Substrate processing apparatus and substrate processing method

Abstract

A substrate processing apparatus (100) is provided with: a substrate holding unit (20) that holds a substrate (W) and rotates the substrate (W); and a mixed solution supply unit (50) that supplies a sulfuric acid / hydrogen peroxide mixed solution in which sulfuric acid and hydrogen peroxide are mixed to the substrate (W) rotated by the substrate holding unit (20). The mixed solution supply unit (50) 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 sulfuric acid in the sulfuric acid and hydrogen peroxide mixed solution in the second period is smaller than the proportion of sulfuric acid in the sulfuric acid and hydrogen peroxide mixed solution in the first period.

Description

Technical Field

[0001] The invention relates to a substrate processing device and a substrate processing method. Background Art

[0002] Conventionally, in the manufacturing process of a device including a substrate such as a semiconductor device or a liquid crystal display device, a substrate processing device for processing 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 process for removing objects fixed to the surface of a substrate, a SPM (sulfuric acid hydrogen peroxide mixture) process is known. In the SPM process, a sulfuric acid hydrogen peroxide mixture containing sulfuric acid and hydrogen peroxide is supplied to the substrate to remove objects fixed to the surface of the substrate.

[0004] Patent document 1 describes an SPM process in which a substrate is treated with a high-temperature SPM. In the substrate processing device of patent document 1, the ejection position of the SPM nozzle is moved from the center of the substrate to the outside according to the resist residue in the SPM photographed by the camera, thereby efficiently peeling off the object fixed to the surface of the substrate. In addition, patent document 1 also describes the following: after treating the substrate with a first SPM containing rich hydrogen peroxide, the substrate is treated with a second SPM containing rich sulfuric acid. According to the method of patent document 1, the remaining object can be well removed by the second SPM.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: Japanese Patent Application Publication No. 2020-107779 Summary of the invention

[0008] Problems to be solved by the invention

[0009] In the substrate processing device of Patent Document 1, a high-temperature SPM is supplied to the substrate, so that the substrate can be efficiently subjected to SPM treatment. However, when the substrate is treated with a high-temperature sulfuric acid and hydrogen peroxide mixture, droplets of the sulfuric acid and hydrogen peroxide mixture on the substrate will splash around. In this way, when droplets of the sulfuric acid and hydrogen peroxide mixture splash from the substrate and adhere to a certain component, the substrate will be contaminated by the attached matter in the subsequent process. On the other hand, when the SPM treatment is performed with a low-temperature SPM, the efficiency of the SPM treatment will be reduced.

[0010] The present invention 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, which can suppress splashing of droplets of sulfuric acid and hydrogen peroxide mixed liquid from a substrate and can efficiently perform SPM processing on the substrate.

[0011] Means for solving problems

[0012] A substrate processing device according to an embodiment of the present invention comprises: a substrate holding portion that holds a substrate and rotates the substrate; and a mixed liquid supply portion that supplies a sulfuric acid-hydrogen peroxide mixed liquid mixed with sulfuric acid and hydrogen peroxide to the substrate rotated by the substrate holding portion. The mixed liquid supply portion 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 smaller than the first flow rate in a second period after 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.

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

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

[0015] In one embodiment, the mixed liquid supply unit supplies the sulfuric acid-hydrogen peroxide mixed liquid generated by mixing the sulfuric acid at a temperature of 130° C. to 200° C. with the hydrogen peroxide at room temperature to the substrate.

[0016] In one embodiment, the mixed liquid supply unit supplies the sulfuric acid-hydrogen peroxide mixed liquid formed by mixing the sulfuric acid and the hydrogen peroxide in a ratio of 4:1 to 9:1 to the substrate during the first period, and supplies the sulfuric acid-hydrogen peroxide mixed liquid formed by mixing the sulfuric acid and the hydrogen peroxide in 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 portion rotates the substrate at a first rotation speed in the first period and then rotates the substrate at a second rotation speed in the second period; the second rotation speed is lower than the first rotation speed.

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

[0020] In one embodiment, the substrate processing apparatus further includes a scattering suppression member configured to suppress scattering of droplets of the sulfuric acid-hydrogen peroxide mixed liquid from the substrate.

[0021] A substrate processing method according to another embodiment of the present invention includes an SPM processing step of supplying a sulfuric acid-hydrogen peroxide mixed solution containing sulfuric acid and hydrogen peroxide to a substrate held and rotated by a substrate holding portion, thereby treating the substrate with the sulfuric acid-hydrogen peroxide mixed solution, wherein the SPM processing step includes: a first processing step of supplying the sulfuric acid-hydrogen peroxide mixed solution to the substrate at a first flow rate during a first period to treat the substrate; and a second processing step of supplying 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 to treat the substrate; 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.

[0022] In one embodiment, the substrate processing method further includes: an etching process, in which the substrate is processed with an etching solution before the SPM processing process.

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

[0024] In one embodiment, in the SPM treatment step, the sulfuric acid-hydrogen peroxide mixed solution generated by mixing the sulfuric acid at 130° C. or higher and 220° C. or lower with the hydrogen peroxide solution at room temperature is supplied to the substrate.

[0025] In one embodiment, in the first treatment process, during the first period, the sulfuric acid-hydrogen peroxide mixed liquid formed by mixing the sulfuric acid and the hydrogen peroxide in a ratio of 4:1 to 9:1 is supplied to the substrate; in the second treatment process, during the second period, the sulfuric acid-hydrogen peroxide mixed liquid formed by mixing the sulfuric acid and the hydrogen peroxide in a ratio of 2:1 to 3:1 is supplied to the substrate.

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

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

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

[0029] In one embodiment, in the SPM treatment step, scattering of droplets of the sulfuric acid-hydrogen peroxide mixed solution is suppressed by a scattering suppression member that faces a position in the substrate where the sulfuric acid-hydrogen peroxide mixed solution reaches the substrate.

[0030] Effects of the Invention

[0031] According to the present invention, a substrate processing apparatus and a substrate processing method can be provided, which can suppress splashing of droplets of sulfuric acid and hydrogen peroxide mixed liquid from a substrate and can efficiently perform SPM processing on the substrate. BRIEF DESCRIPTION OF THE DRAWINGS

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

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

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

[0035] Figure 4 Graph showing the number of droplets of the sulfuric acid-hydrogen peroxide mixed solution splashed from the substrate according to the temperature of the sulfuric acid-hydrogen peroxide mixed solution.

[0036] Figure 5 This is a graph showing the number of droplets of the sulfuric acid-hydrogen peroxide mixed solution splashed from the substrate according to the sulfuric acid ratio and flow rate of the sulfuric acid-hydrogen peroxide mixed solution.

[0037] Figure 6 The table shows the flow rate of the sulfuric acid-hydrogen peroxide mixed solution and the sulfuric acid ratio in the first process and the second process included in the SPM process in the substrate processing method according to the present embodiment.

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

[0039] Figure 8 Flowchart of the substrate processing method according to the present embodiment.

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

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

[0042] Fig.11 Flowchart of the substrate processing method according to the present embodiment.

[0043] Fig.12 It is a schematic diagram of a substrate processing unit in the substrate processing apparatus according to this embodiment.

[0044] Fig.13 It is a schematic top view of a substrate processing unit in the substrate processing apparatus according to the present embodiment.

[0045] Fig.14 Flowchart of the substrate processing method according to the present embodiment. DETAILED DESCRIPTION

[0046] Hereinafter, embodiments of the substrate processing device and the substrate processing method of the present invention are described with reference to the accompanying drawings. In addition, the same reference numerals are attached to the same or equivalent parts in the figures and the description is not repeated. In addition, in order to facilitate the understanding of the present invention, the description of the present application will record the X-axis, Y-axis and Z-axis that are orthogonal to each other. Typically, the X-axis and the 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 a substrate processing apparatus 100 according to the present invention will be described. Figure 1 It is a schematic top view of the substrate processing apparatus 100 according to the present embodiment.

