Substrate processing apparatus and substrate processing method

Abstract

The substrate processing apparatus uses the processing liquid to remove an object to which a substrate is to be removed. The substrate processing apparatus includes: a holding portion for holding a substrate; a liquid supply unit that supplies a processing liquid to the substrate held by the holding unit; an electrode that is disposed so as not to be in contact with the substrate held by the holding unit, and that is in contact with the processing liquid supplied from the liquid supply unit; a power source that applies a voltage to the electrode; and a control unit that controls the liquid supply unit and the power supply. The control unit applies a voltage to the electrode in a state in which the electrode and the substrate are in contact with the processing liquid supplied from the liquid supply unit, thereby generating OH radicals in the processing liquid and applying the OH radicals to the removal target.

Description

Technical Field

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

[0002] In the prior art, in a substrate processing method for etching a resist film, a metal film, a metal nitride film, or a polymer residue (hereinafter collectively referred to as a removal object) on the surface of a substrate, sulfuric acid and a hydrogen peroxide liquid (hydrogen peroxide) are supplied to the removal object on the surface of the substrate. The sulfuric acid and hydrogen peroxide liquid supplied to the surface of the substrate can peel the removal object off the substrate by utilizing its oxidizing power.

[0003] Patent Document 1 discloses a substrate processing apparatus that does not use sulfuric acid in order to reduce environmental load, but irradiates UV light onto droplets of a mixture of oxygen and ozone water and supplies the droplets onto a resist film, thereby removing the resist film.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2021-148955 Summary of the invention

[0007] Technical problem to be solved by the invention

[0008] The present invention provides a technology capable of efficiently removing a removal object from the surface of a substrate.

[0009] Technical means for solving technical problems

[0010] According to one embodiment of the present invention, there is provided a substrate processing device which utilizes a processing liquid to remove a removal object from a substrate, the substrate processing device comprising: a holding portion for holding the substrate; a liquid supply portion for supplying the processing liquid to the substrate held by the holding portion; an electrode which is arranged at a distance from the substrate held by the holding portion and is in contact with the processing liquid supplied from the liquid supply portion; a power supply capable of applying a voltage to the electrode; and a control portion for controlling the liquid supply portion and the power supply, the control portion generating OH radicals in the processing liquid and imparting the OH radicals to the removal object by applying a voltage to the electrode while the electrode and the substrate are in contact with the processing liquid supplied from the liquid supply portion.

[0011] Effects of the Invention

[0012] According to one embodiment, the removal target on the surface of the substrate can be removed efficiently. BRIEF DESCRIPTION OF THE DRAWINGS

[0013] Figure 1This is a schematic diagram showing the overall structure of a substrate processing apparatus according to one embodiment.

[0014] Figure 2 (A) is a schematic plan view showing a facing portion of a first electrode according to one embodiment. Figure 2 (B) is a schematic plan view showing the opposing portion of the first modification example.

[0015] Figure 3 This is an enlarged cross-sectional view showing the generation of OH radicals by electrolysis in a substrate processing apparatus.

[0016] Figure 4 is a flow chart of a substrate processing method according to an embodiment.

[0017] Figure 5 (A) is a schematic plan view showing the opposing portion of the second modification example. Figure 5 (B) is a schematic plan view showing the relative parts of the third modified example.

[0018] Figure 6 This is a schematic diagram partially showing a substrate processing device according to a fourth variant.

[0019] Figure 7 (A) is a schematic plan view showing the first electrode of the fifth modification example. Figure 7 (B) is a schematic top view showing the first electrode of the sixth variation.

[0020] Figure 8 This is a schematic diagram partially showing a substrate processing device according to the seventh variant.

[0021] Fig. 9 This is a schematic diagram partially showing a substrate processing device according to the eighth variant.

[0022] Fig.10 It is a schematic top view partially showing a substrate processing device according to the ninth variant.

[0023] Fig.11 It is a schematic top view partially showing a substrate processing apparatus according to a tenth variation. DETAILED DESCRIPTION

[0024] Hereinafter, the mode for implementing the present invention will be described with reference to the drawings. In each of the drawings, the same components are sometimes denoted by the same reference numerals, and repeated descriptions are omitted.

[0025] like Figure 1 As shown, a substrate processing apparatus 1 according to one embodiment performs the following etching processing as a substrate processing: a processing liquid L is supplied to a removal object A on the surface of a substrate W to remove the removal object A. In addition, Figure 1The substrate processing apparatus 1 shown is constructed as a single-wafer apparatus that processes substrates W one by one.

[0026] As the removal object A removed from the surface of the substrate W, for example, a resist film, a metal film or a metal nitride film, or a polymer (resin) residue remaining on the substrate W can be listed. The resist film contains a resin (polymer) and a photosensitizer. In addition, the resist film can also be obtained by curing by exposure to ion beams. The metal film can be a metal film containing at least one of tungsten (W), titanium nitride (TiN), cobalt (Co), nickel (Ni), ruthenium (Ru), molybdenum (Mo), and aluminum (Al). The metal film can be a single metal or an alloy. As a metal nitride film, for example, titanium nitride (TiN) can be listed. In addition, the polymer residue is a foreign matter of a polymer that accidentally remains on the surface of the substrate W through a substrate treatment different from the present embodiment. Below, an example of removing the resist film on a substrate W having a resist film as the removal object A is described.

[0027] The substrate processing apparatus 1 includes: a processing container 10; a holding unit 20 for holding a substrate W in the processing container 10; a liquid supply unit 30 for supplying a processing liquid L to the substrate W in the processing container 10; a power supply unit 40 for supplying power to the processing liquid L; and a cup-shaped body 50 for recovering the used processing liquid L. In addition, the substrate processing apparatus 1 includes a control unit 90 for controlling each structure of the substrate processing apparatus 1.

[0028] The processing container 10 is formed in a box shape capable of accommodating the holding portion 20 and the cup-shaped body 50 therein. The processing container 10 has a gate 11 and a gate valve 12 for opening and closing the gate 11. The substrate W is transported by the transport device 2, and is transported into the processing container 10 through the gate 11 when the gate valve 12 is open. Thereafter, when the gate valve 12 airtightly closes the gate 11, the etching process can be performed on the substrate W in the processing container 10. When the gate valve 12 is opened after the substrate is processed, the substrate W is handed over to the transport device 2 that enters the processing container 10, and is transported to the outside of the processing container 10 through the gate 11.

