conversely, the control unit 102 controls the valve 44 of the flushing fluid supply unit 40 to close the valve 44, thereby stopping the supply of flushing fluid flowing toward the nozzle 46 within the piping 42.

[0102] The control unit 102 controls valve 54a, thereby switching the state of valve 54a between an open state and a closed state. Specifically, the control unit 102 controls valve 54a to open, thereby allowing sulfuric acid flowing toward nozzle 56 through pipe 52a. Conversely, the control unit 102 controls valve 54a to close, thereby stopping the supply of sulfuric acid flowing toward nozzle 56 through pipe 52a.

[0103] The control unit 102 controls valve 54b, thereby switching the state of valve 54b between an open state and a closed state. Specifically, the control unit 102 controls valve 54b to open, allowing hydrogen peroxide flowing toward nozzle 56 through pipe 52b. Conversely, the control unit 102 controls valve 54b to close, thereby stopping the supply of hydrogen peroxide flowing toward nozzle 56 through pipe 52b.

[0104] Furthermore, the control unit 102 controls valves 54a and 54b to open them, thereby allowing sulfuric acid and hydrogen peroxide to pass through pipes 52a and 52b towards nozzle 56, and spraying the sulfuric acid-hydrogen peroxide mixture from nozzle 56. Conversely, the control unit 102 also controls valves 54a and 54b to close them, thereby stopping the spraying of the sulfuric acid-hydrogen peroxide mixture from nozzle 56.

[0105] The control unit 102 controls the valve 64 of the flushing fluid supply unit 60, thereby switching the state of the valve 64 between an open state and a closed state. Specifically, the control unit 102 controls the valve 64 of the flushing fluid supply unit 60 to open the valve 64, thereby allowing flushing fluid flowing toward the nozzle 66 within the piping 62 to pass through. Conversely, the control unit 102 controls the valve 64 of the flushing fluid supply unit 60 to close the valve 64, thereby stopping the supply of flushing fluid flowing toward the nozzle 66 within the piping 62.

[0106] The control unit 102 can also control the cup 90 to move the cup 90 relative to the substrate W. Specifically, during the period when the etchant supply unit 30, the rinsing solution supply unit 40, the SPM supply unit 50 and / or the rinsing solution supply unit 60 supply etchant, rinsing solution, SPM and / or rinsing solution to the substrate W, the control unit 102 raises the cup 90 vertically upward to the side of the substrate W. Furthermore, at the end of the period when the etchant supply unit 30, the rinsing solution supply unit 40, the SPM supply unit 50 and / or the rinsing solution supply unit 60 supply etchant, rinsing solution, SPM and / or rinsing solution to the substrate W, the control unit 102 lowers the cup 90 vertically downward from the side of the substrate W.

[0107] The substrate processing apparatus 100 of this embodiment is suitable for forming semiconductor elements. For example, the substrate processing apparatus 100 is suitable for processing a substrate W used as a semiconductor element with a stacked structure. The semiconductor element is a so-called 3D structured memory (storage device). As an example, the substrate W is suitable for NAND (NOT-AND) type flash memory.

[0108] When a substrate is treated with a high-temperature sulfuric acid-hydrogen peroxide mixture, droplets of the mixture may splash off the substrate. Treating a hydrophobic substrate with the sulfuric acid-hydrogen peroxide mixture transforms the substrate into a hydrophilic one. In this case, when the sulfuric acid-hydrogen peroxide mixture is at a high temperature, it reacts violently with the substrate, resulting in droplets splashing off the substrate. For example, when a substrate is etched with hydrofluoric acid or diluted hydrofluoric acid, the substrate becomes hydrophobic. Subsequently, when the substrate is treated with a sulfuric acid-hydrogen peroxide mixture to transform it into a hydrophilic one, if the mixture is at a high temperature, droplets may splash off the substrate.

[0109] Next, refer to Figure 4 This describes the splashing of droplets in a sulfuric acid-hydrogen peroxide mixture, corresponding to the temperature and sulfuric acid ratio of the mixture. Figure 4 A graph illustrating the change in the number of droplets of a sulfuric acid-hydrogen peroxide mixture splashed from a substrate corresponding to the heating temperature of sulfuric acid. Figure 4The results are shown for sulfuric acid and hydrogen peroxide mixtures with different sulfuric acid ratios. Figure 4 In the diagram, line L1 represents the result when the ratio of sulfuric acid to hydrogen peroxide in the sulfuric acid-hydrogen peroxide mixture is 6:1, and line L2 represents the result when the ratio of sulfuric acid to hydrogen peroxide in the sulfuric acid-hydrogen peroxide mixture is 2:1.

[0110] like Figure 4 As shown in line L1, even when the sulfuric acid content in the sulfuric acid-hydrogen peroxide mixture is high, the number of droplets of the sulfuric acid-hydrogen peroxide mixture splashed from the substrate remains almost unchanged, even as the temperature of the sulfuric acid increases. On the other hand, as... Figure 4 As shown by line L2, when the sulfuric acid content in the sulfuric acid-hydrogen peroxide mixture is low, the number of droplets increases as the sulfuric acid temperature rises. For example, when the sulfuric acid temperature exceeds 120°C, the number of droplets increases dramatically. This is believed to be because when the sulfuric acid-hydrogen peroxide mixture has a low sulfuric acid content and a high temperature, the mixture reacts violently on the substrate, thus increasing the number of droplets splashed from the substrate (droplet count).

[0111] Next, refer to Figure 5 This describes the degree of splashing of the sulfuric acid-hydrogen peroxide mixture corresponding to its temperature. Figure 5 A graph showing the sulfuric acid ratio and droplet number corresponding to the flow rate in a sulfuric acid-hydrogen peroxide mixture. Figure 5 In the diagram, the X-axis shows the sulfuric acid ratio, the Y-axis shows the flow rate, and the Z-axis shows the number of droplets (droplet count) of the sulfuric acid-hydrogen peroxide mixture splashed from the substrate. Furthermore, in... Figure 5 In the figure, the minimum value of the X-axis is the result of treating the substrate with a sulfuric acid and hydrogen peroxide mixture in a ratio of 2:1, and the maximum value of the X-axis is the result of treating the substrate with a sulfuric acid and hydrogen peroxide mixture in a ratio of 9:1.