[0048] The substrate processing apparatus 100 processes the substrate W. The substrate processing apparatus 100 processes the substrate W by performing at least one of etching, surface processing, imparting characteristics, forming a processing film, removing at least a portion of a film, and cleaning the substrate W.

[0049] The substrate W is used as a semiconductor substrate. The substrate W includes a semiconductor wafer. For example, the substrate W is substantially disk-shaped. Here, the substrate processing apparatus 100 processes the substrate W piece by piece.

[0050] like Figure 1 As shown, the substrate processing apparatus 100 has a plurality of substrate processing units 10, a processing liquid tank 110, a processing liquid tank 120, a plurality of loading ports LP, an indexer robot IR, a central robot CR, and a control device 101. The control device 101 controls the loading port 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 transport unit.

[0051] The loading port LP accommodates a plurality of substrates W in a stacked manner. The indexer robot IR transports the substrates W between the loading port LP and the central robot CR. The central robot CR transports the substrates W between the indexer robot IR and the substrate processing unit 10. The substrate processing unit 10 sprays a processing liquid onto the substrate W to process the substrate W. The processing liquid includes a chemical solution, a rinse solution, a removal liquid and / or a water repellent. The processing liquid cabinet 110 accommodates the processing liquid. In addition, the processing liquid cabinet 110 may also accommodate gas.

[0052] Specifically, the plurality of substrate processing units 10 form a plurality of towers TW (in Figure 1 The towers TW are arranged so as to surround the central robot CR in a plan view. Each tower TW includes a plurality of substrate processing units 10 stacked up and down (in Figure 1 There are three substrate processing units 10 in the figure. The processing liquid tanks 120 correspond to the plurality of towers TW, respectively. The liquid in the processing liquid tank 110 is supplied to all the substrate processing units 10 included in the tower TW corresponding to the processing liquid tank 120 via any processing liquid tank 120. In addition, the gas in the processing liquid tank 110 is supplied to all the substrate processing units 10 included in the tower TW corresponding to the processing liquid tank 120 via any processing liquid tank 120.

[0053] Typically, the treatment liquid cabinet 110 has a storage tank (tank) for modulating the treatment liquid. The treatment liquid cabinet 110 may also have a storage tank for one type of treatment liquid, or may have storage tanks for a plurality of types of treatment liquids. In addition, the treatment liquid cabinet 110 may also have a pump, a valve, and / or a filter for circulating the treatment liquid.

[0054] The control device 101 controls various operations of the substrate processing apparatus 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 includes a processor. The control unit 102 includes, for example, a central processing unit (CPU). Alternatively, the control unit 102 may include a general-purpose computing unit.

[0056] The storage unit 104 stores data and computer programs. The data includes recipe data. The recipe data includes information for indicating a plurality of recipes. The plurality of recipes respectively define the processing contents 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 a removable media. The control unit 102 executes the computer program stored in the storage unit 104 to perform the substrate processing operation.

[0058] Next, refer to Figure 2 The substrate processing unit 10 in the substrate processing apparatus 100 according to the present embodiment will be described. Figure 2 Schematic diagram of a substrate processing unit 10 in a substrate processing apparatus 100 .

[0059] The substrate processing unit 10 includes a chamber 11 , a blower unit 12 , a substrate holding unit 20 , an etching liquid supply unit 30 , a rinse liquid supply unit 40 , an SPM supply unit 50 , and a rinse liquid supply unit 60 .

[0060] The chamber 11 is substantially box-shaped with an internal space. The chamber 11 accommodates the substrate W. Here, the substrate processing apparatus 100 is a single-chip type for processing the substrate W piece by piece, and the substrate W is accommodated piece by piece in the chamber 11. The substrate W is accommodated in the chamber 11 and processed in the chamber 11. The chamber 11 accommodates at least a part of each of the substrate holding part 20, the etching liquid supply part 30, the rinse liquid supply part 40, the SPM supply part 50, and the rinse liquid supply part 60.

[0061] The 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 (downflow) is formed in the chamber 11 by the air supply unit 12 and the exhaust device (not shown).

[0062] The substrate holding part 20 holds the substrate W. The substrate holding part 20 holds the substrate W horizontally in a manner that the upper surface (front surface) Wa of the substrate W faces upward and the back surface (lower surface) Wb of the substrate W faces vertically downward. In addition, the substrate holding part 20 rotates the substrate W while holding the substrate W. For example, a stacked structure having a recess is provided on the upper surface Wa of the substrate W. The substrate holding part 20 rotates the substrate W while holding the substrate W.

[0063] For example, the substrate holding portion 20 may be a clamping type for clamping the end of the substrate W. Alternatively, the substrate holding portion 20 may have any mechanism for holding the substrate W from the back side Wb. For example, the substrate holding portion 20 may be a vacuum type. In this case, the substrate holding portion 20 holds the substrate W horizontally by adsorbing the central portion of the back side Wb of the substrate W, which is the non-device forming surface, to the upper surface. Alternatively, the substrate holding portion 20 may be a combination of a clamping type in which a plurality of clamp pins are in contact with the peripheral end surface of the substrate W and a vacuum type.

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

[0065] The shaft 23 extends in the vertical direction along the rotation axis Ax. The spin base 21 is coupled to the upper end of the shaft 23. The substrate W is placed above the spin base 21.

[0066] The rotating base 21 is in the shape of a disk. The clamp member 22 supports the substrate W horizontally. The shaft 23 extends downward from the center of the rotating base 21. The rotating motor 24 applies a rotational force to the shaft 23. The rotating motor 24 rotates the shaft 23 in the rotation direction, thereby rotating the substrate W and the rotating base 21 around the rotation axis Ax. The housing 25 accommodates the shaft 23 and the rotating motor 24.

[0067] The etching liquid supply unit 30 supplies the etching liquid to the substrate W. Typically, the etching liquid supply unit 30 supplies the etching liquid to the upper surface Wa of the substrate W. At least a part of the etching liquid supply unit 30 is accommodated in the chamber 11 .

[0068] The etching liquid supply unit 30 supplies etching liquid to the upper surface Wa of the substrate W. The etching liquid includes hydrofluoric acid or diluted hydrofluoric acid. For example, the hydrofluoric acid may be heated to 40° C. to 70° C. or 50° C. to 60° C. However, the hydrofluoric acid may not be heated.

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

[0070] The valve 34 opens and closes the flow path in the pipe 32. The valve 34 adjusts the opening of the pipe 32 to adjust the flow rate of the etching solution supplied to the pipe 32. Specifically, the valve 34 includes: a valve body (not shown) having a valve seat disposed therein; a valve body that opens and closes the valve seat; and an actuator (not shown) that moves the valve body between an open position and a closed position.

[0071] The nozzle 36 may also be configured to be movable relative to the substrate W. The etching liquid supply unit 30 may also include a nozzle moving unit 38. The nozzle moving unit 38 may move the nozzle 36 up and down, or may rotate the nozzle 36 horizontally around the rotation axis. The nozzle moving unit 38 moves the nozzle 36 up and down. For example, the nozzle moving unit 38 includes: a ball screw mechanism; and an electric motor that applies a driving force to the ball screw mechanism. In addition, the nozzle moving unit 38 rotates the nozzle 36 horizontally. For example, the nozzle moving unit 38 includes an electric motor.

[0072] The rinse liquid supply unit 40 supplies the rinse liquid to the substrate W. Typically, the rinse liquid supply unit 40 supplies the rinse liquid to the upper surface Wa of the substrate W. At least a portion of the rinse liquid supply unit 40 is accommodated in the chamber 11 .

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

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

[0075] The valve 44 opens and closes the flow path in the pipe 42. The valve 44 adjusts the opening of the pipe 42 to adjust the flow rate of the flushing liquid supplied to the pipe 42. Specifically, the valve 44 includes: a valve body (not shown) having a valve seat disposed therein; a valve body that opens and closes the valve seat; and an actuator (not shown) that moves the valve body between an open position and a closed position.

[0076] The nozzle 46 may be movable. The nozzle 46 may be movable in the horizontal direction and / or the vertical direction by a moving mechanism controlled by the control unit 102 .