[0029] The holding unit 20 holds the substrate W horizontally in the processing container 10 during substrate processing. The holding unit 20 includes a disc-shaped base 21 and a chuck mechanism (suction cup mechanism) 22 for holding the substrate W with the surface of the substrate W (removal object A) facing upward in the vertical direction. The chuck mechanism 22 is used in Figure 1 The mechanical chuck for holding the outer periphery of the substrate W is used, but it is not limited thereto, and may be, for example, a vacuum adsorption chuck, an electrostatic chuck, etc. In addition, the holding portion 20 is provided with a plurality of lifting pins (not shown), which float the substrate W from the chuck mechanism 22 and receive and transfer the substrate W to and from the conveying device 2.

[0030] The holding portion 20 is supported by a substrate rotating portion 61, which is a part of the rotating portion 60 of the substrate processing apparatus 1. The rotating portion 60 rotates at least one of the substrate W and the first electrode 41 of the power supply portion 40 relative to the other. In addition, the rotating portion 60 in this embodiment is configured to rotate both the substrate W and the first electrode 41.

[0031] The substrate rotating part 61 includes: a holding shaft part 62 that fixes the base 21 of the holding part 20 at the upper end thereof; and a rotating unit 63 that supports the lower end of the holding shaft part 62 and can rotate the holding shaft part 62. The rotating unit 63 has a motor and a drive transmission mechanism that are not shown, and is connected to the control part 90 in a manner that can communicate with the control part 90. The rotating unit 63 drives the motor under the control of the control part 90 to rotate the substrate W held by the holding part 20 at a target rotation speed via the holding shaft part 62.

[0032] The liquid supply unit 30 discharges (i.e., releases) liquid onto the surface of the substrate W held by the holding unit 20. The liquid supply unit 30 includes, for example, a tubular nozzle 31 having a liquid flow path therein, and a nozzle moving unit 32 that moves the nozzle 31 within the processing container 10. In addition, the liquid supply unit 30 includes an external supply unit 70 that supplies liquid to the nozzle 31 from the outside of the processing container 10.

[0033] The nozzle 31 is disposed above the substrate W held by the holding portion 20. The nozzle 31 is L-shaped when viewed from the side, horizontally extending from the side wall of the processing container 10 toward the center of the holding portion 20, and has a protruding end portion that bends downward near the center of the holding portion 20. A discharge port 31a that is connected to the flow path of the nozzle 31 and discharges liquid onto the surface of the substrate W is provided at the lower end of the protruding end portion.

[0034] The nozzle moving unit 32 moves the nozzle 31 in the horizontal direction and the vertical direction. The nozzle moving unit 32 has a motor and a drive transmission mechanism (not shown), and is connected to the control unit 90 in a manner that can communicate with the control unit 90. The nozzle moving unit 32 operates under the control of the control unit 90 to arrange the nozzle 31 at the nozzle evacuation position evacuated from the cup-shaped body 50 and the ejection position where the ejection port 31a is located substantially at the center of the substrate W.

[0035] The external supply unit 70 supplies liquid from the outside of the processing container 10 to the nozzle 31 during substrate processing. Examples of the liquid used in substrate processing include a processing liquid L (chemical solution) used for etching processing and a rinse liquid used to replace the processing liquid L after etching processing. Figure 1, a structure in which one nozzle 31 sequentially discharges the processing liquid L and the rinsing liquid is illustrated, but the substrate processing apparatus 1 may also be configured to discharge different types of processing liquids L through a plurality of nozzles 31. In addition, the external supply unit 70 may be configured to discharge a drying liquid (for example, an organic solvent such as isopropyl alcohol) having a higher volatility than the rinsing liquid after discharging the rinsing liquid, thereby replacing the rinsing liquid with the drying liquid.

[0036] The processing liquid L is preferably an aqueous solution containing an appropriate electrolyte according to the type (anode, cathode) of the first electrode 41 of the power supply part 40 opposite to the substrate W. For example, when the first electrode 41 is an anode, an aqueous solution containing at least one of HF, HCl, NH4OH, TMAH (tetramethylammonium hydroxide: Me4NOH), H2SO4, H3PO4, HNO3, etc. can be used. In particular, when the removal object A is a resist film, an alkaline aqueous solution is more preferred to promote dissolution. In addition, when the first electrode 41 is a cathode, an aqueous solution containing H2O2 can be used, for example, SC1 (NH4OH + H2O2), SC2 (HCl + H2O2), etc. can be cited. On the other hand, the rinse liquid is, for example, DIW (deionized water).

[0037] The external supply unit 70 includes: a treatment liquid supply path 71 for supplying a treatment liquid L to the nozzle 31, a treatment liquid source 72 disposed upstream of the treatment liquid supply path 71, a rinse liquid supply path 73 for supplying a rinse liquid to the nozzle 31, and a rinse liquid source 74 disposed upstream of the rinse liquid supply path 73. The treatment liquid supply path 71 and the rinse liquid supply path 73 are composed of a tube having a flow path for liquid circulation on the inner side, and include valves 71v and 73v for opening and closing the flow path at a midway position. Moreover, the treatment liquid supply path 71 and the rinse liquid supply path 73 are provided with: a pump for pressurizing the treatment liquid L, a flow regulator for adjusting the flow of the treatment liquid L, a temperature regulator for adjusting the temperature of the treatment liquid L, etc. (none of which are shown in the figure). In addition, the rinse liquid supply path 73 merges at a midway position of the treatment liquid supply path 71. Thus, the external supply unit 70 can selectively supply the treatment liquid L and the rinse liquid to the nozzle 31 under the control of the control unit 90.

[0038] The power supply unit 40 has a pair of electrodes for applying voltage to the processing liquid L discharged during the etching process, and the pair of electrodes electrolyzes the processing liquid L to generate OH radicals (hydroxyl radicals) in the processing liquid L. The power supply unit 40 includes: a first electrode 41 and a second electrode 42 as a pair of electrodes; a power supply 43 for applying voltage to the pair of electrodes; an electrode rotating unit 44 for rotating the first electrode 41; and an electrode moving unit 45 for moving the first electrode 41. That is, the electrode rotating unit 44 constitutes a part of the rotating unit 60 for rotating the first electrode 41 relative to the substrate W. In addition, the electrode moving unit 45 moves the first electrode 41 and arranges the first electrode 41 at a processing position relative to the substrate W held by the holding unit 20 and an electrode avoidance position avoided to the outside of the cup-shaped body 50.

[0039] The first electrode 41 is an electrode that is arranged at a distance from a position adjacent to the substrate W held by the holding portion 20 and generates OH radicals in the contacted processing liquid L. The first electrode 41 can be either an anode or a cathode depending on the connection method with the power supply 43. However, when an anode is used, the processing liquid L (electrolyte aqueous solution) and the material of the electrode corresponding to the anode are used, and when a cathode is used, the processing liquid L and the material of the electrode corresponding to the cathode are used.