[0112] from Figure 5 The variation along the Y-axis reveals the following trend: the greater the flow rate of the sulfuric acid-hydrogen peroxide mixture, the greater the number of droplets. Furthermore, from... Figure 5 The variation along the X-axis reveals the following trend: the lower the sulfuric acid ratio in the sulfuric acid-hydrogen peroxide mixture, the greater the increase in the number of droplets. This is generally attributed to the fact that as the sulfuric acid-hydrogen peroxide ratio increases from 2:1, the temperature rise of the mixture decreases.

[0113] Since an increase in the number of droplets makes them more likely to adhere to the chamber, it becomes difficult to properly process the substrate. Therefore, from the viewpoint of reducing the number of droplets, it is preferable to process the substrate with a sulfuric acid-hydrogen peroxide mixture at a lower temperature and with a higher sulfuric acid content. On the other hand, from the viewpoint of SPM treatment of the substrate, it is preferable to process the substrate with a sulfuric acid-hydrogen peroxide mixture at a higher temperature and with a lower sulfuric acid content.

[0114] Based on the above insights, in the substrate processing apparatus 100 of this embodiment, when the substrate W is subjected to SPM treatment with a sulfuric acid-hydrogen peroxide mixture, the substrate W is first treated with a sulfuric acid-hydrogen peroxide mixture with a high flow rate and a high sulfuric acid ratio, and then the substrate W is treated with a sulfuric acid-hydrogen peroxide mixture with a low flow rate and a low sulfuric acid ratio.

[0115] Next, refer to Figures 1 to 6 The substrate processing method of this embodiment will be explained. Figure 6 This is a table showing the SPM process in the substrate processing method of this embodiment.

[0116] like Figure 6 As shown, in this embodiment, the SPM process includes a first process and a second process. The SPM process begins with the first process. The first process is performed during a first period. The second process begins after the first process has ended. The second process is performed during a second period after the first period. Typically, the second period begins immediately after the first period has ended.

[0117] First, in the first process, the substrate W is treated with a sulfuric acid and hydrogen peroxide mixture with a high flow rate and a high sulfuric acid ratio. For example, the opening degrees of valves 54a and 54b are set to a large value, and the flow rates of sulfuric acid and hydrogen peroxide flowing in pipes 52a and 52b are set to a large value. Furthermore, considering the total flow rates of sulfuric acid and hydrogen peroxide flowing in pipes 52a and 52b, the proportion of sulfuric acid flow rate in pipe 52a is set to a high value.

[0118] In the second process following the first process, the substrate W is treated with a sulfuric acid and hydrogen peroxide mixture at a low flow rate and a low sulfuric acid ratio. For example, the opening degrees of valves 54a and 54b are set to a small value, and the flow rates of sulfuric acid and hydrogen peroxide flowing in pipes 52a and 52b are set to a small value. Furthermore, the total flow rate of sulfuric acid and hydrogen peroxide flowing in pipes 52a and 52b is set to a low proportion of the sulfuric acid flow rate in pipe 52a.

[0119] According to the substrate processing method of this embodiment, in the first processing, the substrate W is treated with a high-flow-rate sulfuric acid-hydrogen peroxide mixture. Therefore, the sulfuric acid-hydrogen peroxide mixture can quickly cover the upper surface Wa of the substrate W, thereby suppressing the adhesion of particles to the substrate W. Furthermore, in the first processing, since the sulfuric acid content of the sulfuric acid-hydrogen peroxide mixture is high, liquid splashing of the sulfuric acid-hydrogen peroxide mixture can be suppressed.

[0120] According to the substrate processing method of this embodiment, the substrate W is treated with a sulfuric acid-hydrogen peroxide mixture with a low sulfuric acid ratio in the second processing. Because the sulfuric acid ratio in the sulfuric acid-hydrogen peroxide mixture is low in the second processing, the substrate W can be treated with the sulfuric acid-hydrogen peroxide mixture for a short time. Furthermore, because the substrate W is treated with a low flow rate of the sulfuric acid-hydrogen peroxide mixture in the second processing, the consumption of the sulfuric acid-hydrogen peroxide mixture in the SPM processing can be reduced.

[0121] In addition, after referring to Figures 4 to 6 In the above description, although liquid splashing depends on the temperature, sulfuric acid ratio, and flow rate of the sulfuric acid-hydrogen peroxide mixture, it also depends on the rotational speed of the substrate W. Typically, the higher the rotational speed of the substrate W, the easier it is for liquid splashing to occur, and the lower the rotational speed of the substrate W, the less likely it is for liquid splashing to occur. Therefore, in the first process, the rotational speed of the substrate W is preferably lower than a threshold value.

[0122] On the other hand, in the second process, the temperature of the sulfuric acid-hydrogen peroxide mixture on the substrate W is preferably maintained at a relatively high level. Furthermore, when the rotational speed of the substrate W in the second process is high, the liquid film may become thinner and the efficiency of the SPM process may decrease. Therefore, the rotational speed of the substrate W in the second process can also be lower than the rotational speed of the substrate W in the first process.

[0123] Next, refer to Figures 1 to 7 The substrate processing method of this embodiment is explained. Figure 7 (a) to (c) in the figure are schematic diagrams of the substrate processing method of this embodiment.

[0124] like Figure 7 As shown in (a), rinsing fluid is supplied to the substrate W. Under the control of the control unit 102, the rinsing fluid supply unit 40 supplies rinsing fluid to the substrate W from the nozzle 46. Therefore, the substrate W is rinsed.

[0125] The rinsing fluid is supplied from nozzle 46 to the rotating substrate W. When the rinsing fluid is sprayed to the center of the substrate W, it expands radially from the center of the substrate W by centrifugal force and covers the entire upper surface Wa of the substrate W. At this time, the rinsing fluid forms a film with a thickness L0.