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

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

[0079] Here, the nozzle 56 is connected to the pipe 52a and the pipe 52b. Sulfuric acid is supplied to the pipe 52a from a supply source. The valve 54a opens and closes the flow path in the pipe 52a. The valve 54a adjusts the opening of the pipe 52a to adjust the flow rate of sulfuric acid supplied to the pipe 52a. Specifically, the valve 54a includes: a valve body (not shown) having a valve seat provided therein; a valve body that opens and closes the valve seat; and an actuator (not shown) that moves the valve body between an open position and a closed position.

[0080] The pump 57a allows sulfuric acid to flow through the pipe 52a. The heater 55a heats the sulfuric acid flowing through the pipe 52a. The temperature of the sulfuric acid can be adjusted by the heater 55a. The heater 55a heats the sulfuric acid flowing through the pipe 52a and adjusts the temperature of the sulfuric acid (for example, about 70° C. to 220° C.). The heater 55a can also heat the sulfuric acid and measure the temperature of the sulfuric acid.

[0081] Hydrogen peroxide is supplied from a supply source to the pipe 52b. The valve 54b opens and closes the flow path in the pipe 52b. The valve 54b adjusts the opening of the pipe 52b to adjust the flow rate of the hydrogen peroxide supplied to the pipe 52b. Specifically, the valve 54b includes: a valve body (not shown) having a valve seat disposed therein; a valve body that opens and closes the valve seat; and an actuator (not shown) that moves the valve body between an open position and a closed position.

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

[0083] The nozzle 56 may also be configured to be movable relative to the substrate W. The SPM supply unit 50 may also include a nozzle moving unit 58. The nozzle moving unit 58 may also move the nozzle 56 up and down, or may rotate the nozzle 56 horizontally around the rotation axis. The nozzle moving unit 58 moves the nozzle 56 up and down. For example, the nozzle moving unit 58 includes: a ball screw mechanism; and an electric motor that provides a 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] In addition, when the valve 54a is opened so that sulfuric acid flows in the pipe 52a and the valve 54b is opened so that hydrogen peroxide flows in the pipe 52b, the SPM supply unit 50 supplies the sulfuric acid-hydrogen peroxide mixed liquid from the nozzle 56 to the substrate W. In addition, when the valve 54a is closed so that sulfuric acid does not flow in the pipe 52a and the valve 54b is opened so that hydrogen peroxide flows in the pipe 52b, the SPM supply unit 50 supplies hydrogen peroxide to the substrate W from the nozzle 56. Furthermore, when the valve 54a is opened so that sulfuric acid flows in the pipe 52a and the valve 54b is closed so that hydrogen peroxide does not flow in the pipe 52b, the SPM supply unit 50 supplies sulfuric acid to the substrate W from the nozzle 56.

[0085] The rinse liquid supply unit 60 supplies the rinse liquid to the substrate W. Typically, the rinse liquid supply unit 60 supplies the rinse liquid to the upper surface Wa of the substrate W. At least a portion of the rinse liquid supply unit 60 is accommodated in the chamber 11 .

[0086] The rinse liquid supply unit 60 supplies the rinse liquid to the upper surface Wa of the substrate W. For example, deionized water (DIW), carbonated water, electrolytic ionized water, ozone water, ammonia water, diluted hydrochloric acid water (e.g., about 10 ppm to 100 ppm), and reduced water (hydrogen water) can be cited as the rinse liquid.

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

[0088] The valve 64 opens and closes the flow path in the pipe 62. The valve 64 adjusts the opening of the pipe 62 to adjust the flow rate of the flushing liquid supplied to the pipe 62. Specifically, the valve 64 includes: a valve body (not shown) having a valve seat disposed therein; a valve body that opens and closes the valve seat; and an actuator (not shown) that moves the valve body between an open position and a closed position.

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

[0090] The substrate processing unit 10 further includes a cup 90. The cup 90 recovers the processing liquid scattered from the substrate W. The cup 90 is raised and lowered. For example, while the etching liquid supply unit 30, the rinsing liquid supply unit 40, the SPM supply unit 50 and / or the rinsing liquid supply unit 60 are supplying etching liquid, rinsing liquid, SPM and / or rinsing liquid to the substrate W, the cup 90 rises vertically upward to the side of the substrate W. In this case, the cup 90 recovers the etching liquid, rinsing liquid, SPM and / or rinsing liquid scattered from the substrate W due to the rotation of the substrate W. In addition, when the etching liquid supply unit 30, the rinsing liquid supply unit 40, the SPM supply unit 50 and / or the rinsing liquid supply unit 60 are supplying etching liquid, rinsing liquid, SPM and / or rinsing liquid to the substrate W, the cup 90 descends vertically downward from the side of the substrate W.

[0091] As described above, the control device 101 includes the control unit 102 and the storage unit 104. The control unit 102 controls the air supply unit 12, the substrate holding unit 20, the etching liquid supply unit 30, the rinse liquid supply unit 40, the SPM supply unit 50, the rinse liquid 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, the valves 34, 44, 54a, 54b, 64, the nozzle moving units 38, 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 a semiconductor element provided with a semiconductor. Typically, in a semiconductor element, 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 change, etc.) the conductive layer and / or the insulating layer when manufacturing a semiconductor element.

[0093] Next, refer to Figures 1 to 3 A substrate processing apparatus 100 according to this embodiment will be described. Figure 3 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 indexer robot IR, the center robot CR, the air supply unit 12, the substrate holding part 20, the etching liquid supply part 30, the rinse liquid supply part 40, the SPM supply part 50, the rinse liquid supply part 60, and the cup 90. Specifically, the control device 101 controls the indexer robot IR, the center robot CR, the air supply unit 12, the substrate holding part 20, the etching liquid supply part 30, the rinse liquid supply part 40, the SPM supply part 50, the rinse liquid supply part 60, and the cup 90 by sending control signals to the indexer robot IR, the center robot CR, the air supply unit 12, the substrate holding part 20, the etching liquid supply part 30, the rinse liquid supply part 40, the SPM supply part 50, the rinse liquid supply part 60, and the cup 90.

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

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

[0097] The control unit 102 controls the central robot CR to transfer the substrates W. For example, the central robot CR receives an unprocessed substrate W and carries the substrate W into any one of the plurality of chambers 11. In addition, the central robot CR receives a processed substrate W from the chamber 11 and carries the substrate W out.

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

[0099] The control unit 102 controls the substrate holding unit 20 to control loading and unloading of the substrate W, starting rotation of the substrate W, changing the rotation speed of the substrate W, and stopping the rotation of the substrate W. For example, the control unit 102 controls the substrate holding unit 20 to change 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 rotation motor 24 of the substrate holding unit 20.

[0100] The control unit 102 controls the valve 34 of the etching liquid supply unit 30, so that the state of the valve 34 can be switched between the open state and the closed state. Specifically, the control unit 102 controls the valve 34 of the etching liquid supply unit 30 to open the valve 34, so that the etching liquid flowing in the pipe 32 toward the nozzle 36 can pass through. In addition, the control unit 102 controls the valve 34 of the etching liquid supply unit 30 to close the valve 34, so that the supply of the etching liquid flowing in the pipe 32 toward the nozzle 36 can be stopped.

[0101] The control unit 102 controls the valve 44 of the flushing liquid supply unit 40, so that the state of the valve 44 can be switched between the open state and the closed state. Specifically, the control unit 102 controls the valve 44 of the flushing liquid supply unit 40 to open the valve 44, so that the flushing liquid flowing in the pipe 42 toward the nozzle 46 can pass through. In addition, the control unit 102 controls the valve 44 of the flushing liquid supply unit 40 to close the valve 44, so that the supply of the flushing liquid flowing in the pipe 42 toward the nozzle 46 can be stopped.