[0040] The first electrode 41 includes a relative portion 411 that can be arranged relative to the holding portion 20 and an electrode shaft portion 412 that supports the center of the relative portion 411. The relative portion 411 is formed in a perfect circle having a diameter substantially the same as that of the substrate W in a plan view, and has an electrode surface 411a that is opposite to the entire surface of the substrate W. When the relative portion 411 is arranged at the processing position, the center of the relative portion 411 is aligned with the center of the substrate W and is supported by the electrode shaft portion 412 in a manner parallel to the surface of the substrate W held by the holding portion 20. A processing space PS is formed between the electrode surface 411a and the surface of the substrate W, through which the processing liquid L can flow during the etching process.

[0041] The width of the processing space PS (the distance D between the electrode surface 411a of the facing portion 411 and the surface of the substrate W: see Figure 3 ) is preferably set to a range of 0.5 mm to 5 mm, for example. Thus, the OH radicals of the generated processing liquid L can be smoothly applied to the resist film A as the removal object. Assuming that the width of the processing space PS is less than 0.5 mm, the processing liquid L ejected from the nozzle 31 may have difficulty entering the processing space PS. In addition, when the width of the processing space PS exceeds 5 mm, the OH radicals generated by the first electrode 41 are unlikely to reach the substrate W and disappear, and the processing efficiency may be reduced.

[0042] The material constituting the relative portion 411 is preferably selected from appropriate materials according to the type of electrode (anode, cathode) as described above. For example, in the case where the first electrode 41 is an anode, boron-doped diamond (hereinafter referred to as BDD) can be applied. The boron doping concentration of the BDD used as the first electrode 41 is preferably set to a mass in the range of 1000ppm to 20000ppm. By applying this BDD, even when the voltage applied to the processing liquid L is increased by the first electrode 41, the oxygen overvoltage can be increased, and oxygen is not easily generated from the processing liquid L. Therefore, the power supply portion 40 can apply a high voltage, and can effectively generate active oxygen such as OH radicals instead of oxygen.

[0043] On the other hand, when the first electrode 41 is a cathode, a chemically resistant noble metal, carbon, or BDD can be applied. As types of chemically resistant noble metals, gold (Au) and palladium (Pd) can be cited. However, platinum (Pt), which is one of the noble metals, is preferably not applied to the first electrode 41. This is because platinum will become a catalyst and decompose H2O2 as an aqueous solution. In addition, the first electrode 41 can also be composed of other conductive materials to form a disc-shaped base portion, and the above-mentioned materials (gold, palladium, carbon, BDD) are used to form a coating only on the electrode surface 411a.

[0044] like Figure 2 As shown in (A), the relative portion 411 of the first electrode 41 includes a plurality of holes (four through holes 413) at a short distance from the center (electrode shaft portion 412) to the radial outside. Each through hole 413 is spaced the same distance from the electrode shaft portion 412 and is arranged at equal intervals from each other. Each through hole 413 allows the processing liquid L ejected from the nozzle 31 to pass through the processing space PS on the electrode surface 411a side from the upper surface side of the relative portion 411. The processing liquid L supplied to the processing space PS is supplied to the entire radial direction of the substrate W due to centrifugal force. Of course, the number of through holes 413 is not particularly limited.

[0045] Alternatively, the first electrode 41 is not limited to a structure having a plurality of through holes 413 near the center of the flat plate-shaped opposing portion 411, and various opposing portions 411 may be used. Figure 3 B, the facing portion 411A may be formed by weaving a plurality of electrode wires 414 to have a mesh as a whole. Thus, the facing portion 411A can more easily guide the processing liquid L ejected from the nozzle 31 to the processing space PS below the facing portion 411A.

[0046] The electrode shaft 412 is formed of a conductive material in a rod shape. The upper end of the electrode shaft 412 is connected to the electrode rotating part 44 and the electrode moving part 45 inside the processing container 10. The lower end of the electrode shaft 412 is fixed to the center of the opposite part 411. The opposite part 411 and the electrode shaft 412 can be made of different materials and connected by a suitable bonding method, or they can be formed of the same material as a whole.

[0047] The electrode rotating part 44 is composed of a motor and a drive transmission mechanism not shown in the figure, and is connected to the control part 90. Under the control of the control part 90, the electrode rotating part 44 rotates the electrode shaft part 412 and the relative part 411 at a target rotation speed. The rotation direction of the first electrode 41 can be set to, for example, a direction opposite to the rotation direction of the substrate W based on the substrate rotating part 61. As a result, the first electrode 41 and the substrate W are opposite to the discharge port 31a of the nozzle 31 at different timings, respectively, so that the processing liquid L discharged from the discharge port 31a can be smoothly extended to the entire surface of the substrate W. In addition, the rotating part 60 can also make the rotation direction of the first electrode 41 and the rotation direction of the second electrode 42 the same direction, and change the relative position of the first electrode 41 and the substrate W by staggering each other's target rotation speeds.

[0048] The electrode moving part 45 is composed of a motor and a drive transmission mechanism (not shown), and is connected to the control part 90. The electrode rotating part 44 moves the electrode shaft part 412 and the relative part 411 in the horizontal direction and the vertical direction under the control of the control part 90, and arranges the first electrode 41 at the treatment position and the electrode avoidance position as described above. In addition, the power supply part 40 may also include a mechanism part that integrates the electrode rotating part 44 and the electrode moving part 45.

[0049] The second electrode 42 is provided at a midway position of the nozzle 31 and in the flow path, so that it can stably contact the processing liquid L flowing through the nozzle 31. The material of the second electrode 42 is not particularly limited as long as it has conductivity and chemical resistance.

[0050] The power source 43 is connected to the first electrode 41 via a wiring 46 and is connected to the second electrode 42 via a wiring 47. The wiring method of the power source 43 can be arbitrarily set according to the polarity of the first electrode 41 facing the substrate W. Figure 1 As shown in FIG. 1 , a case where the first electrode 41 is used as an anode and the second electrode 42 is used as a cathode will be described.

[0051] The power supply 43 is connected to the control unit 90 in a manner that allows communication with the control unit 90, and applies a DC voltage to the first electrode 41 and the second electrode 42 under the control of the control unit 90. The output value of the voltage applied by the power supply 43 can be, for example, in the range of 1.8V to 2.2V. Here, a common electrode such as glassy carbon will generate oxygen if the voltage of the anode is increased, but the first electrode 41 to which BDD is applied is difficult to generate oxygen even if the oxygen overvoltage is large. Therefore, the power supply 43 can apply a high voltage, and active oxygen such as OH radicals can be well generated around the first electrode 41.