[0126] like Figure 7As shown in (b), a sulfuric acid-hydrogen peroxide mixture is supplied to substrate W to perform a first treatment on substrate W. Under the control of control unit 102, SPM supply unit 50 supplies the sulfuric acid-hydrogen peroxide mixture to substrate W from nozzle 56. Here, valve 54a is opened to allow sulfuric acid to flow in pipe 52a, and valve 54b is opened to allow hydrogen peroxide to flow in pipe 52b, and the sulfuric acid-hydrogen peroxide mixture generated by mixing sulfuric acid and hydrogen peroxide in nozzle 56 is ejected from nozzle 56.

[0127] A sulfuric acid-hydrogen peroxide mixture is supplied from nozzle 56 to a rotating substrate W. When the sulfuric acid-hydrogen peroxide mixture is sprayed to the center of substrate W, it expands radially from the center of substrate W by centrifugal force and spreads throughout the entire upper surface Wa of substrate W. At this time, the sulfuric acid-hydrogen peroxide mixture forms a film with a liquid thickness L1.

[0128] Thus, a sulfuric acid-hydrogen peroxide mixture is supplied to the rotating substrate W, thereby treating the substrate W with the sulfuric acid-hydrogen peroxide mixture. Therefore, the substrate W is treated with the sulfuric acid-hydrogen peroxide mixture in the first period.

[0129] In this first process, the flow rate of sulfuric acid flowing in pipe 52a is Fs1, and the temperature of the sulfuric acid is Ts1. In the first process, the flow rate of hydrogen peroxide flowing in pipe 52b is Fh1, and the temperature of the hydrogen peroxide is Th1. Furthermore, in the first process, the flow rate of the sulfuric acid-hydrogen peroxide mixture is Fc1, the temperature of the sulfuric acid-hydrogen peroxide mixture is Tc1, and the sulfuric acid ratio in the sulfuric acid-hydrogen peroxide mixture is Rc1. Furthermore, in the first process, the rotation speed of the substrate W is Rr1.

[0130] Sulfuric acid and hydrogen peroxide are mixed to form a sulfuric acid-hydrogen peroxide mixture. At this point, the sulfuric acid and hydrogen peroxide undergo an exothermic reaction. Therefore, the temperature Tc1 of the sulfuric acid-hydrogen peroxide mixture is higher than the temperature Ts1 of the sulfuric acid and the temperature Th1 of the hydrogen peroxide.

[0131] For example, the temperature Ts1 of sulfuric acid is above 70°C and below 220°C, or it can be above 100°C and below 200°C. Furthermore, the temperature Th1 of hydrogen peroxide is room temperature. For example, the temperature Tc1 of a sulfuric acid-hydrogen peroxide mixture is above 90°C and below 240°C.

[0132] The substrate W is hydrophilically treated in the first process. Here, the flow rate Fc1 of the sulfuric acid-hydrogen peroxide mixture is relatively large, so that the sulfuric acid-hydrogen peroxide mixture can quickly cover the substrate W.

[0133] Furthermore, in the first process, the sulfuric acid-hydrogen peroxide mixture supplied to the substrate W may splash off the substrate W and adhere to the chamber 11. Therefore, the first process is preferably performed in a manner that prevents droplets of the sulfuric acid-hydrogen peroxide mixture from splashing off the substrate W. For example, in the first process, when the sulfuric acid ratio of the sulfuric acid-hydrogen peroxide mixture is low, the sulfuric acid-hydrogen peroxide mixture may splash off the substrate W and adhere to the chamber 11. Therefore, it is preferable to set the sulfuric acid ratio of the sulfuric acid-hydrogen peroxide mixture to a higher level.

[0134] Typically, the flow rate of sulfuric acid, Fs1, is greater than the flow rate of hydrogen peroxide, Fh1. For example, in the first treatment, sulfuric acid and hydrogen peroxide are mixed in a ratio of 4:1 to 9:1 (that is, the flow rate of sulfuric acid is set to be more than four times but less than nine times the flow rate of hydrogen peroxide).

[0135] Furthermore, in the first process, when the rotational speed of the substrate W is relatively high, a mixture of sulfuric acid and hydrogen peroxide may splash from the substrate W and adhere to the chamber 11. Therefore, the rotational speed Rr1 of the substrate W in the first process is preferably lower than a threshold value. For example, the rotational speed Rr1 of the substrate W in the first process is 700 rpm or more and 1400 rpm or less, or it may be 800 rpm or more and 1200 rpm or less.

[0136] like Figure 7 As shown in (c), a sulfuric acid-hydrogen peroxide mixture is supplied to the substrate W, thereby performing a second treatment on the substrate W. Under the control of the control unit 102, the SPM supply unit 50 continuously supplies the sulfuric acid-hydrogen peroxide mixture to the substrate W from the nozzle 56. The conditions for the second treatment differ from those for the first treatment. Here, the sulfuric acid-hydrogen peroxide mixture is supplied to the substrate W, thereby treating the substrate W with the sulfuric acid-hydrogen peroxide mixture.

[0137] In the second process, substrate W is treated with a sulfuric acid-hydrogen peroxide mixture at a low flow rate and with a low sulfuric acid ratio. At this time, the sulfuric acid-hydrogen peroxide mixture forms a film of thickness L2. The film thickness L2 in the second process is smaller than the film thickness L1 in the first process.

[0138] In the second process, the opening degree of at least one of valves 54a and 54b from the first process is changed. For example, in the second process, the opening degree of valve 54a from the first process is reduced, thereby reducing the flow rate of sulfuric acid. Furthermore, in the second process, the opening degree of valve 54b from the first process can also be changed, thereby changing the flow rate of hydrogen peroxide.

[0139] In this second process, the flow rate of sulfuric acid flowing in pipe 52a is Fs2, and the temperature of the sulfuric acid is Ts2. In the second process, the flow rate of hydrogen peroxide flowing in pipe 52b is Fh2, and the temperature of the hydrogen peroxide is Th2. Furthermore, in the second process, the flow rate of the sulfuric acid-hydrogen peroxide mixture is Fc2, the temperature of the sulfuric acid-hydrogen peroxide mixture is Tc2, and the sulfuric acid ratio in the sulfuric acid-hydrogen peroxide mixture is Rc2. Furthermore, in the second process, the rotation speed of the substrate W is Rr2.