[0102] The control unit 102 controls the valve 54a so that the state of the valve 54a can be switched between the open state and the closed state. Specifically, the control unit 102 controls the valve 54a so that the valve 54a becomes the open state, thereby allowing the sulfuric acid flowing in the pipe 52a toward the nozzle 56 to pass. In addition, the control unit 102 controls the valve 54a so that the valve 54a becomes the closed state, thereby stopping the supply of sulfuric acid flowing in the pipe 52a toward the nozzle 56.

[0103] The control unit 102 controls the valve 54b so as to switch the state of the valve 54b between the open state and the closed state. Specifically, the control unit 102 controls the valve 54b so as to open the valve 54b so as to allow the hydrogen peroxide solution flowing in the pipe 52b toward the nozzle 56 to pass through. In addition, the control unit 102 controls the valve 54b so as to close the valve 54b so as to stop the supply of the hydrogen peroxide solution flowing in the pipe 52b toward the nozzle 56.

[0104] Furthermore, the control unit 102 controls the valves 54a and 54b to open the valves 54a and 54b, thereby allowing sulfuric acid and hydrogen peroxide to pass through the pipes 52a and 52b toward the nozzle 56, respectively, and spraying the sulfuric acid and hydrogen peroxide mixed solution from the nozzle 56. Furthermore, the control unit 102 controls the valves 54a and 54b to close the valves 54a and 54b, thereby stopping spraying the sulfuric acid and hydrogen peroxide mixed solution from the nozzle 56.

[0105] The control unit 102 controls the valve 64 of the rinse liquid supply unit 60, so that the state of the valve 64 can be switched between the open state and the closed state. Specifically, the control unit 102 controls the valve 64 of the rinse liquid supply unit 60 to open the valve 64, so that the rinse liquid flowing in the pipe 62 toward the nozzle 66 can pass through. In addition, the control unit 102 controls the valve 64 of the rinse liquid supply unit 60 to close the valve 64, so that the supply of the rinse liquid flowing in the pipe 62 toward the nozzle 66 can be stopped.

[0106] The control unit 102 may also control the cup 90 so that the cup 90 moves relative to the substrate W. Specifically, while the etching liquid supply unit 30, the rinse liquid supply unit 40, the SPM supply unit 50, and / or the rinse liquid supply unit 60 are supplying etching liquid, rinse liquid, SPM, and / or rinse liquid to the substrate W, the control unit 102 causes the cup 90 to rise vertically upward to the side of the substrate W. Furthermore, when the etching liquid supply unit 30, the rinse liquid supply unit 40, the SPM supply unit 50, and / or the rinse liquid supply unit 60 are supplying etching liquid, rinse liquid, SPM, and / or rinse liquid to the substrate W, the control unit 102 causes the cup 90 to fall vertically downward from the side of the substrate W.

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

[0108] When a substrate is treated with a high-temperature sulfuric acid and hydrogen peroxide mixture, droplets of the sulfuric acid and hydrogen peroxide mixture may splash from the substrate. A hydrophobic substrate is treated with a sulfuric acid and hydrogen peroxide mixture, so that the substrate becomes hydrophilic. At this time, when the sulfuric acid and hydrogen peroxide mixture is at a high temperature, the sulfuric acid and hydrogen peroxide mixture reacts violently with the substrate, so that droplets of the sulfuric acid and hydrogen peroxide mixture may splash from the substrate. For example, when a substrate is etched with hydrofluoric acid or diluted hydrofluoric acid, the substrate becomes hydrophobic. Afterwards, when the substrate is treated with a sulfuric acid and hydrogen peroxide mixture to change the substrate to hydrophilic, if the sulfuric acid and hydrogen peroxide mixture is at a high temperature, droplets of the sulfuric acid and hydrogen peroxide mixture may splash from the substrate.

[0109] Next, refer to Figure 4 The splashing of droplets of a sulfuric acid / hydrogen peroxide mixture corresponding to the temperature of the sulfuric acid / hydrogen peroxide mixture and the sulfuric acid ratio is described. Figure 4 This is a graph showing the change in the number of droplets of the sulfuric acid-hydrogen peroxide mixture splashing from the substrate corresponding to the heating temperature of the sulfuric acid. Figure 4The results for sulfuric acid and hydrogen peroxide mixtures with different sulfuric acid ratios are shown in FIG. Figure 4 In the figure, 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 ratio of the sulfuric acid-hydrogen peroxide mixture is high, even if the temperature of the sulfuric acid increases, the number of droplets of the sulfuric acid-hydrogen peroxide mixture splashing from the substrate hardly changes. Figure 4 As shown in line L2, when the sulfuric acid ratio of the sulfuric acid-hydrogen peroxide mixture is low, the number of droplets increases when the temperature of the sulfuric acid becomes higher. For example, when the temperature of the sulfuric acid exceeds 120°C, the number of droplets increases sharply. This is believed to be because when the sulfuric acid ratio of the sulfuric acid-hydrogen peroxide mixture is low and the temperature of the sulfuric acid-hydrogen peroxide mixture is high, the sulfuric acid-hydrogen peroxide mixture reacts violently on the substrate, so the number of droplets of the sulfuric acid-hydrogen peroxide mixture splashed from the substrate (the number of droplets) increases.

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

[0112] from Figure 5 The change along the Y axis in shows the following tendency: the more the flow rate of the sulfuric acid and hydrogen peroxide mixture increases, the more the number of droplets increases. Figure 5 The change along the X-axis in shows the following tendency: the lower the sulfuric acid ratio of the sulfuric acid-hydrogen peroxide mixture, the more the number of droplets increases. This is generally considered to be because the sulfuric acid ratio of the sulfuric acid-hydrogen peroxide mixture is 2:1, and the more the ratio of sulfuric acid to hydrogen peroxide increases, the less the degree of temperature rise of the sulfuric acid-hydrogen peroxide mixture.

[0113] As the number of droplets increases, the droplets are more likely to adhere to the chamber, making it difficult to properly process the substrate. Therefore, from the perspective of reducing the number of droplets, it is preferred to process the substrate with a sulfuric acid-hydrogen peroxide mixed solution at a lower temperature and a higher sulfuric acid ratio. On the other hand, from the perspective of SPM processing of the substrate, it is preferred to process the substrate with a sulfuric acid-hydrogen peroxide mixed solution at a higher temperature and a lower sulfuric acid ratio.

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

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

[0116] like Figure 6 As shown, in this embodiment, the SPM process includes a first process and a second process. The SPM process starts from the first process. The first process is performed in a first period. The second process is started after the first process ends. The second process is performed in a second period after the first period. Typically, the second period starts continuously after the first period ends.

[0117] First, in the first process, the substrate W is processed with a sulfuric acid-hydrogen peroxide mixed solution having a high flow rate and a high sulfuric acid ratio. For example, the openings of valves 54a and 54b are set to be large, and the flow rates of sulfuric acid and hydrogen peroxide flowing through pipes 52a and 52b are set to be large. In addition, the ratio of the flow rate of sulfuric acid flowing through pipe 52a to the total flow rate of sulfuric acid and hydrogen peroxide flowing through pipes 52a and 52b is set to be high.

[0118] In the second treatment after the first treatment, the substrate W is treated with a sulfuric acid-hydrogen peroxide mixed solution with a low flow rate and a low sulfuric acid ratio. For example, the openings of the valves 54a and 54b are set to be small, and the flow rates of sulfuric acid and hydrogen peroxide flowing in the pipes 52a and 52b are set to be small. In addition, the ratio of the flow rate of sulfuric acid flowing in the pipe 52a to the total flow rate of sulfuric acid and hydrogen peroxide flowing in the pipes 52a and 52b is set to be low.

[0119] According to the substrate processing method of this embodiment, in the first process, the substrate W is processed with the sulfuric acid-hydrogen peroxide mixed liquid at a high flow rate. Therefore, the upper surface Wa of the substrate W can be quickly covered with the sulfuric acid-hydrogen peroxide mixed liquid, thereby suppressing the adhesion of particles to the substrate W. In addition, in the first process, since the sulfuric acid ratio of the sulfuric acid-hydrogen peroxide mixed liquid is high, liquid splashing of the sulfuric acid-hydrogen peroxide mixed liquid can be suppressed.