[0052] The first electrode 41 and the second electrode 42 configured as described above are electrically connected to each other through the processing liquid L during the etching process. Figure 3 As shown, the processing liquid L (for example, TMAH) existing in the nozzle 31 and the processing space PS contacts the electrode surface 411a of the opposing portion 411 of the first electrode 41 and the second electrode 42. In this state, the power supply unit 40 applies a voltage of a predetermined output value (for example, 2V) to the first electrode 41 and the second electrode 42. As a result, the following reactions [1] and [2] occur around the electrode surface 411a.

[0053] [1]2H2O=O2+4H + +4e -

[0054] [2]H2O=·OH+H + +e -

[0055] That is, OH radicals (·OH) can be directly generated by reaction [2]. Furthermore, near the electrode surface 411a, by applying a high voltage, the following reactions [3] and [4] occur to generate ozone (O3) and hydrogen peroxide liquid (H2O2). Moreover, the following reaction [5] further occurs through the ozone (O3) and hydrogen peroxide liquid (H2O2) generated by the reaction, thereby indirectly generating OH radicals.

[0056] [3]2H2O=H2O2+2H + +2e -

[0057] [4]3H2O=O3+6H + +6e -

[0058] [5]O3+H2O2=·OH+HO2+O2

[0059] The lifetime of the OH radicals generated by the above reaction is short, being less than 200 μs. However, by configuring the electrode surface 411a at a position sufficiently close to the surface of the substrate W (the width of the processing space PS is less than 5 mm), the OH radicals can be easily guided to the resist film as the removal object A. The OH radicals have a strong oxidizing power and oxidize the resist film they come into contact with. As a result, the resist film can be smoothly stripped from the surface of the substrate W.

[0060] return Figure 1 The cup-shaped body 50 disposed inside the processing container 10 surrounds the outer periphery of the substrate W held by the holding portion 20, and receives the processing liquid L scattered from the outer periphery of the substrate W. The cup-shaped body 50 does not rotate in this embodiment, but may also be a structure that rotates together with the holding shaft portion 62. The bottom wall of the cup-shaped body 50 is provided with: a drain pipe 51 for discharging the liquid accumulated inside the cup-shaped body 50; and an exhaust pipe 52 for discharging the gas accumulated inside the cup-shaped body 50.

[0061] In addition, the substrate processing apparatus 1 includes a detection unit 80 at a position different from the processing container 10 (outside the processing container 10), and the detection unit 80 detects OH radicals generated by applying voltage to the processing liquid L. The detection unit 80 includes: an extraction path 81 branched from the processing liquid supply path 71, a reaction liquid source 82 that supplies a reaction liquid that reacts with OH radicals, a reaction liquid supply path 83 for the reaction liquid source 82 to flow, and a reactor 84 for the mixed liquid of the processing liquid L and the reaction liquid to flow into. The extraction path 81 and the reaction liquid supply path 83 merge at a confluence path 85 on the upstream side of the reactor 84 to form a mixed liquid. In addition, a detection mechanism 86 for detecting the amount of OH radicals generated in the mixed liquid is provided on the downstream side of the reactor 84.

[0062] The extraction path 81 is composed of a tube having a flow path inside which the treatment liquid L can flow, and includes a valve 81v for opening and closing the flow path at a midpoint. Similarly, the reaction liquid supply path 83 is composed of a tube having a flow path inside which the reaction liquid can flow, and is connected to a reaction liquid source 82 at its upstream end, and includes a valve 83v for opening and closing the flow path at a midpoint.

[0063] As the reaction liquid supplied by the reaction liquid source 82, a scavenger of OH radicals can be listed, and terephthalic acid (TA) which does not react with other radicals (O2 radicals, HO2 radicals, H2O2 radicals) is used. Terephthalic acid is non-fluorescent before reacting with OH radicals, but becomes 2-hydroxyterephthalic acid (HTA) and has fluorescence when reacting with OH radicals. Therefore, the detection mechanism 86 can detect the amount of OH radicals by irradiating the mixed liquid discharged from the reactor 84 with excitation light of a predetermined wavelength and receiving the fluorescence of HTA.

[0064] The reactor 84 into which the mixed liquid flows has a structure capable of temporarily storing the mixed liquid and applying a voltage to the mixed liquid. Specifically, the reactor 84 includes a cylindrical container 841, a first detection electrode 842 connected to the wiring 46 between the power source 43 and the first electrode 41, and a second detection electrode 843 connected to the wiring 47 between the power source 43 and the second electrode 42. The container 841 is connected to a confluence path 85 at one axial end and to a detection mechanism 86 at the other axial end.

[0065] The first detection electrode 842 and the second detection electrode 843 are exposed in the container 841 and contact the mixed liquid flowing into the container 841 from the confluence path 85. The distance between the first detection electrode 842 and the second detection electrode 843 is preferably set to be substantially the same as the distance between the first electrode 41 and the second electrode 42 of the processing container 10. Thus, the detection unit 80 can make the conditions for applying a voltage to the first detection electrode 842 and the second detection electrode 843 in the reactor 84 to electrolyze the mixed liquid the same as the conditions for applying a voltage to the first electrode 41 and the second electrode 42 in the processing container 10 to electrolyze the processing liquid L.

[0066] The detection mechanism 86 optically detects the fluorescent substance generated in the reactor. The detection mechanism 86 includes: a sample tube 861, which is connected to the reactor 84; an irradiation unit 862, which irradiates the excitation light to the detection unit 861a of the sample tube 861; and a light receiving unit 863, which receives the fluorescence generated by the detection unit 861a. The irradiation unit 862 is connected to the control unit 90, and under the control of the control unit 90, irradiates the detection unit 861a with excitation light having a wavelength of, for example, 310nm. The light receiving unit 863 is connected to the control unit 90, and sends an electrical signal corresponding to the received fluorescence amount to the control unit 90. The control unit 90 calculates the amount of OH radicals generated in the mixed solution based on the electrical signal.

[0067] The control unit 90 of the substrate processing device 1 is a control computer having a processor 91, a memory 92, an input / output interface (not shown), and an electronic circuit. The processor 91 is a combination of one or more of a CPU (Central Processing Unit), a GPU (Graphics Processing Unit), an ASIC (Application Specific Integrated Circuit), an FPGA (Field-Programmable Gate Array), and a circuit composed of a plurality of discrete semiconductors. The memory 92 includes a non-volatile memory (e.g., an optical disk, a DVD, a hard disk, a flash memory, etc.) and a volatile memory, and forms a storage unit of the control unit 90.

[0068] The control unit 90 controls the overall operation of the substrate processing device 1 by executing the program stored in the memory 92 through the processor 91. During the substrate processing, the control unit 90 causes the holding unit 20, the liquid supply unit 30 (including the external supply unit 70), the power supply unit 40, the rotating unit 60, and the detection unit 80 to sequentially perform the prescribed steps in conjunction with each other. In addition, the substrate processing device 1 can be configured such that the control unit 90 directly controls a plurality of structures, or can be configured such that each of the plurality of structures includes a control circuit board, and the control unit 90 sends instructions to each control circuit board to control the operation through each control circuit board.