[0140] In the second process, the hydrophilized substrate W is treated with a sulfuric acid-hydrogen peroxide mixture. Here, from the viewpoint of reducing costs and minimizing environmental impact, the flow rate Fc2 of the sulfuric acid-hydrogen peroxide mixture for the substrate W is preferably low. Furthermore, the sulfuric acid-hydrogen peroxide mixture is preferably prepared at a ratio that efficiently treats the substrate W.

[0141] Typically, here, the flow rate of sulfuric acid, Fs2, is greater than the flow rate of hydrogen peroxide, Fh2. For example, in the second treatment, sulfuric acid and hydrogen peroxide are mixed in a ratio of 2:1 to 3:1 (that is, the flow rate of sulfuric acid is set to be more than two times but less than three times the flow rate of hydrogen peroxide).

[0142] For example, the temperature Ts2 of sulfuric acid is above 70°C and below 220°C, or it can be above 100°C and below 200°C. Furthermore, the temperature Th2 of hydrogen peroxide is room temperature. For example, the temperature Tc2 of a sulfuric acid-hydrogen peroxide mixture is above 90°C and below 240°C.

[0143] Here, comparing the first and second processes, the flow rate Fc2 of the sulfuric acid-hydrogen peroxide mixture in the second process is smaller than the flow rate Fc1 of the sulfuric acid-hydrogen peroxide mixture in the first process. Therefore, the substrate W can be rapidly coated with the sulfuric acid-hydrogen peroxide mixture, thereby suppressing particle adhesion to the substrate W, and reducing the consumption of the sulfuric acid-hydrogen peroxide mixture. For example, the flow rate Fc2 of the sulfuric acid-hydrogen peroxide mixture in the second process is 30% or more and 85% or less of the flow rate Fc1 of the sulfuric acid-hydrogen peroxide mixture in the first process, or it can be 40% or more and 75% or less.

[0144] For example, the temperature Ts2 of the sulfuric acid in the second treatment can also be equal to the temperature Ts1 of the sulfuric acid in the first treatment. In this case, the heating temperature of the heater 55a can remain unchanged in both the first and second treatments. Similarly, the temperature Th2 of the hydrogen peroxide in the second treatment can also be equal to the temperature Th1 of the hydrogen peroxide in the first treatment.

[0145] Furthermore, even if the temperatures of sulfuric acid (Ts2) and hydrogen peroxide (Th2) in the second treatment are equal to those in the first treatment (Ts1 and Th1), the temperature (Tc2) of the sulfuric acid-hydrogen peroxide mixture in the second treatment is different from that in the first treatment. Typically, the temperature (Tc2) of the sulfuric acid-hydrogen peroxide mixture in the second treatment becomes higher than that in the first treatment. This is because the sulfuric acid ratio (Rs2) in the sulfuric acid-hydrogen peroxide mixture is smaller than that in the first treatment (Rs1).

[0146] Furthermore, the sulfuric acid ratio Rc2 in the sulfuric acid-hydrogen peroxide mixture in the second treatment is smaller than the sulfuric acid-hydrogen peroxide ratio Rc1 in the first treatment. Therefore, SPM treatment of the substrate W can be performed efficiently with a smaller amount of sulfuric acid-hydrogen peroxide mixture.

[0147] The rotational speed Rr2 of the substrate W in the second process can also be smaller than the rotational speed Rr1 of the substrate W in the first process. Therefore, SPM treatment of the substrate W can be performed efficiently with a smaller amount of sulfuric acid-hydrogen peroxide mixture.

[0148] However, if the rotation speed Rr2 of the substrate W in the second process is too low, the sulfuric acid-hydrogen peroxide mixture on the substrate W may drip downwards from the substrate W and adhere to the substrate holding portion 20. Therefore, the rotation speed Rr2 of the substrate W in the second process is preferably greater than a predetermined value. For example, the rotation speed Rr2 of the substrate W in the second process may be 100 rpm or more and 500 rpm or less, or 150 rpm or more and 300 rpm or less.

[0149] Next, refer to Figures 1 to 8 The substrate processing method of this embodiment is explained. Figure 8 This is a flowchart of the substrate processing method according to this embodiment.

[0150] like Figure 8 As shown, in step S110, the substrate W is moved into the chamber 11. Under the control of the control unit 102, the central robot CR moves the substrate W into the chamber 11, and the substrate holding unit 20 holds the moved substrate W.

[0151] In step S120, the rotation of the substrate W begins. Under the control of the control unit 102, the substrate holding unit 20 begins the rotation of the substrate W while holding the substrate W in a state.

[0152] In step S130, an etching solution is supplied to the substrate W to perform an etching process on the substrate W. Under the control of the control unit 102, the etching solution supply unit 30 supplies etching solution from the nozzle 36 to the substrate W, which is rotating through the substrate holding unit 20. For example, the etching solution supply unit 30 supplies hydrofluoric acid as the etching solution. In this case, the natural oxide film on the substrate W is removed by the hydrofluoric acid, and the substrate W is hydrophobicated.

[0153] In step S140, rinsing fluid is supplied to the substrate W to perform a rinsing process on the substrate W. Under the control of the control unit 102, the rinsing fluid supply unit 40 supplies rinsing fluid from the nozzle 46 to the substrate W. For example, the rinsing fluid supply unit 40 supplies carbonated water as the rinsing fluid.

[0154] In step S150, a sulfuric acid-hydrogen peroxide mixture is supplied to the substrate W to perform SPM treatment on the substrate W. Under the control of the control unit 102, the SPM supply unit 50 supplies the sulfuric acid-hydrogen peroxide mixture to the substrate W from the nozzle 56. Through SPM treatment, organic matter is removed from the substrate W and a chemical oxide film is generated.

[0155] Step S150 includes: step S152, performing a first process during a first period; and step S154, performing a second process during a second period following the first period. The second period of the second process is longer than the first period of the first process. Typically, the first period is less than 10 seconds, but may also be more than 1 second and less than 5 seconds. On the other hand, the second period is more than 30 seconds, but may also be more than 1 minute and less than 5 minutes.

[0156] In step S152, the substrate W is treated with a sulfuric acid-hydrogen peroxide mixture during the first period. In this first treatment, the substrate W is treated with a sulfuric acid-hydrogen peroxide mixture at a flow rate Fc1 and a sulfuric acid ratio Rc1. At this time, the substrate W rotates at a rotational speed Rr1.