[0120] According to the substrate processing method of this embodiment, in the second process, the substrate W is processed with the sulfuric acid-hydrogen peroxide mixed solution having a low sulfuric acid ratio. In the second process, since the sulfuric acid ratio of the sulfuric acid-hydrogen peroxide mixed solution is low, the substrate W can be processed with the sulfuric acid-hydrogen peroxide mixed solution for a short time. In addition, in the second process, since the substrate W is processed with the sulfuric acid-hydrogen peroxide mixed solution at a low flow rate, the consumption of the sulfuric acid-hydrogen peroxide mixed solution in the SPM process can be reduced.

[0121] In addition, 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, liquid splashing also depends on the rotation speed of the substrate W. Typically, the higher the rotation speed of the substrate W, the easier it is for liquid splashing to occur, and the lower the rotation speed of the substrate W, the harder it is for liquid splashing to occur. Therefore, in the first process, the rotation speed of the substrate W is preferably lower than the threshold value.

[0122] On the other hand, in the second process, the temperature of the acid-hydrogen peroxide mixed liquid on the substrate W is preferably kept high. In addition, when the rotation speed of the substrate W in the second process is high, there is a case where the liquid film becomes thinner and the efficiency of the SPM process becomes lower. Therefore, the rotation speed of the substrate W in the second process may be lower than the rotation speed of the substrate W in the first process.

[0123] Next, refer to Figures 1 to 7 A substrate processing method according to this embodiment will be described. Figure 7 (a) to (c) are schematic diagrams of the substrate processing method according to this embodiment.

[0124] like Figure 7 As shown in (a) of FIG. 1 , the rinsing liquid is supplied to the substrate W. Under the control of the control unit 102 , the rinsing liquid supply unit 40 supplies the rinsing liquid from the nozzle 46 to the substrate W. Thus, the substrate W is rinsed.

[0125] The rinse liquid is supplied from the nozzle 46 to the rotating substrate W. When the rinse liquid is ejected to the center of the substrate W, the rinse liquid spreads radially from the center of the substrate W by centrifugal force and spreads over the entire upper surface Wa of the substrate W. At this time, the rinse liquid forms a film with a liquid thickness L0.

[0126] like Figure 7As shown in (b) of FIG. 1 , a sulfuric acid-hydrogen peroxide mixed solution is supplied to the substrate W, thereby performing a first treatment on the substrate W. Under the control of the control unit 102, the SPM supply unit 50 supplies the sulfuric acid-hydrogen peroxide mixed solution to the substrate W from the nozzle 56. Here, the valve 54a is opened to allow sulfuric acid to flow through the pipe 52a, and the valve 54b is opened to allow hydrogen peroxide to flow through the pipe 52b, and the sulfuric acid-hydrogen peroxide mixed solution generated by mixing sulfuric acid and hydrogen peroxide in the nozzle 56 is ejected from the nozzle 56.

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

[0128] In this manner, the sulfuric acid-hydrogen peroxide mixed solution is supplied to the rotating substrate W, so that the sulfuric acid-hydrogen peroxide mixed solution is used to process the substrate W. Therefore, the substrate W is processed by the sulfuric acid-hydrogen peroxide mixed solution in the first period.

[0129] Here, in the first process, the flow rate of sulfuric acid flowing in the pipe 52a is Fs1, and the temperature of sulfuric acid is Ts1. In the first process, the flow rate of hydrogen peroxide flowing in the pipe 52b is Fh1, and the temperature of hydrogen peroxide is Th1. In addition, in the first process, the flow rate of sulfuric acid and hydrogen peroxide mixed liquid is Fc1, the temperature of sulfuric acid and hydrogen peroxide mixed liquid is Tc1, and the sulfuric acid ratio of sulfuric acid and hydrogen peroxide mixed liquid is Rc1. In addition, 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 mixed liquid. At this time, sulfuric acid and hydrogen peroxide react with each other to generate heat. Therefore, the temperature Tc1 of the sulfuric acid-hydrogen peroxide mixed liquid 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 70° C. to 220° C., or 100° C. to 200° C. In addition, the temperature Th1 of hydrogen peroxide is room temperature. For example, the temperature Tc1 of the sulfuric acid-hydrogen peroxide mixture is 90° C. to 240° C.

[0132] The first treatment is used to hydrophilize the substrate W. Here, the flow rate Fc1 of the sulfuric acid-hydrogen peroxide mixed solution is large, so that the substrate W can be quickly covered with the sulfuric acid-hydrogen peroxide mixed solution.

[0133] In addition, in the first treatment, the sulfuric acid-hydrogen peroxide mixed solution supplied to the substrate W may splash from the substrate W and adhere to the chamber 11. Therefore, the first treatment is preferably performed in a manner that does not cause droplets of the sulfuric acid-hydrogen peroxide mixed solution to splash from the substrate W. For example, in the first treatment, when the sulfuric acid ratio of the sulfuric acid-hydrogen peroxide mixed solution is low, the sulfuric acid-hydrogen peroxide mixed solution may splash from 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 mixed solution to be high.

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

[0135] In addition, in the first process, when the rotation speed of the substrate W is high, the sulfuric acid and hydrogen peroxide mixed liquid may splash from the substrate W and adhere to the chamber 11. Therefore, the rotation speed Rr1 of the substrate W in the first process is preferably smaller than the threshold value. For example, the rotation speed Rr1 of the substrate W in the first process is greater than 700 rpm and less than 1400 rpm, and may also be greater than 800 rpm and less than 1200 rpm.

[0136] like Figure 7 As shown in (c) of FIG. 1 , a sulfuric acid-hydrogen peroxide mixed solution 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 mixed solution to the substrate W from the nozzle 56. The conditions of the second treatment are different from those of the first treatment. Here, the sulfuric acid-hydrogen peroxide mixed solution is supplied to the substrate W, thereby treating the substrate W with the sulfuric acid-hydrogen peroxide mixed solution.

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

[0138] In the second process, the opening of at least one of the valve 54a and the valve 54b in the first process is changed. For example, in the second process, the opening of the valve 54a in the first process is reduced to reduce the flow of sulfuric acid. In addition, in the second process, the opening of the valve 54b in the first process may be changed to change the flow of hydrogen peroxide.

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

[0140] In the second treatment, the hydrophilized substrate W is treated with a sulfuric acid and hydrogen peroxide mixed solution. Here, from the perspective of reducing costs and the impact on the environment, the flow rate Fc2 of the sulfuric acid and hydrogen peroxide mixed solution to the substrate W is preferably small. In addition, the sulfuric acid and hydrogen peroxide mixed solution is preferably prepared at a ratio that allows the substrate W to be treated efficiently.

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

[0142] For example, the temperature Ts2 of sulfuric acid is 70° C. to 220° C., or 100° C. to 200° C. In addition, the temperature Th2 of hydrogen peroxide is room temperature. For example, the temperature Tc2 of the sulfuric acid-hydrogen peroxide mixture is 90° C. to 240° C.

[0143] Here, comparing the first treatment and the second treatment, the flow rate Fc2 of the sulfuric acid and hydrogen peroxide mixed solution in the second treatment is smaller than the flow rate Fc1 of the sulfuric acid and hydrogen peroxide mixed solution in the first treatment. Therefore, the substrate W can be quickly coated with the sulfuric acid and hydrogen peroxide mixed solution to suppress the attachment of particles to the substrate W, and the consumption of the sulfuric acid and hydrogen peroxide mixed solution can be reduced. For example, the flow rate Fc2 of the sulfuric acid and hydrogen peroxide mixed solution in the second treatment is greater than 30% and less than 85% of the flow rate Fc1 of the sulfuric acid and hydrogen peroxide mixed solution in the first treatment, and can also be greater than 40% and less than 75%.

[0144] For example, the temperature Ts2 of sulfuric acid in the second treatment may be equal to the temperature Ts1 of sulfuric acid in the first treatment. In this case, the heating temperature of the heater 55a may not be changed between the first treatment and the second treatment. Similarly, the temperature Th2 of hydrogen peroxide in the second treatment may be equal to the temperature Th1 of hydrogen peroxide in the first treatment.