[0069] The substrate processing apparatus 1 of this embodiment is basically configured as described above. Figure 4 The operation (substrate processing method) is explained by the flowchart.

[0070] In the substrate processing of removing the resist film (removal object A) of the substrate W, the control unit 90 of the substrate processing device 1 first delivers the substrate W into the processing container 10 (step S1). At this time, the control unit 90 performs the following actions: the gate valve 12 is opened, the substrate W is moved to the upper part of the holding part 20 by the conveying device 2, and the substrate W is delivered to the rising plurality of lift pins. Then, after the conveying device 2 retreats, the control unit 90 lowers the lift pins, and further operates the chuck mechanism (suction cup mechanism) 22, and the substrate W is horizontally held by the holding part 20. In addition, the processing container 10 is sealed by the gate valve 12.

[0071] Next, the control unit 90 operates the detection unit 80 provided outside the processing container 10 to adjust the voltage applied to the processing liquid L and performs a voltage adjustment process (step S2). Alternatively, the voltage adjustment process may be performed before the substrate W is introduced into the processing container 10.

[0072] In the voltage adjustment process, the control unit 90 opens the valves 81v and 83v while the valves 71v and 73v are closed. As a result, the treatment liquid L (TMAH) flows from the treatment liquid source 72 into the extraction path 81, and the reaction liquid (TA) flows from the reaction liquid source 82 into the reaction liquid supply path 83, and the treatment liquid L and the reaction liquid merge in the merging path 85. Then, the mixed liquid of the treatment liquid L and the reaction liquid flows from the merging path 85 into the reactor 84.

[0073] In this state, the control unit 90 starts electrolysis of the mixed solution in the reactor 84. The control unit 90 applies a predetermined voltage to the first detection electrode 842 and the second detection electrode 843, so that the mixed solution in the reactor 84 generates OH radicals. The OH radicals react with the mixed reaction solution to become fluorescent 2-hydroxyterephthalic acid (HTA). The mixed solution containing HTA corresponding to the reaction state of the reactor 84 flows into the sample tube 861 of the detection mechanism 86. The detection mechanism 86 irradiates the excitation light from the irradiation unit 862 to the detection part 861a of the sample tube 861, and when the light receiving part 863 receives the fluorescence of HTA, an electrical signal corresponding to the fluorescence amount is sent to the control unit 90.

[0074] The control unit 90 calculates the amount of OH radicals based on the electrical signal and determines whether the calculated amount of OH radicals is within the target range. When it is outside the target range, the voltage applied from the power supply 43 to the first detection electrode 842 and the second detection electrode 843 is adjusted. For example, when the calculated amount of OH radicals is less than the target range, the voltage is increased, and when the calculated amount of OH radicals is more than the target range, the voltage is decreased. Thus, the substrate processing device 1 can optimize the voltage actually applied by the power supply 43 to the first electrode 41 and the second electrode 42 in the processing container 10 in advance.

[0075] In addition, the voltage adjustment process is not limited to being performed each time a substrate W is processed, and can be performed as needed. For example, the control unit 90 can be configured to perform the voltage adjustment process at the beginning of the substrate processing device 1 or after maintenance, and not perform the voltage adjustment process in the subsequent substrate processing. Alternatively, the control unit 90 can also be configured to perform the voltage adjustment process when the processing liquid source 72 is filled with the processing liquid L.

[0076] When the voltage to be applied is adjusted in the voltage adjustment process, the control unit 90 closes the valves 81v and 83v to end the voltage adjustment process and transfer to the etching process as the substrate process (steps S3 to S7). In the etching process, the control unit 90 first operates the rotating unit 60 to rotate the substrate W and the first electrode 41 (step S3). At this time, the substrate rotating unit 61 rotates the substrate W in a predetermined rotation direction and at a set target rotation speed for the substrate. In addition, the electrode rotating unit 44 rotates the first electrode 41 at a target rotation speed for the electrode set in a direction opposite to the rotation direction of the substrate W.

[0077] Then, the control unit 90 opens the valve 71v of the processing liquid supply path 71, so that the processing liquid L of the processing liquid source 72 flows into the nozzle 31, and the processing liquid L is supplied to the substrate W from the discharge port 31a of the nozzle 31 (step S4). The processing liquid L falling from the discharge port 31a hits the surface of the substrate W through the through holes 413 of the first electrode 41. Moreover, the processing liquid L wets and spreads radially outward of the substrate W due to the centrifugal force generated by the rotation of the substrate W and the relative part 411. As a result, the entire electrode surface 411a of the first electrode 41 and the entire surface of the substrate W are in contact with the processing liquid L in the processing space PS.

[0078] The control unit 90 activates the power supply unit 40, and applies a voltage of a predetermined output value (e.g., 2V) from the power supply 43 to the first electrode 41 and the second electrode 42 in contact with the processing liquid L (step S5). As a result, the first electrode 41 and the second electrode 42 are connected through the processing liquid L, and the processing liquid L is electrolyzed. Along with the electrolysis, OH radicals are generated in the processing liquid L near the electrode surface 411a of the first electrode 41. The OH radicals react with the resist film of the removal object A of the substrate W, so that the resist film is separated from the substrate W. The substrate processing device 1 can remove the resist film on the entire surface of the substrate W uniformly using the opposing portion 411 opposing the entire surface of the substrate W.

[0079] The control unit 90 measures the implementation period of the etching process as the electrolysis of the processing liquid L starts, and determines whether a predetermined set period has passed (step S6). The set period is obtained by finding the period for removing the resist film of the substrate W by OH radicals through experiments or simulations. The substrate processing device 1 continues the relative rotation of the substrate W and the first electrode 41, the supply of the processing liquid L, and the power supply (electrolysis) to the processing liquid L until the implementation period of the etching process passes the set period, thereby being able to reliably remove the resist film.

[0080] When the etching process execution period exceeds the set period, the control unit 90 ends the etching process (step S7 ). At this time, the control unit 90 stops supplying power to the first electrode 41 and the second electrode 42 and closes the valve 71 v to stop supplying the processing liquid L to the nozzle 31 .

[0081] After that, the control unit 90 performs a rinsing and cleaning process of the substrate W as substrate processing in order to discharge the processing liquid L remaining on the surface of the substrate W (step S8). In the rinsing and cleaning process, the valve 73v is opened, and the substrate W is rotated by the rotating unit 60, while the rinsing liquid of the rinsing liquid source 74 flows into the nozzle 31, and the rinsing liquid is supplied to the substrate W from the discharge port 31a of the nozzle 31. The rinsing liquid wets and spreads on the surface of the substrate W due to the centrifugal force of the rotation, and the processing liquid L is discharged from the surface of the substrate W.

