WO2023243409A1 - Substrate treatment device and substrate treatment method - Google Patents

Substrate treatment device and substrate treatment method Download PDF

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Publication number
WO2023243409A1
WO2023243409A1 PCT/JP2023/020290 JP2023020290W WO2023243409A1 WO 2023243409 A1 WO2023243409 A1 WO 2023243409A1 JP 2023020290 W JP2023020290 W JP 2023020290W WO 2023243409 A1 WO2023243409 A1 WO 2023243409A1
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Prior art keywords
substrate
electrode
liquid
processing apparatus
processing
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PCT/JP2023/020290
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French (fr)
Japanese (ja)
Inventor
倫太郎 樋口
光則 中森
至 菅野
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東京エレクトロン株式会社
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Publication of WO2023243409A1 publication Critical patent/WO2023243409A1/en

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/02—Etching
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/02—Etching
    • C25F3/04—Etching of light metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/02—Etching
    • C25F3/06—Etching of iron or steel
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/02—Etching
    • C25F3/08—Etching of refractory metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
    • H01L21/3063—Electrolytic etching

Definitions

  • the present disclosure relates to a substrate processing apparatus and a substrate processing method.
  • the removal target in the substrate processing method that etches the resist film, metal film, metal nitride film, and polymer residue (hereinafter collectively referred to as the removal target) on the surface of the substrate, sulfuric acid and hydrogen peroxide solution are used as the removal target on the surface of the substrate. is supplied to.
  • the sulfuric acid and hydrogen peroxide solution supplied to the surface of the substrate can peel off the object to be removed from the substrate by their oxidizing power.
  • UV light is irradiated onto droplets of a mixture of oxygen gas and ozone water without using sulfuric acid, and the droplets are applied to a resist film.
  • a substrate processing apparatus is disclosed that removes a resist film by supplying a resist film.
  • the target to be removed on the surface of the substrate can be efficiently removed.
  • FIG. 7(A) is a schematic plan view showing a first electrode according to a fifth modification.
  • FIG. 7(B) is a schematic plan view showing the first electrode according to the sixth modification.
  • FIG. 7 is a schematic explanatory diagram partially showing a substrate processing apparatus according to a seventh modification. It is a schematic explanatory view partially showing a substrate processing apparatus according to an eighth modification.
  • FIG. 12 is a schematic plan view partially showing a substrate processing apparatus according to a ninth modification.
  • FIG. 7 is a schematic plan view partially showing a substrate processing apparatus according to a tenth modification.
  • the substrate processing apparatus 1 performs an etching process to remove the removal target A by supplying a processing liquid L to the removal target A on the surface of the substrate W as substrate processing. Further, the substrate processing apparatus 1 shown in FIG. 1 is configured as a single-wafer type apparatus that processes the substrates W one by one.
  • the polymer residue is a polymer foreign substance that remains unintentionally on the surface of the substrate W due to substrate processing different from this embodiment.
  • an example of removing a resist film on a substrate W having a resist film as a removal target A will be described.
  • the holding unit 20 holds the substrate W horizontally inside the processing container 10 during substrate processing.
  • the holding unit 20 includes a disk-shaped base 21 and a chuck mechanism 22 that holds the surface of the substrate W (removal target A) in a state facing upward in the vertical direction.
  • the chuck mechanism 22 is a mechanical chuck that grips the outer peripheral edge of the substrate W in FIG. 1, it is not limited to this, and may be, for example, a vacuum chuck, an electrostatic chuck, or the like.
  • the holding unit 20 is provided with a plurality of lift pins (not shown) that levitate the substrate W from the chuck mechanism 22 and receive and transfer the substrate W to and from the transport device 2 .
  • the holding section 20 is supported by a substrate rotating section 61, which is one of the rotating sections 60 of the substrate processing apparatus 1.
  • the rotating section 60 rotates at least one of the substrate W and the first electrode 41 of the power feeding section 40 relative to the other. Note that the rotating section 60 according to this embodiment is configured to rotate both the substrate W and the first electrode 41.
  • the liquid supply unit 30 discharges a 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 inside the processing container 10.
  • the liquid supply unit 30 also includes an external supply unit 70 that supplies liquid to the nozzle 31 from outside the processing container 10 .
  • the nozzle 31 is arranged above the substrate W held by the holding part 20.
  • the nozzle 31 has an L-shape in side view, extends horizontally from the side wall of the processing container 10 toward the vicinity of the center of the holding part 20 , and has a protruding end portion bent downward near the center of the holding part 20 . are doing.
  • a discharge port 31a that communicates with 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.
  • the nozzle moving unit 32 moves the nozzle 31 in the horizontal and vertical directions.
  • the nozzle moving section 32 has a motor and a drive transmission mechanism (not shown), and is communicably connected to the control section 90.
  • the nozzle moving unit 32 operates under the control of the control unit 90 to arrange the nozzle 31 at a nozzle retracted position where the nozzle is retracted from the cup 50 and at an ejection position where the ejection port 31a is located approximately at the center of the substrate W.
  • the external supply unit 70 supplies liquid to the nozzle 31 from outside the processing container 10 during substrate processing.
  • the liquid used for substrate processing include a processing liquid L (chemical liquid) used for etching processing and a rinsing liquid for replacing processing liquid L after etching processing.