[0145] Furthermore, even if the temperature Ts2 of sulfuric acid and the temperature Th2 of hydrogen peroxide in the second treatment are equal to the temperature Ts1 of sulfuric acid and the temperature Th1 of hydrogen peroxide in the first treatment, the temperature Tc2 of the sulfuric acid-hydrogen peroxide mixed solution in the second treatment is different from the temperature Tc1 of the sulfuric acid-hydrogen peroxide mixed solution in the first treatment. Typically, the temperature Tc2 of the sulfuric acid-hydrogen peroxide mixed solution in the second treatment becomes higher than the temperature Tc1 of the sulfuric acid-hydrogen peroxide mixed solution in the first treatment. This is because the sulfuric acid ratio Rs2 of the sulfuric acid-hydrogen peroxide mixed solution is smaller than the sulfuric acid ratio Rs1 of the sulfuric acid-hydrogen peroxide mixed solution.

[0146] Furthermore, the sulfuric acid ratio Rc2 of the sulfuric acid / hydrogen peroxide mixed solution in the second process is smaller than the sulfuric acid ratio Rc1 of the sulfuric acid / hydrogen peroxide mixed solution in the first process. Therefore, the SPM process can be efficiently performed on the substrate W using a smaller amount of the sulfuric acid / hydrogen peroxide mixed solution.

[0147] The rotation speed Rr2 of the substrate W in the second process may be lower than the rotation speed Rr1 of the substrate W in the first process. Therefore, the SPM process can be efficiently performed on the substrate W using a smaller amount of the sulfuric acid-hydrogen peroxide mixed liquid.

[0148] However, when the rotation speed Rr2 of the substrate W in the second process is too small, the sulfuric acid and hydrogen peroxide mixed liquid on the substrate W may drip downward 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 greater than 100 rpm and less than 500 rpm, or may be greater than 150 rpm and less than 300 rpm.

[0149] Next, refer to Figures 1 to 8 A substrate processing method according to this embodiment will be described. Figure 8 Flowchart of the substrate processing method according to the present embodiment.

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

[0151] In step S120 , the rotation of the substrate W is started. Under the control of the control unit 102 , the substrate holding unit 20 starts rotating the substrate W while holding the substrate W.

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

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

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

[0155] Step S150 includes: step S152, performing a first process in a first period; and step S154, performing a second process in a second period after 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, and may be more than 1 second and less than 5 seconds. On the other hand, the second period is more than 30 seconds, and may be more than 1 minute and less than 5 minutes.

[0156] In step S152, the substrate W is processed with the sulfuric acid and hydrogen peroxide mixed solution in the first period. In the first process, the substrate W is processed with the sulfuric acid and hydrogen peroxide mixed solution having a flow rate Fc1 and a sulfuric acid ratio Rc1. At this time, the substrate W is rotated at a rotation speed Rr1.

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

[0158] In step S160, hydrogen peroxide is supplied to the substrate W, thereby treating the substrate W with hydrogen peroxide. Here, the supply of sulfuric acid to the substrate W is stopped, and the supply of hydrogen peroxide to the substrate W is continued. Specifically, the valve 54a is closed to stop the flow of sulfuric acid in the pipe 52a, while the flow of hydrogen peroxide in the pipe 52b is continued with the valve 54b open. However, the opening of the valve 54b may be changed as needed to change the flow rate of hydrogen peroxide in the pipe 52b.

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

[0160] In step S180 , the substrate W is dried. Under the control of the control unit 102 , the substrate holding unit 20 increases the rotation speed of the substrate W and spins off the rinse liquid on the substrate W by centrifugal force.

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

[0162] In step S200, the substrate W is taken out from the substrate processing unit 10. Under the control of the control unit 102, the substrate holding unit 20 releases the substrate W, and the central robot CR takes the substrate W out of the chamber 11. Thereafter, the substrate W is transported to the outside of the substrate processing apparatus 100 by the indexer robot IR.

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

[0164] Next, refer to Figures 1 to 10 A substrate processing method in the substrate processing apparatus 100 according to the present embodiment will be described. Fig. 9 (a) to Fig.10 (c) is a schematic diagram of the substrate processing method of this embodiment.

[0165] like Fig. 9 As shown in (a) of FIG. 1 , the substrate holding unit 20 holds the substrate W. The substrate holding unit 20 holds the substrate W being conveyed under the control of the control unit 102 .

[0166] like Fig. 9As shown in (b) of FIG. 1 , the substrate W is rotated and the etching liquid is supplied to the substrate W, thereby performing an etching process on the substrate W. Under the control of the control unit 102, the substrate holding unit 20 rotates the held substrate W, and the etching liquid supply unit 30 supplies the etching liquid to the substrate W from the nozzle 36, thereby performing an etching process on the substrate W. For example, hydrofluoric acid is supplied to the substrate W from the nozzle 36, thereby performing a hydrofluoric acid process on the substrate W. The natural oxide film of the substrate W can be removed by the hydrofluoric acid process. The substrate W is hydrophobized by the hydrofluoric acid process.

[0167] like Fig. 9 As shown in (c) of FIG. 1 , the rinsing liquid is supplied to the substrate W, thereby performing a rinsing treatment on the substrate W. Under the control of the control unit 102, the rinsing liquid supply unit 40 supplies the rinsing liquid to the substrate W from the nozzle 46, thereby performing a rinsing treatment on the substrate W. For example, carbonated water is supplied to the substrate W from the nozzle 46, thereby performing a rinsing treatment on the substrate W.

[0168] like Fig. 9 As shown in (d) of FIG. 1 , the substrate W is treated with a sulfuric acid and hydrogen peroxide mixed solution. In the first treatment, the substrate W is treated with a sulfuric acid and hydrogen peroxide mixed solution having a flow rate Fc1 and a sulfuric acid ratio Rc1. Under the control of the control unit 102, the SPM supply unit 50 supplies the sulfuric acid and hydrogen peroxide mixed solution to the substrate W from the nozzle 56, thereby performing the SPM treatment on the substrate W. Specifically, the valve 54a is opened to allow sulfuric acid to flow through the pipe 52a, and the valve 54b is opened to allow hydrogen peroxide to flow through the pipe 52b.

[0169] like Fig. 9 As shown in (e) of FIG. 1 , the substrate W is treated with a sulfuric acid and hydrogen peroxide mixed solution. In the second treatment, the substrate W is treated with a sulfuric acid and hydrogen peroxide mixed solution having 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 and hydrogen peroxide mixed solution to the substrate W from the nozzle 56, thereby continuously performing the SPM treatment on the substrate W.

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

[0171] like Fig.10As shown in (a) of FIG. 1 , hydrogen peroxide is supplied to the substrate W, thereby treating the substrate W with hydrogen peroxide. Under the control of the control unit 102, the SPM supply unit 50 supplies hydrogen peroxide to the substrate W from the nozzle 56, thereby treating the substrate W with hydrogen peroxide. Here, the supply of sulfuric acid to the substrate W is stopped, and hydrogen peroxide is continuously supplied to the substrate W. In detail, hydrogen peroxide is allowed to flow in the pipe 52b with the valve 54b opened, and in this state, the valve 54a is closed to stop the flow of sulfuric acid in the pipe 52a. At this time, the opening of the valve 54b may be changed to change the flow rate of hydrogen peroxide flowing in the pipe 52b.

[0172] like Fig.10 As shown in (b) of FIG. 1 , the rinsing liquid is supplied to the substrate W, thereby performing a rinsing process on the substrate W. Under the control of the control unit 102 , the rinsing liquid supply unit 60 supplies the rinsing liquid to the substrate W from the nozzle 66 , thereby performing a rinsing process on the substrate W.

[0173] like Fig.10 As shown in (c) of FIG. 1 , 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. Thereafter, the rotation of the substrate W is stopped, and the substrate W is taken out from the substrate processing unit 10 .