[0082] After the rinsing and cleaning process, the control unit 90 performs a spin drying process as a substrate treatment in order to dry the rinse liquid on the surface of the substrate W (step S9). In the spin drying process, the rinse liquid on the surface of the substrate W is dried by rotating the substrate W using the rotating unit 60. In addition, in the substrate treatment, before the spin drying process, a drying liquid as the treatment liquid L may be supplied from the liquid supply unit 30 to the surface of the substrate W to replace the rinse liquid with the drying liquid. When the spin drying process is completed, the substrate treatment of the substrate W accommodated in the processing container 10 is completed.

[0083] Finally, the control unit 90 releases the substrate W held by the holding unit 20, opens the gate valve 12 to allow the conveying device 2 to enter the processing container 10, and delivers the substrate W to the conveying device 2, thereby delivering the substrate W from the inside of the processing container 10 (step S10). As a result, the substrate processing device 1 can obtain the substrate W with the resist film removed well.

[0084] As described above, the substrate processing apparatus 1 and the substrate processing method apply voltage to the first electrode 41 and the second electrode 42 in a state where the first electrode 41 and the substrate W are in contact with the processing liquid L supplied from the liquid supply unit 30. Therefore, OH radicals can be generated in the processing liquid L near the first electrode 41, and the OH radicals can be smoothly given to the removal object A of the substrate W. Thus, the substrate processing apparatus 1 and the substrate processing method can efficiently remove the removal object A on the surface of the substrate W. In addition, the substrate processing apparatus 1 can eliminate the processing required for discarding sulfuric acid by not using sulfuric acid, and as a result, the environmental load can be reduced.

[0085] In addition, the substrate processing apparatus 1 can easily spread the processing liquid L supplied to the surface of the substrate W to the entire surface by rotating at least one of the first electrode 41 and the substrate W using the rotating part 60. In addition, the first electrode 41 can increase the oxygen overvoltage and easily generate OH radicals in the processing liquid L by having a layer of at least one of gold, palladium, carbon, and boron-doped diamond (BDD) on the electrode surface 411a. In particular, when the first electrode 41 is an anode, by applying BDD, OH radicals can be more effectively generated through the first electrode 41. In addition, the opposing parts 411 and 411A of the first electrode 41 have holes (through holes 413, meshes) through which the processing liquid L ejected (discharged) from the nozzle 31 above passes, so that the processing liquid L can be stably and continuously supplied to the surface of the substrate W.

[0086] Furthermore, the substrate processing apparatus 1 and the substrate processing method can promote electrolysis of the processing liquid L by using an aqueous solution containing an electrolyte as the processing liquid L. In particular, by containing at least one of HF, HCl, NH4OH, TMAH, H2O2, H2SO4, H3PO4, and HNO3 as the aqueous solution, OH radicals can be sufficiently generated.

[0087] In addition, the substrate processing apparatus 1 and the substrate processing method can adjust the voltage applied by the power supply unit 40 with high accuracy by detecting the OH radicals generated in the processing liquid L separately from the processing container 10 using the detection unit 80. In particular, the substrate processing apparatus 1 can easily detect the amount of OH radicals by detecting the fluorescent substance generated by the reaction with the OH radicals in the reactor 84 using the detection mechanism 86 for optical detection. The substrate processing apparatus 1 uses terephthalic acid as the reaction liquid, which reacts with the OH radicals to have fluorescence, and can stably detect the amount of OH radicals.

[0088] In addition, the substrate processing device 1 and the substrate processing method of the present invention are not limited to the above-mentioned embodiments, and various modifications can be adopted. For example, in the above description, the substrate processing device 1 uses the resist film as the removal object A, but the same substrate processing can also be performed on the metal film, metal nitride film, and polymer residue located on the surface of the substrate W. For example, because the metal film is at least one of W, TiN, Co, Ni, Ru, Mo, and Al, it can be well removed by using the OH radicals generated in the processing liquid L.

[0089] Below, refer to Figure 5 to Figure 11 A description will be given of a substrate processing apparatus 1 and a substrate processing method according to other modified examples.

[0090] like Figure 5As in the second modification example shown in (A) of FIG. 1 , the following structure may be adopted: the first electrode 41 has a facing portion 411B partially covering the surface of the substrate W, and the first electrode 41 is rotated by the electrode rotating portion 44 (see FIG. 1 ). Figure 1 ) rotates the relative portion 411B. The relative portion 411B is, for example, formed as a thin and long rectangular flat plate extending to a length greater than the diameter of the substrate W, and can be opposite to the entire surface of the substrate W as it rotates. In addition, when the relative portion 411B is not opposite to the discharge port 31a, the processing liquid L discharged from the nozzle 31 is supplied to the surface of the substrate W. In this case, the power supply unit 40 also generates OH radicals near the relative portion 411B by supplying power, thereby being able to remove the removal object A of the substrate W well.

[0091] like Figure 5 As in the third modification example shown in (B) of FIG. 1 , the following structure may be adopted: the first electrode 41 has a sector-shaped opposing portion 411C having a smaller width at the center and a larger width at the outer periphery, and the opposing portion 411C is rotated by the electrode rotating portion 44. By using the opposing portion 411C in this way, the opposing portion 411C faces the surface near the outer periphery of the substrate W for a longer period of time, and the removal object A near the outer periphery of the substrate W can be removed more stably.

[0092] like Figure 6 As shown in the fourth modification, the rotating part 60 may not include the electrode rotating part 44 (see Figure 1 ) and includes a fixed structure 48 for fixing the first electrode 41. In this case, the rotating unit 60 rotates the substrate W through the substrate rotating unit 61, so that the processing liquid L supplied to the surface of the substrate W spreads to the entire surface of the substrate W. In addition, the power supply unit 40 can generate OH radicals in the processing liquid L by applying a voltage to the first electrode 41 via the fixed structure 48. In short, as long as the substrate processing device 1 can generate OH radicals on the entire surface of the substrate W, the structure of supplying the processing liquid L to the entire surface of the substrate W is not particularly limited. For example, even if the rotating unit 60 adopts a structure including the electrode rotating unit 44 but not including the substrate rotating unit 61 (the substrate W is not rotated), the processing liquid L can be spread on the surface of the substrate W as the first electrode 41 rotates.