[0157] In step S154, the substrate W is treated with a sulfuric acid-hydrogen peroxide mixture during the second period. In this second treatment, the substrate W is treated with a sulfuric acid-hydrogen peroxide mixture with a flow rate Fc2 and a sulfuric acid ratio Rc2. Here, the flow rate Fc2 is smaller than the flow rate Fc1. Furthermore, the sulfuric acid ratio Rc2 is smaller than the sulfuric acid ratio Rc1. At this time, the substrate W rotates at a rotation speed Rr2. The rotation speed Rr2 can also be lower than the rotation speed Rr1.

[0158] In step S160, hydrogen peroxide is supplied to substrate W to treat substrate W with hydrogen peroxide. Here, the supply of sulfuric acid to substrate W is stopped, while the supply of hydrogen peroxide to substrate W continues. Specifically, valve 54a is closed to stop the flow of sulfuric acid in pipe 52a, while the flow of hydrogen peroxide in pipe 52b continues with valve 54b open. However, the opening degree of valve 54b can be changed as needed to vary the flow rate of hydrogen peroxide in pipe 52b.

[0159] In step S170, rinsing fluid is supplied to the substrate W to perform a rinsing process on the substrate W. Under the control of the control unit 102, the rinsing fluid supply unit 60 supplies rinsing fluid to the substrate W from the nozzle 66. For example, the rinsing fluid supply unit 60 supplies pure water as the rinsing fluid.

[0160] In step S180, the substrate W is dried. Under the control of the control unit 102, the substrate holding unit 20 increases the rotational speed of the substrate W and uses centrifugal force to throw off the rinsing liquid on the substrate W.

[0161] In step S190, the rotation of the substrate W is stopped. The substrate holding unit 20 stops the rotation of the substrate W under the control of the control unit 102.

[0162] In step S200, substrate W is removed from substrate processing unit 10. Under the control of control unit 102, substrate holding unit 20 releases substrate W, and central robot CR removes substrate W from chamber 11. Afterward, substrate W is transported to the outside of substrate processing apparatus 100 via indexing robot IR.

[0163] As described above, the substrate processing method according to this embodiment can process substrate W. According to this embodiment, it can suppress the splashing of sulfuric acid-hydrogen peroxide mixture from substrate W and remove organic matter from substrate W.

[0164] Next, refer to Figures 1 to 10 The substrate processing method in the substrate processing apparatus 100 of this embodiment will be explained. Figure 9 (a) to Figure 10 (c) in this embodiment is a schematic diagram of the substrate processing method.

[0165] like Figure 9 As shown in (a), the substrate holding section 20 holds the substrate W. Under the control of the control section 102, the substrate holding section 20 holds the transported substrate W.

[0166] like Figure 9As shown in (b), the substrate W is rotated and etchant is supplied to the substrate W to perform etching. Under the control of the control unit 102, the substrate holding unit 20 rotates the held substrate W, and the etchant supply unit 30 supplies etchant to the substrate W from the nozzle 36 to perform etching. For example, hydrofluoric acid is supplied to the substrate W from the nozzle 36 to perform hydrofluoric acid treatment on the substrate W. Hydrofluoric acid treatment removes the native oxide film on the substrate W. Hydrofluoric acid treatment hydrophobizes the substrate W.

[0167] like Figure 9 As shown in (c), rinsing fluid is supplied to substrate W to perform a rinsing process on substrate W. Under the control of control unit 102, rinsing fluid supply unit 40 supplies rinsing fluid to substrate W from nozzle 46 to perform a rinsing process on substrate W. For example, carbonated water is supplied to substrate W from nozzle 46 to perform a rinsing process on substrate W.

[0168] like Figure 9 As shown in (d), substrate W is treated with a sulfuric acid-hydrogen peroxide mixture. In the first treatment, substrate W is treated with a sulfuric acid-hydrogen peroxide mixture at a flow rate Fc1 and a sulfuric acid ratio Rc1. Under the control of control unit 102, SPM supply unit 50 supplies the sulfuric acid-hydrogen peroxide mixture to substrate W from nozzle 56, thereby performing SPM treatment on substrate W. Specifically, valve 54a is opened to allow sulfuric acid to flow in pipe 52a, and valve 54b is opened to allow hydrogen peroxide to flow in pipe 52b.

[0169] like Figure 9 As shown in (e), the substrate W is treated with a sulfuric acid-hydrogen peroxide mixture. In the second process, the substrate W is treated with a sulfuric acid-hydrogen peroxide mixture with a flow rate Fc2 and a sulfuric acid ratio Rc2. Under the control of the control unit 102, the SPM supply unit 50 continuously supplies the sulfuric acid-hydrogen peroxide mixture to the substrate W from the nozzle 56, thereby continuously performing SPM treatment on the substrate W.

[0170] In the second process, the flow rate Fc2 is set to be smaller than the flow rate Fc1, and the sulfuric acid ratio Rc2 is set to be smaller than the sulfuric acid ratio Rc1. Specifically, the opening of valve 54a is reduced, thereby decreasing the flow rate of sulfuric acid flowing in pipe 52a. At this time, the opening of valve 54b can also be changed, thereby changing the flow rate of hydrogen peroxide flowing in pipe 52b.

[0171] like Figure 10As shown in (a), hydrogen peroxide is supplied to substrate W, thereby treating substrate W with hydrogen peroxide. Under the control of control unit 102, SPM supply unit 50 supplies hydrogen peroxide to substrate W from nozzle 56, thereby treating substrate W with hydrogen peroxide. Here, the supply of sulfuric acid to substrate W is stopped, while the supply of hydrogen peroxide to substrate W is continuous. Specifically, hydrogen peroxide flows in pipe 52b with valve 54b open, and in this state, valve 54a is closed to stop the flow of sulfuric acid in pipe 52a. At this time, the opening degree of valve 54b can also be changed, thereby changing the flow rate of hydrogen peroxide flowing in pipe 52b.

[0172] like Figure 10 As shown in (b), rinsing fluid is supplied to substrate W to perform rinsing treatment on substrate W. Under the control of control unit 102, rinsing fluid supply unit 60 supplies rinsing fluid to substrate W from nozzle 66 to perform rinsing treatment on substrate W.