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

[0175] In addition, in reference Figures 1 to 10 In the above description, the SPM treatment is divided into two steps and performed, while the hydrogen peroxide treatment is performed in one step, however, the present embodiment is not limited thereto. The hydrogen peroxide treatment may also be divided into two steps and performed.

[0176] Next, refer to Fig.11 A substrate processing method according to this embodiment will be described. Fig.11 Flowchart of the substrate processing method according to the present embodiment. Fig.11 The flow chart is the same as reference except that the hydrogen peroxide treatment includes two treatment steps. Figure 8 The above flowchart is the same as that of the above flowchart, so repeated descriptions are omitted to avoid redundancy.

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

[0178] In step S160, the substrate W after the SPM treatment is treated with hydrogen peroxide. Here, hydrogen peroxide is supplied to the substrate W, so that the substrate W is treated with hydrogen peroxide. The valve 54a is closed, and the valve 54b is maintained in an open state. The opening of the 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 of the second hydrogen peroxide treatment is longer than the treatment period of the first hydrogen peroxide treatment.

[0180] In step S162, hydrogen peroxide is supplied to the substrate W, thereby performing a first hydrogen peroxide treatment. In the first hydrogen peroxide treatment, the flow rate of hydrogen peroxide flowing in the pipe 52b is Fhh1, and the substrate W is treated with sulfuric acid hydrogen peroxide at the flow rate Fhh1. In addition, in the first hydrogen peroxide treatment, the substrate W is subjected to hydrogen peroxide treatment with sulfuric acid hydrogen peroxide at the flow rate Fhh1.

[0181] In step S164, a second hydrogen peroxide treatment is performed by supplying hydrogen peroxide to the substrate W. In the second hydrogen peroxide treatment, the flow rate of hydrogen peroxide flowing through the pipe 52b is Fhh2, which is greater than the flow rate Fhh1 in the first hydrogen peroxide treatment.

[0182] Afterwards, with Figure 8 Similarly, step S170 to step S200 are performed.

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

[0184] Furthermore, since the flow rate Fhh1 of the first hydrogen peroxide treatment after the SPM treatment of the substrate W is small, it is possible to suppress the excessive reaction between the residual sulfuric acid components on the substrate W and the hydrogen peroxide to cause liquid splashing. In addition, thereafter, in the second hydrogen peroxide treatment, the hydrogen peroxide with a higher flow rate Fhh2 is supplied, so that the residual sulfuric acid components on the substrate W can be effectively removed.

[0185] Next, refer to Figures 1 to 13 A substrate processing apparatus 100 according to this embodiment will be described. Fig.12 is a schematic diagram of a substrate processing unit 10 in a substrate processing apparatus 100 according to this embodiment. Fig.13 for Fig.12 Schematic top view of the substrate processing unit 10. Fig.12The substrate processing unit 10 further includes a chemical solution supply unit 70 and a rinse liquid supply unit 80, the nozzle 36 of the etching solution supply unit 30, the nozzle 56 of the SPM supply unit 50 and the nozzle 66 of the rinse liquid supply unit 60 are integrally provided, and a scattering suppression member 59 is installed on the nozzle 56 for spraying SPM in an inclined direction. In addition to the above points, Fig.12 The substrate processing unit 10 has Figure 2 The substrate processing units 10 in the substrate processing apparatus 100 shown have the same configuration, and therefore, duplicate descriptions are omitted to avoid redundancy.

[0186] like Fig.12 As shown, the substrate processing unit 10 further includes a chemical liquid supply unit 70 and a rinse liquid supply unit 80. The chemical liquid supply unit 70 supplies chemical liquid to the substrate W. Typically, the chemical liquid supply unit 70 supplies chemical liquid to the upper surface Wa of the substrate W. At least a portion of the chemical liquid supply unit 70 is accommodated in the chamber 11.

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

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

[0189] The valve 74 opens and closes the flow path in the pipe 72. The valve 74 adjusts the opening of the pipe 72 to adjust the flow rate of the liquid medicine supplied to the pipe 72. Specifically, the valve 74 includes: a valve body (not shown) having a valve seat disposed therein; a valve body that opens and closes the valve seat; and an actuator (not shown) that moves the valve body between an open position and a closed position.

[0190] The nozzle 76 may also be configured to be movable relative to the substrate W. The liquid medicine supply unit 70 may also include a nozzle moving unit 78. The nozzle moving unit 78 may move the nozzle 76 up and down, or may rotate the nozzle 76 horizontally around the rotation axis. The nozzle moving unit 78 moves the nozzle 76 up and down. For example, the nozzle moving unit 78 includes: a ball screw mechanism; and an electric motor that applies a driving force to the ball screw mechanism. In addition, the nozzle moving unit 78 rotates the nozzle 76 horizontally. For example, the nozzle moving unit 78 includes an electric motor.

[0191] The rinse liquid supply unit 80 supplies the rinse liquid to the substrate W. Typically, the rinse liquid supply unit 80 supplies the rinse liquid to the upper surface Wa of the substrate W. At least a portion of the rinse liquid supply unit 80 is accommodated in the chamber 11 .

[0192] The rinse liquid supply unit 80 supplies rinse liquid to the upper surface Wa of the substrate W. The rinse liquid includes deionized water (DIW), electrolytic ion water or ozone water. Alternatively, the rinse liquid may be a liquid other than these liquids. As an example, ammonia water, hydrochloric acid water with a diluted concentration (e.g., about 10 ppm to 100 ppm) and reduced water (hydrogen water) may also be listed as the rinse liquid.

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

[0194] The valve 84 opens and closes the flow path in the pipe 82. The valve 84 adjusts the opening of the pipe 82 to adjust the flow rate of the rinse liquid supplied to the pipe 82. Specifically, the valve 84 includes: a valve body (not shown) having a valve seat disposed therein; a valve body that opens and closes the valve seat; and an actuator (not shown) that moves the valve body between an open position and a closed position. The nozzle 86 may also be configured to be movable relative to the substrate W.

[0195] The nozzle 36 of the etching liquid supply unit 30, the nozzle 56 of the SPM supply unit 50, and the nozzle 66 of the rinse liquid supply unit 60 are integrally provided. Therefore, when the type of liquid supplied to the substrate W is switched, the moving time of the nozzles 36, 56, 66 can be shortened, thereby increasing the processing throughput of the substrate processing.

[0196] Here, the nozzle 56 ejects the sulfuric acid and hydrogen peroxide mixture in an oblique direction to the lower right. The nozzle 56 ejects the sulfuric acid and hydrogen peroxide mixture in an oblique direction, thereby preventing the sulfuric acid and hydrogen peroxide mixture droplets from scattering from the substrate W from adhering to the nozzle 56.

[0197] Furthermore, a scattering suppression member 59 is attached to the nozzle 56. The scattering suppression member 59 is attached to the nozzle 56 along the direction in which the sulfuric acid-hydrogen peroxide mixed liquid is ejected from the nozzle 56. The scattering suppression member 59 is opposite to a position in the substrate W where the sulfuric acid-hydrogen peroxide mixed liquid ejected from the nozzle 56 reaches the substrate W. Thus, even if the sulfuric acid-hydrogen peroxide mixed liquid ejected to the substrate W splashes from the substrate W, the scattering suppression member 59 can suppress droplets from the substrate W from adhering to the surroundings.

[0198] In addition, if Fig.13As shown, the scattering suppression member 59 is housed together with the nozzle 56 in the standby end 92. When the nozzle 56 is arranged at the standby position, the standby port 92 is arranged at a position overlapping with the nozzle 56 and the scattering suppression member 59. The standby end 92 houses the nozzle 56 and the scattering suppression member 59. In addition, it is preferable that the nozzle 56 and the scattering suppression member 59 can be cleaned in the standby end 92.

[0199] Next, refer to Figure 12 to Figure 14 A substrate processing method according to this embodiment will be described. Fig.14 Flowchart of the substrate processing method according to the present embodiment. Fig.14 The flowchart includes points for chemical treatment and flushing treatment, which is similar to the reference Figure 8 The above flowchart is the same as that of the above flowchart, so repeated descriptions are omitted to avoid redundancy.