[0093] like Figure 7As shown in (A), the first electrode 41A of the fifth modified example is not a structure for removing the removal object A from the entire surface of the substrate W as in the above-mentioned embodiment, but a structure for removing the removal object A near the outer periphery of the substrate W. Specifically, the first electrode 41A has: a connecting portion 415 fixed to the fixing structure 48; and a protrusion 416 supported by the connecting portion 415 and protruding relatively short above the surface of the substrate W. The protrusion 416 is set to a length that can only be opposite to the outer periphery of the substrate W, and is close to a circumferential portion of the outer periphery of the substrate W. The substrate processing device 1 rotates the substrate W by the rotating portion 60 (substrate rotating portion 61), supplies the processing liquid L to the surface of the substrate W from the nozzle 31, and applies a voltage to the first electrode 41A and the second electrode 42 by the power supply portion 40. Thus, the protrusion 416 of the first electrode 41A generates OH radicals in the processing liquid L near the outer peripheral edge of the substrate W, and the removal target near the outer peripheral edge can be removed satisfactorily using the OH radicals.

[0094] like Figure 7 As shown in (B), the first electrode 41B of the sixth variation has a ring portion 417 surrounding the periphery of the substrate instead of the protrusion 416 in order to remove the removal object A near the periphery of the substrate W. In this case, the substrate processing apparatus 1 can also remove the removal object near the periphery of the substrate W well.

[0095] like Figure 8 As shown, the substrate processing apparatus 1 of the seventh modified example forms a flow path 412a inside the electrode shaft portion 412 of the first electrode 41C, and the protruding end portion of the nozzle 31 is inserted into the flow path 412a. The flow path 412a is connected to an opening formed in the center of the opposing portions 411, 411A to 411C of the first electrode 41. The liquid supply unit 30 and the power supply unit 40 allow the processing liquid L ejected from the ejection port 31a of the nozzle 31 to flow into the processing space PS from the opening. In addition, in this case, the electrode moving unit 45 is configured to be able to move the nozzle 31 and the first electrode 41 integrally.

[0096] In this way, even if a structure is adopted in which the processing liquid L is supplied through the inside of the electrode shaft portion 412, the substrate processing apparatus 1 can stably supply the processing liquid L to the processing space PS between the electrode surface 411a and the surface of the substrate W, and electrolyze the processing liquid L. Therefore, the OH radicals generated near the first electrode 41 can well remove the removal object A of the substrate W. In particular, when this structure is adopted, it is not necessary to provide the through hole 413 in the opposing portion 411, so splashing caused by the processing liquid L hitting the upper surface of the opposing portion 411 can be reliably avoided.

[0097] like Fig. 9As shown in FIG. 1 , the substrate processing apparatus 1A of the eighth modification is configured to apply voltage to the first electrode 41 and the second electrode 42 in a state where the substrate W is immersed in the processing liquid L. Specifically, the holding portion 20 includes a chuck mechanism 22 for vacuum-adsorbing the substrate W, and includes a frame portion 23 that protrudes radially outward from the substrate W to a position above the substrate W and surrounds the substrate W in an annular shape in the circumferential direction. Thus, the placement surface on which the substrate W is placed and the inner side of the frame portion 23 form a storage space 24 in which the processing liquid L can be stored.

[0098] The liquid supply unit 30 has a nozzle 31 for supplying the processing liquid L above the storage space 24. The nozzle 31 is retracted from the cup-shaped body 50 after supplying the processing liquid L. In addition, the nozzle 31 may be configured to wait above the storage space 24 during the etching process, and replenish the processing liquid L when the processing liquid L in the storage space 24 is reduced.

[0099] The power supply unit 40 includes: a first electrode 41 having a facing portion 411 facing the substrate W; and a second electrode 42 inserted into the storage space 24 outside the horizontal direction of the first electrode 41. The first electrode 41 is connected to the electrode moving unit 45. In addition, in this modification, the structure does not include the rotating unit 60 (substrate rotating unit 61 and electrode rotating unit 44), but the substrate processing apparatus 1A may also be a structure including the rotating unit 60 that rotates the substrate W and the first electrode 41.

[0100] When the substrate processing apparatus 1A thus configured applies voltage to the first electrode 41 and the second electrode 42 by the power supply 43 while the processing liquid L is stored in the storage space 24, OH radicals are generated near the electrode surface 411a of the first electrode 41. Therefore, according to the substrate processing apparatus 1A, the generated OH radicals can also be used to remove the removal object A on the surface of the substrate W. In particular, the substrate processing apparatus 1A can remove the removal object A more uniformly by suppressing the turbulence (turbulent flow) of the processing liquid L during electrolysis.

[0101] Fig.10 The substrate processing apparatus 1B of the ninth variation shown in (A) to (C) is configured to clean the first electrode 41 that has been etched at the same time during the rinsing and cleaning process of the substrate W. Specifically, the substrate processing apparatus 1B includes a support arm 45a for supporting the first electrode 41 and an arm rotating unit 45b for rotating the support arm 45a as an electrode moving unit 45. Fig.10 As shown in (A), during the etching process, the substrate processing device 1B arranges the first electrode 41 on the upper side of the substrate W in the vertical direction and near the substrate W, generates OH radicals in the processing liquid L, and thus removes the removal object A of the substrate W.

[0102] After the etching process, the substrate processing apparatus 1B rotates the support arm 45a by the arm rotating unit 45b to move the first electrode 41 to the electrode retreat position. Thus, the surface of the substrate W is exposed and the first electrode 41 can perform other processes at the electrode retreat position.

[0103] The substrate processing apparatus 1B performs the above-mentioned rinsing and cleaning process and spin drying process on the exposed substrate W (see also Figure 4 For example, in the rinsing and cleaning step, the substrate processing apparatus 1B moves the cleaning nozzle 33 that discharges the rinsing liquid (DIW) to above the substrate W, and rotates the substrate W while supplying the rinsing liquid.

[0104] On the other hand, the first electrode 41 disposed at the electrode avoidance position is sequentially subjected to an electrode rinsing process and an air-drying process. For example, in the electrode rinsing process, the substrate processing apparatus 1B moves the strip nozzle 34 that discharges the rinsing liquid (DIW) to the top (or bottom) of the first electrode 41, and slides the strip nozzle 34 while supplying the rinsing liquid. In this way, the first electrode 41 used in the electrolysis can be cleaned. In the subsequent air-drying process, the substrate processing apparatus 1B also moves the blower (not shown) to the top (or bottom) of the first electrode 41 to remove the rinsing liquid attached to the first electrode 41. In this way, the substrate processing apparatus 1B can improve the durability of the first electrode 41 by cleaning the first electrode 41, and use the first electrode 41 for a long time.