[0173] like Figure 10 As shown in (c), the substrate W is dried. Under the control of the control unit 102, the substrate holding unit 20 increases the rotation speed of the rotating substrate W. Then, the rotation of the substrate W is stopped, and the substrate W is removed from the substrate processing unit 10.

[0174] As described above, substrate W can be processed. In this embodiment, substrate W is first treated with a sulfuric acid-hydrogen peroxide mixture with a high flow rate and a high sulfuric acid ratio, and then treated with a sulfuric acid-hydrogen peroxide mixture with a low flow rate and a low sulfuric acid ratio. Therefore, it is possible to suppress the splashing of sulfuric acid-hydrogen peroxide mixture droplets from substrate W and to efficiently perform SPM treatment on substrate W.

[0175] In addition, in reference Figures 1 to 10 In the above description, the SPM treatment is performed in two steps, while the hydrogen peroxide treatment is performed in one step. However, this embodiment is not limited to this. The hydrogen peroxide treatment can also be performed in two steps.

[0176] Next, refer to Figure 11 The substrate processing method of this embodiment is explained. Figure 11 This is a flowchart of the substrate processing method according to this embodiment. Figure 11 The flowchart, except for the point that hydrogen peroxide treatment includes two processing steps, is consistent with the reference. Figure 8 The flowchart above is the same, therefore, to avoid being too lengthy, repeated explanations are omitted.

[0177] like Figure 11 As shown, steps S110 to S154 are... Figure 8 same.

[0178] In step S160, the substrate W, after SPM treatment, is treated with hydrogen peroxide. Here, hydrogen peroxide is supplied to the substrate W, thereby treating the substrate W with hydrogen peroxide. Valve 54a is closed, while valve 54b remains open. The opening degree of valve 54b can also be changed as needed.

[0179] Step S160 includes: step S162, performing a first hydrogen peroxide treatment; and step S164, performing a second hydrogen peroxide treatment. The treatment period for the second hydrogen peroxide treatment is longer than that for the first hydrogen peroxide treatment.

[0180] In step S162, hydrogen peroxide is supplied to the substrate W to perform a first hydrogen peroxide treatment. In this first hydrogen peroxide treatment, the flow rate of hydrogen peroxide flowing in pipe 52b is Fhh1, and the substrate W is treated with hydrogen peroxide at a flow rate of Fhh1. Furthermore, in this first hydrogen peroxide treatment, the substrate W is treated with hydrogen peroxide at a flow rate of Fhh1.

[0181] In step S164, hydrogen peroxide is supplied to the substrate W to perform a second hydrogen peroxide treatment. In the second hydrogen peroxide treatment, the flow rate of hydrogen peroxide flowing in the pipe 52b is Fhh2, and the flow rate Fhh2 in the second hydrogen peroxide treatment is greater than the flow rate Fhh1 in the first hydrogen peroxide treatment.

[0182] After that, with Figure 8 Similarly, proceed to steps S170 to S200.

[0183] As described above, substrate W can be processed. In this embodiment, substrate W is first treated with a sulfuric acid-hydrogen peroxide mixture with a high flow rate and a high sulfuric acid ratio, and then treated with a sulfuric acid-hydrogen peroxide mixture with a low flow rate and a low sulfuric acid ratio. Therefore, it is possible to suppress the splashing of sulfuric acid-hydrogen peroxide mixture droplets from substrate W and to efficiently perform SPM treatment on substrate W.

[0184] Furthermore, since the flow rate Fhh1 of the first hydrogen peroxide treatment after SPM treatment of the substrate W is relatively low, excessive reaction between residual sulfuric acid on the substrate W and hydrogen peroxide, preventing liquid splashing, can be suppressed. In addition, a higher flow rate Fhh2 of hydrogen peroxide is supplied in the subsequent second hydrogen peroxide treatment, thereby effectively removing residual sulfuric acid from the substrate W.

[0185] Next, refer to Figures 1 to 13 The substrate processing apparatus 100 of this embodiment will be described. Figure 12 This is a schematic diagram of the substrate processing unit 10 in the substrate processing apparatus 100 of this embodiment. Figure 13 for Figure 12 A schematic top view of the substrate processing unit 10. Figure 12The substrate processing unit 10 also includes a chemical supply unit 70 and a rinsing liquid supply unit 80. The nozzles 36 of the etching liquid supply unit 30, the nozzles 56 of the SPM supply unit 50, and the nozzles 66 of the rinsing liquid supply unit 60 are integrally provided. A scattering suppression member 59 is installed on the nozzle 56 for ejecting SPM in an inclined direction. In addition to the above points, Figure 12 The substrate processing unit 10 has a common feature with Figure 2 The substrate processing unit 10 in the substrate processing apparatus 100 shown has the same configuration, so repeated descriptions are omitted to avoid being too lengthy.

[0186] like Figure 12 As shown, the substrate processing unit 10 also includes a drug supply unit 70 and a rinsing solution supply unit 80. The drug supply unit 70 supplies drug solution to the substrate W. Typically, the drug supply unit 70 supplies drug solution to the upper surface Wa of the substrate W. At least a portion of the drug supply unit 70 is housed within the chamber 11.

[0187] The solution supply unit 70 supplies a solution to the upper surface Wa of the substrate W. The solution includes SC1 (a mixture of ammonia, hydrogen peroxide, and water).

[0188] The drug supply unit 70 includes a pipe 72, a valve 74, and a nozzle 76. The nozzle 76 sprays drug solution onto the upper surface Wa of the substrate W. The nozzle 76 is connected to the pipe 72. Drug solution is supplied to the pipe 72 from a supply source. The valve 74 opens and closes the flow path within the pipe 72.

[0189] Valve 74 opens and closes the flow path within piping 72. Valve 74 adjusts the opening degree of piping 72 to regulate the flow rate of the liquid medicine supplied to piping 72. Specifically, valve 74 includes: a valve body (not shown) with a valve seat disposed internally; a valve body for opening and closing the valve seat; and an actuator (not shown) for moving the valve body between an open position and a closed position.