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

[0201] After step S170 , in step S200 , the chemical liquid is supplied to the substrate W. Thus, the chemical liquid treatment is performed on the substrate W. The chemical liquid supply unit 70 supplies the chemical liquid to the substrate W from the nozzle 76 under the control of the control unit 102 .

[0202] In step S210 , the rinsing liquid is supplied to the substrate W. Thus, the substrate W is subjected to a rinsing process. The rinsing liquid supply unit 80 supplies the rinsing liquid to the substrate W from the nozzle 86 under the control of the control unit 102 .

[0203] After step S210, the substrate W is dried in step S180. Therefore, the substrate W is dried. Figure 8 The same, therefore the description is omitted.

[0204] The embodiments of the present invention are 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 gist of the present invention. In addition, the plurality of constituent elements disclosed in the above embodiments can be appropriately changed. For example, a constituent element of all constituent elements shown in a certain embodiment can be added to a constituent element of another embodiment, or some constituent elements of all constituent elements shown in a certain embodiment can be deleted from the embodiment.

[0205] In order to facilitate the understanding of the present invention, the drawings show each component element principally and schematically, and the thickness, length, number, spacing, etc. of each component element shown in the drawings may be different from the actual situation due to the drawing relationship of the drawings. In addition, the configuration of each component element shown in the above embodiment is an example and is not particularly limited. Various changes can be made within the scope that does not substantially deviate from the technical effect of the present invention.

[0206] For example, in Figure 2 , Figure 7 , Fig. 9 , Fig.10 as well as Fig.12 In the substrate processing unit 10 shown, the sulfuric acid-hydrogen peroxide mixture is generated by mixing sulfuric acid and hydrogen peroxide in the nozzle 56 in the chamber 11 , but the present embodiment is not limited thereto. The sulfuric acid-hydrogen peroxide mixture may also be generated by mixing sulfuric acid and hydrogen peroxide outside the chamber 11 .

[0207] Industrial Applicability

[0208] The present invention can be used in the fields of a substrate processing apparatus and a substrate processing method.

[0209] Description of reference numerals:

[0210] 20: Substrate holding part

[0211] 30: Etching liquid supply unit

[0212] 40: Flushing liquid supply unit

[0213] 50: SPM supply department

[0214] 60: Flushing liquid supply unit

[0215] 100: Substrate processing device

[0216] 101: Control Devices

[0217] 102: Control Department

[0218] 104: Storage

Claims

1. A substrate processing device, wherein: have: a substrate holding portion that holds the substrate and rotates the substrate; as well as a mixed liquid supplying unit for supplying a sulfuric acid-hydrogen peroxide mixed liquid containing sulfuric acid and hydrogen peroxide to the substrate rotated by the substrate holding unit; The mixed liquid supply unit supplies the sulfuric acid and hydrogen peroxide mixed liquid to the substrate at a first flow rate in a first period, and supplies the sulfuric acid and hydrogen peroxide mixed liquid to the substrate at a second flow rate smaller than the first flow rate in a second period after the first period; The ratio of the sulfuric acid in the sulfuric acid-hydrogen peroxide mixed solution during the second period is smaller than the ratio of the sulfuric acid in the sulfuric acid-hydrogen peroxide mixed solution during the first period.

2. The substrate processing apparatus according to claim 1, wherein: The substrate processing apparatus further includes an etching liquid supply unit configured to supply etching liquid to the substrate before the mixed liquid supply unit 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 unit supplies hydrofluoric acid or diluted hydrofluoric acid as the etching liquid to the substrate.

4. The substrate processing apparatus according to any one of claims 1 to 3, wherein: The mixed liquid supply unit supplies the sulfuric acid-hydrogen peroxide mixed liquid generated by mixing the sulfuric acid at a temperature of 130° C. or higher and 200° C. or lower with the hydrogen peroxide solution 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 unit supplies the sulfuric acid-hydrogen peroxide mixed liquid formed by mixing the sulfuric acid and the hydrogen peroxide in a ratio of 4:1 to 9:1 to the substrate during the first period, and supplies the sulfuric acid-hydrogen peroxide mixed liquid formed by mixing the sulfuric acid and the hydrogen peroxide in a ratio of 2:1 to 3:1 to the substrate during the second period.

6. The substrate processing apparatus according to any one of claims 1 to 5, wherein: The second period is longer than the first period.

7. The substrate processing apparatus according to any one of claims 1 to 6, wherein: The substrate holding unit rotates the substrate at a first rotation speed during the first period, and then rotates the substrate at a second rotation speed during the second period; The second rotation speed is lower than the first rotation speed.

8. The substrate processing apparatus according to any one of claims 1 to 7, wherein: The mixed liquid supply unit supplies the hydrogen peroxide solution to the substrate after the second period.

9. The substrate processing apparatus according to any one of claims 1 to 8, wherein: The substrate processing apparatus further includes a scattering suppression member that suppresses droplets of the sulfuric acid-hydrogen peroxide mixed liquid from scattering from the substrate.

10. A substrate processing method, comprising a sulfuric acid-hydrogen peroxide mixed solution treatment step of supplying a sulfuric acid-hydrogen peroxide mixed solution containing sulfuric acid and hydrogen peroxide to a substrate held and rotated by a substrate holding portion, thereby treating the substrate with the sulfuric acid-hydrogen peroxide mixed solution, wherein: The sulfuric acid and hydrogen peroxide mixed liquid treatment process comprises: a first processing step of supplying the sulfuric acid and hydrogen peroxide mixed solution to the substrate at a first flow rate during a first period to process the substrate; and a second treatment step of supplying the sulfuric acid and hydrogen peroxide mixed solution to the substrate at a second flow rate smaller than the first flow rate in a second period after the first period to treat the substrate; The ratio of the sulfuric acid in the sulfuric acid-hydrogen peroxide mixed solution during the second period is smaller than the ratio of the sulfuric acid in the sulfuric acid-hydrogen peroxide mixed solution during the first period.

11. The substrate processing method according to claim 10, wherein: The substrate processing method further includes: an etching process, in which the substrate is processed with an etching solution before the sulfuric acid and hydrogen peroxide mixed solution processing process.

12. The substrate processing method according to claim 11, wherein: In the etching step, hydrofluoric acid or diluted hydrofluoric acid is supplied to the substrate as the etching solution.

13. The substrate processing method according to any one of claims 10 to 12, wherein: In the sulfuric acid-hydrogen peroxide mixed solution treatment step, the sulfuric acid-hydrogen peroxide mixed solution 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 processing method according to any one of claims 10 to 13, wherein: The first treatment step supplies the sulfuric acid-hydrogen peroxide mixed solution, which is a mixture of the sulfuric acid and the hydrogen peroxide in a ratio of 4:1 to 9:1, to the substrate during the first period; In the second treatment step, during the second period, the sulfuric acid-hydrogen peroxide mixed solution, which is a mixture of the sulfuric acid and the hydrogen peroxide at a ratio of 2:1 to 3:1, is supplied to the substrate.

15. The substrate processing method according to any one of claims 10 to 14, wherein: The second period is longer than the first period.

16. The substrate processing method according to any one of claims 10 to 15, wherein: In the sulfuric acid and hydrogen peroxide mixed liquid treatment step, after rotating the substrate at a first rotation speed during the first period, the substrate is rotated at a second rotation speed during the second period; The second rotation speed is lower than the first rotation speed.

17. The substrate processing method according to any one of claims 10 to 16, wherein: The method further includes supplying the hydrogen peroxide solution to the substrate after the second period to treat the substrate with the hydrogen peroxide solution.

18. The substrate processing method according to any one of claims 10 to 17, wherein: In the sulfuric acid-hydrogen peroxide mixed solution treatment step, scattering of droplets of the sulfuric acid-hydrogen peroxide mixed solution is suppressed by a scattering suppression member that faces a position in the substrate where the sulfuric acid-hydrogen peroxide mixed solution reaches the substrate.

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