[0105] In addition, if Fig.11 As shown in the 10th variation, the substrate processing apparatus 1C may be configured as a batch type apparatus that processes a plurality of substrates W at a time. The batch type substrate processing apparatus 1C has a processing tank 15 (processing container) that stores the processing liquid L and can accommodate a plurality of substrates W, and the plurality of substrates W can be immersed in the processing liquid L stored in the processing tank 15 at once. For example, each substrate W is held by a holding portion (not shown) so as to extend in the vertical direction. In addition, the substrate processing apparatus 1C has a liquid supply portion (not shown) that supplies the processing liquid L into the processing tank 15.

[0106] Furthermore, the substrate processing apparatus 1C respectively arranges the first electrode 41 at the position near each substrate W in the holding state. In addition, the second electrode 42 is arranged at an appropriate position in the processing tank 15. Thus, the substrate processing apparatus 1C can generate OH radicals for each of the plurality of first electrodes 41 by applying an appropriate voltage from the power supply 43 to the first electrode 41 and the second electrode 42. The substrate W arranged adjacent to each first electrode 41 is well removed by the OH radicals to remove the removal object A.

[0107] The substrate processing device 1 and the substrate processing method of the embodiment of the present invention are illustrative in all aspects and are not intended to limit the present invention. The embodiment can be changed and improved in various ways without departing from the claims and their gist. The matters described in the above multiple embodiments can adopt other structures within the scope of non-contradiction and can be combined within the scope of non-contradiction.

[0108] This application claims the priority of basic application No. 2022-095874 filed with the Japan Patent Office on June 14, 2022, the entire contents of which are hereby referenced and cited.

[0109] Description of Reference Numerals

[0110] 1 substrate processing device; 20 holding part

[0111] 30 liquid supply unit; 41 first electrode

[0112] 42 second electrode; 43 power supply

[0113] 90 control unit; A remove object

[0114] L: treatment liquid; W: substrate.

Claims

1. A substrate processing device, which uses a processing liquid to remove a removal object from a substrate, wherein the substrate processing device is characterized in that it comprises: a holding portion for holding the substrate; a liquid supplying section for supplying the processing liquid to the substrate held by the holding section; an electrode arranged at a distance from the substrate held by the holding portion and in contact with the processing liquid supplied from the liquid supply portion; a power source capable of applying a voltage to the electrodes; and a control unit for controlling the liquid supply unit and the power supply, The control unit generates OH radicals in the processing liquid and provides the OH radicals to the removal target by applying a voltage to the electrode in a state where the electrode and the substrate are in contact with the processing liquid supplied from the liquid supply unit.

2. The substrate processing device according to claim 1, characterized in that: having a rotating portion capable of rotating at least one of the electrode and the substrate held by the holding portion relative to the other, The control unit rotates the rotating unit at a set target rotation speed during substrate processing.

3. The substrate processing device according to claim 1, characterized in that: The electrodes include a first electrode and a second electrode, The first electrode contacts the processing liquid flowing between the first electrode and the substrate. The second electrode is electrically connected to the first electrode at a position farther from the substrate than the first electrode through the processing liquid continuously supplied by the liquid supply unit.

4. The substrate processing device according to claim 3, characterized in that: The first electrode has a layer of at least one of gold, palladium, carbon, and boron-doped diamond on an electrode surface.

5. The substrate processing device according to claim 4, characterized in that: The first electrode is an anode, The anode has boron-doped diamond on the electrode face.

6. The substrate processing device according to claim 3, characterized in that: The distance between the first electrode and the substrate held by the holding portion is set to a range of 0.5 mm to 5 mm.

7. The substrate processing device according to claim 3, characterized in that: The first electrode has a facing portion facing the entire surface of the substrate held by the holding portion, The facing portion has a plurality of holes through which the processing liquid discharged from the liquid supply portion passes.

8. The substrate processing device according to claim 3, characterized in that: having a rotating portion capable of rotating the first electrode, The first electrode has a rectangular facing portion extending from the center to the outer periphery of the substrate held by the holding portion.

9. The substrate processing device according to claim 3, characterized in that: having a rotating portion capable of rotating the first electrode, The first electrode has a sector-shaped facing portion whose circumferential width increases from the center of the substrate toward the periphery.

10. The substrate processing device according to claim 3, characterized in that: having a rotating portion capable of rotating the substrate, The first electrode has a protrusion that faces only a portion in a circumferential direction of an outer peripheral edge of the substrate held by the holding portion.

11. The substrate processing device according to claim 3, characterized in that: The first electrode has a ring portion extending in a circumferential direction at an outer peripheral edge of the substrate held by the holding portion.

12. The substrate processing device according to claim 3, characterized in that: The first electrode includes: a facing portion facing the surface of the substrate held by the holding portion; and an electrode shaft portion supporting the facing portion. The liquid supply portion supplies the processing liquid to a position between the facing portion and the surface of the substrate via a flow path inside the electrode shaft portion.

13. The substrate processing device according to claim 1, wherein: The treatment solution is an aqueous solution containing an electrolyte.

14. The substrate processing device according to claim 13, characterized in that: The aqueous solution comprises at least one of HF, HCl, NH4OH, TMAH, H2O2, H2SO4, H3PO4, and HNO3.

15. The substrate processing device according to claim 1, wherein: The object to be removed is a resist film, a metal film or a metal nitride film formed on the surface of the substrate, or a polymer residue remaining on the surface of the substrate.

16. The substrate processing device according to claim 15, characterized in that: The removal target includes at least one of W, Co, Ni, Ru, Mo, and Al when the removal target is the metal film, and includes TiN when the removal target is the metal nitride film.

17. The substrate processing device according to any one of claims 1 to 16, characterized in that: include: a processing container for processing the substrate; and The detection unit provided separately from the processing container can cause the processing liquid to be supplied to the processing container to flow separately into the detection unit. The detection unit detects the OH radical generated in the processing liquid by applying the same voltage as the voltage of the electrode of the processing container to the inflowing processing liquid.

18. The substrate processing device according to claim 17, characterized in that: The detection unit has: a reactor capable of applying a voltage to a mixed solution of a reaction solution and the treatment solution, wherein the reaction solution can react with the generated OH radicals to generate a substance having fluorescence; and A detection mechanism for optically detecting the fluorescent substance generated in the reactor.

19. The substrate processing device according to claim 18, characterized in that: The reaction liquid is terephthalic acid.

20. A substrate processing method, using a processing liquid to remove a removal object from a substrate, the substrate processing method is characterized by comprising: A step of holding the substrate by a holding portion; a step of supplying the processing liquid to the substrate held by the holding portion; and a step of applying a voltage from a power source to an electrode arranged at a distance from the substrate held by the holding portion, In the step of supplying the treatment liquid, the electrode and the substrate are brought into contact with the treatment liquid. In the step of applying the voltage, OH radicals are generated in the processing liquid in contact with the electrode along with the application of the voltage, and the OH radicals are provided to the removal object.

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