[0190] The nozzle 76 can also be configured to move relative to the substrate W. The liquid supply unit 70 may also include a nozzle moving part 78. The nozzle moving part 78 can raise and lower the nozzle 76, and can also rotate the nozzle 76 horizontally about a rotation axis. The nozzle moving part 78 raises and lowers the nozzle 76. For example, the nozzle moving part 78 includes a ball screw mechanism and an electric motor that provides driving force to the ball screw mechanism. Furthermore, the nozzle moving part 78 rotates the nozzle 76 horizontally. For example, the nozzle moving part 78 includes an electric motor.

[0191] The rinsing fluid supply unit 80 supplies rinsing fluid to the substrate W. Typically, the rinsing fluid supply unit 80 supplies rinsing fluid to the upper surface Wa of the substrate W. At least a portion of the rinsing fluid supply unit 80 is housed within the chamber 11.

[0192] The rinsing fluid supply unit 80 supplies rinsing fluid to the upper surface Wa of the substrate W. The rinsing fluid includes deionized water (DIW), electrolyzed water, or ozone water. Alternatively, the rinsing fluid may be a liquid other than these. For example, ammonia, hydrochloric acid diluted to a concentration of approximately 10 ppm to 100 ppm, and reduced water (hydrogen water) may also be used as rinsing fluids.

[0193] The rinsing fluid supply unit 80 includes a pipe 82, a valve 84, and a nozzle 86. The nozzle 86 sprays rinsing fluid onto the upper surface Wa of the substrate W. The nozzle 86 is connected to the pipe 82. Rinsing fluid is supplied to the pipe 82 from a supply source. The valve 84 opens and closes the flow path within the pipe 82. The nozzle 86 may also be configured to be movable relative to the substrate W.

[0194] Valve 84 opens and closes the flow path within piping 82. Valve 84 adjusts the opening degree of piping 82 to regulate the flow rate of flushing fluid supplied to piping 82. Specifically, valve 84 includes: a valve body (not shown) with a valve seat disposed internally; a valve body for opening and closing the valve seat; and an actuator (not shown) for moving the valve body between an open position and a closed position. Nozzle 86 may also be configured to be movable relative to the substrate W.

[0195] The nozzles 36 of the etching solution supply unit 30, 56 of the SPM supply unit 50, and 66 of the rinsing solution supply unit 60 are integrally provided. Therefore, when switching the type of liquid supplied to the substrate W, the travel time of the nozzles 36, 56, and 66 can be shortened, thereby increasing the processing capacity of the substrate.

[0196] Here, nozzle 56 sprays a mixture of sulfuric acid and hydrogen peroxide in a downward-right direction. Because nozzle 56 sprays the mixture in an inclined direction, even if droplets of the sulfuric acid and hydrogen peroxide mixture splash from the substrate W, it can prevent droplets from adhering to nozzle 56.

[0197] Furthermore, a splash suppression member 59 is installed on the nozzle 56. The splash suppression member 59 is installed on the nozzle 56 in the direction in which the sulfuric acid-hydrogen peroxide mixture is ejected from the nozzle 56. The splash suppression member 59 is opposite to the position in the substrate W where the sulfuric acid-hydrogen peroxide mixture ejected from the nozzle 56 reaches the substrate W. Thus, even if the sulfuric acid-hydrogen peroxide mixture ejected onto the substrate W splashes from the substrate W, the splash suppression member 59 can suppress droplets from the substrate W from adhering to the surrounding area.

[0198] In addition, such as Figure 13As shown, the scattering suppression member 59 is housed together with the nozzle 56 in the standby port 92. When the nozzle 56 is positioned in the standby position, the standby port 92 is positioned overlapping with the nozzle 56 and the scattering suppression member 59. The standby port 92 houses the nozzle 56 and the scattering suppression member 59. Furthermore, it is preferable that the nozzle 56 and the scattering suppression member 59 can be cleaned within the standby port 92.

[0199] Next, refer to Figures 12 to 14 The substrate processing method of this embodiment is explained. Figure 14 This is a flowchart of the substrate processing method according to this embodiment. Figure 14 In addition to the points for drug treatment and rinsing, the flowchart also includes reference points. Figure 8 The flowchart above is the same, so repeated explanations are omitted to avoid being too lengthy.

[0200] like Figure 14 As shown, steps S110 to S170 are... Figure 8 same.

[0201] Following step S170, in step S200, a chemical solution is supplied to the substrate W. Therefore, the substrate W is treated with the chemical solution. Under the control of the control unit 102, the chemical solution supply unit 70 supplies the chemical solution to the substrate W from the nozzle 76.

[0202] In step S210, rinsing fluid is supplied to the substrate W. Therefore, the substrate W is rinsed. Under the control of the control unit 102, the rinsing fluid supply unit 80 supplies rinsing fluid to the substrate W from the nozzle 86.

[0203] After step S210, the substrate W is dried in step S180. Therefore, the substrate W is dried. Since steps S180 to S200 are related to... Figure 8 Since they are the same, the explanation is omitted.

[0204] The embodiments of the present invention have been described above with reference to the accompanying drawings. However, the present invention is not limited to the above embodiments and can be implemented in various embodiments without departing from the spirit of the invention. Furthermore, the plurality of constituent elements disclosed in the above embodiments can be appropriately modified. For example, one of the constituent elements shown in one embodiment may be added to the constituent elements of another embodiment, or several of the constituent elements shown in one embodiment may be deleted from the embodiment.

[0205] To facilitate understanding of the present invention, the accompanying drawings illustrate the main components schematically. The thickness, length, number, and spacing of the illustrated components may differ from the actual figures due to the nature of the drawings. Furthermore, the configuration of the components shown in the above embodiments is an example and is not particularly limited; various modifications can be made without substantially departing from the technical effects of the present invention.

[0206] For example, in Figure 2 , Figure 7 , Figure 9 , Figure 10 as well as Figure 12 In the substrate processing unit 10 shown, although the sulfuric acid and hydrogen peroxide mixture is generated by mixing sulfuric acid and hydrogen peroxide in the nozzle 56 within the chamber 11, this embodiment is not limited to this. The sulfuric acid and hydrogen peroxide mixture can also be generated by mixing sulfuric acid and hydrogen peroxide outside the chamber 11.

[0207] Industrial availability

[0208] This invention can be applied to the fields of substrate processing apparatus and substrate processing methods.

[0209] Explanation of reference numerals in the attached figures:

[0210] 20: Substrate holding section

[0211] 30: Etching Solution Supply Department

[0212] 40: Fluid Supply Department

[0213] 50: SPM Supply Department

[0214] 60: Fluid Supply Department

[0215] 100: Substrate processing apparatus

[0216] 101: Control device

[0217] 102: Control Department

[0218] 104: Storage Department

Claims

1. A substrate processing apparatus, wherein there is provided: a substrate holding section that holds a substrate and rotates the substrate; and a mixed liquid supply section that supplies a sulfuric acid hydrogen peroxide mixed liquid, in which sulfuric acid and hydrogen peroxide are mixed, to the substrate that is rotated by the substrate holding section; the mixed liquid supply section supplies the sulfuric acid hydrogen peroxide mixed liquid to the substrate at a first flow rate in a first period, and supplies the sulfuric acid hydrogen peroxide mixed liquid to the substrate at a second flow rate that is smaller than the first flow rate in a second period that follows the first period; the proportion of the sulfuric acid in the sulfuric acid hydrogen peroxide mixed liquid in the second period is smaller than the proportion of the sulfuric acid in the sulfuric acid hydrogen peroxide mixed liquid in the first period.

2. The substrate processing apparatus according to claim 1, wherein the substrate processing apparatus further has an etching liquid supply section that supplies an etching liquid to the substrate before the mixed liquid supply section supplies the sulfuric acid hydrogen peroxide mixed liquid to the substrate.

3. The substrate processing apparatus according to claim 2, wherein the etching liquid supply section supplies hydrofluoric acid or diluted hydrofluoric acid as the etching liquid to the substrate.

4. The substrate processing apparatus according to claim 1, wherein the mixed liquid supply section supplies the sulfuric acid hydrogen peroxide mixed liquid, which is generated by mixing the sulfuric acid at 130°C or higher and 200°C or lower with the hydrogen peroxide at room temperature, to the substrate.

5. The substrate processing apparatus according to any one of claims 1 to 4, wherein the mixed liquid supply section supplies the sulfuric acid hydrogen peroxide mixed liquid, in which the sulfuric acid and the hydrogen peroxide are mixed at a ratio of 4: 1 to 9: 1, to the substrate in the first period, and supplies the sulfuric acid hydrogen peroxide mixed liquid, in which the sulfuric acid and the hydrogen peroxide are mixed at a ratio of 2: 1 to 3: 1, to the substrate in the second period.

6. The substrate processing apparatus according to claim 1, wherein the second period is longer than the first period.

7. The substrate processing apparatus according to claim 1, wherein the substrate holding section rotates the substrate at a first rotation speed in the first period, and rotates the substrate at a second rotation speed in the second period that follows the first period; the second rotation speed is smaller than the first rotation speed.

8. The substrate processing apparatus according to claim 1, wherein the mixed liquid supply section supplies the hydrogen peroxide to the substrate after the second period.

9. The substrate processing apparatus according to claim 1, wherein the substrate processing apparatus further has a flying inhibition member that inhibits droplets of the sulfuric acid hydrogen peroxide mixed liquid from flying from the substrate.

10. A substrate processing method, comprising a sulfuric acid hydrogen peroxide mixed liquid processing step of supplying a sulfuric acid hydrogen peroxide mixed liquid, in which sulfuric acid and hydrogen peroxide are mixed, to a substrate that is held and rotated by a substrate holding section, and thereby processing the substrate with the sulfuric acid hydrogen peroxide mixed liquid, wherein the sulfuric acid hydrogen peroxide mixed liquid processing step includes: a first processing step of processing the substrate by supplying the sulfuric acid hydrogen peroxide mixed liquid to the substrate at a first flow rate in a first period; and a second treatment step of treating the substrate with the sulfuric acid hydrogen peroxide mixture at a second flow rate smaller than the first flow rate during a second period after the first period; the proportion of the sulfuric acid in the sulfuric acid hydrogen peroxide mixture during the second period is smaller than the proportion of the sulfuric acid in the sulfuric acid hydrogen peroxide mixture during the first period.

11. The substrate treatment method according to claim 10, wherein the substrate treatment method further includes an etching step of treating the substrate with an etching liquid before the sulfuric acid hydrogen peroxide mixture treatment step.

12. The substrate treatment method according to claim 11, wherein in the etching step, hydrofluoric acid or diluted hydrofluoric acid is supplied to the substrate as the etching liquid.

13. The substrate treatment method according to claim 10, wherein in the sulfuric acid hydrogen peroxide mixture treatment step, the sulfuric acid hydrogen peroxide mixture generated by mixing the sulfuric acid at 130°C or higher and 220°C or lower with the hydrogen peroxide at room temperature is supplied to the substrate.

14. The substrate treatment method according to any one of claims 10 to 13, wherein the first treatment step supplies the sulfuric acid hydrogen peroxide mixture in which the sulfuric acid and the hydrogen peroxide are mixed at a ratio of 4: 1 to 9: 1 to the substrate during the first period; the second treatment step supplies the sulfuric acid hydrogen peroxide mixture in which the sulfuric acid and the hydrogen peroxide are mixed at a ratio of 2: 1 to 3: 1 to the substrate during the second period.

15. The substrate treatment method according to claim 10, wherein the second period is longer than the first period.

16. The substrate treatment method according to claim 10, wherein in the sulfuric acid hydrogen peroxide mixture treatment step, the substrate is rotated at a second rotation speed during the second period after the substrate is rotated at a first rotation speed during the first period; the second rotation speed is smaller than the first rotation speed.

17. The substrate treatment method according to claim 10, further comprising a step of supplying the hydrogen peroxide to the substrate after the second period, thereby treating the substrate with the hydrogen peroxide.

18. The substrate treatment method according to claim 10, wherein in the sulfuric acid hydrogen peroxide mixture treatment step, droplet scattering of the sulfuric acid hydrogen peroxide mixture is suppressed by a scattering suppression member opposite to a position on the substrate at which the sulfuric acid hydrogen peroxide mixture reaches the substrate. ​

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