  • FIG. 1 illustrates a configuration in which one nozzle 31 sequentially discharges a processing liquid L and a rinsing liquid
  • the substrate processing apparatus 1 may also have a configuration in which a plurality of nozzles 31 discharge different types of processing liquid L. good.
  • the external supply unit 70 further discharges a drying liquid (for example, an organic solvent such as isopropylene alcohol) that is more volatile than the rinsing liquid to replace the rinsing liquid with the drying liquid.
  • a drying liquid for example, an organic solvent such as isopropylene alcohol
  • It can also be a configuration.
  • the processing liquid L it is preferable to select an aqueous solution containing an appropriate electrolyte depending on the type (anode, cathode) of the first electrode 41 of the power supply section 40 facing the substrate W, and the like.
  • the first electrode 41 is an anode
  • Me4NOH tetramethylammonium hydroxide: Me4NOH
  • H2SO4 tetramethylammonium hydroxide: Me4NOH
  • H2SO4 tetramethylammonium hydroxide: H2SO4 , H3PO4 , HNO3, etc.
  • an alkaline aqueous solution is more preferable in order to promote dissolution.
  • an aqueous solution containing H 2 O 2 may be used, such as SC1 (NH 4 OH+H 2 O 2 ), SC2 (HCl+H 2 O 2 ), and the like.
  • the rinsing liquid is, for example, DIW (deionized water).
  • the external supply unit 70 includes a processing liquid supply path 71 that supplies the processing liquid L to the nozzle 31, a processing liquid source 72 provided upstream of the processing liquid supply path 71, and a rinsing liquid supply path that supplies the rinsing liquid to the nozzle 31. 73 and a rinsing liquid source 74 provided upstream of the rinsing liquid supply path 73.
  • the processing liquid supply path 71 and the rinsing liquid supply path 73 are constituted by tubes each having a flow path through which a liquid can flow, and are provided with valves 71v and 73v at intermediate positions to open and close the flow path.
  • the processing liquid supply path 71 and the rinsing liquid supply path 73 are provided with a pump that pumps the processing liquid L, a flow rate regulator that adjusts the flow rate of the processing liquid L, a temperature regulator that adjusts the temperature of the processing liquid L, and the like. (both not shown). Further, the rinsing liquid supply path 73 joins the processing liquid supply path 71 at an intermediate position. Thereby, the external supply unit 70 can selectively supply the processing liquid L and the rinsing liquid to the nozzle 31 under the control of the control unit 90.
  • the power supply unit 40 has a pair of electrodes that apply a voltage to the processing liquid L discharged during the etching process, and generates OH radicals (hydroxyl radicals) in the processing liquid L by electrolysis of the processing liquid L by the pair of electrodes.
  • the power supply unit 40 includes a pair of electrodes, a first electrode 41 and a second electrode 42 , a power source 43 that applies voltage to the pair of electrodes, an electrode rotation unit 44 that rotates the first electrode 41 , and a first electrode 41 .
  • an electrode moving section 45 that moves the electrode. That is, the electrode rotating section 44 constitutes a part of the rotating section 60 that rotates the first electrode 41 relative to the substrate W. Further, the electrode moving unit 45 moves the first electrode 41 between a processing position facing the substrate W held by the holding unit 20 and an electrode retraction position where the first electrode 41 is retracted to the outside of the cup 50. Place.
  • the first electrode 41 is an electrode that is arranged at a distance from the substrate W held by the holding unit 20 and generates OH radicals in the processing liquid L that comes into contact with it.
  • the first electrode 41 may be either an anode or a cathode depending on the connection form with the power source 43. However, if an anode is used, the treatment liquid L (electrolyte aqueous solution) and electrode material will be applied depending on the anode, and if a cathode is used, the treatment liquid L and electrode material will be applied according to the cathode. do.
  • the first electrode 41 includes a facing part 411 that is arranged to face the holding part 20 and an electrode shaft part 412 that supports the center of the facing part 411.
  • the opposing portion 411 is formed in a perfect circular shape having approximately the same diameter as the substrate W in plan view, and has an electrode surface 411a facing the entire surface of the substrate W.
  • the electrode shaft part 411 is arranged so that its center coincides with the center of the substrate W and is parallel to the surface of the substrate W held by the holding part 20.
  • Supported by 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 etching processing.
  • the width of the processing space PS (distance D between the electrode surface 411a of the opposing portion 411 and the surface of the substrate W: see FIG. 3) is preferably set in a range of 0.5 mm to 5 mm, for example. Thereby, the OH radicals of the generated processing liquid L are smoothly applied to the resist film that is the removal target A. If the width of the processing space PS is less than 0.5 mm, it may be difficult for the processing liquid L discharged from the nozzle 31 to enter the processing space PS. Furthermore, if the width of the processing space PS exceeds 5 mm, there is a high possibility that the OH radicals generated at the first electrode 41 will disappear without reaching the substrate W, and there is a possibility that the processing efficiency will decrease.
  • the first electrode 41 is an anode
  • boron-doped diamond hereinafter referred to as BDD
  • the boron doping concentration of the BDD used as the first electrode 41 is preferably set to a mass in the range of 1000 ppm to 20000 ppm.
  • the first electrode 41 when the first electrode 41 is a cathode, chemically resistant noble metal, carbon, or BDD may be used.
  • chemically resistant noble metals include gold (Au) and palladium (Pd).
  • platinum (Pt) which is one of the noble metals, is preferably not applied to the first electrode 41. This is because platinum acts as a catalyst and decomposes H 2 O 2 in an aqueous solution.
  • the first electrode 41 may have a disk-shaped base portion made of another conductive material, and only the electrode surface 411a may be coated with the above-mentioned material (gold, palladium, carbon, BDD).
  • the facing part 411 of the first electrode 41 has a plurality of holes (four through holes 413) at a short distance from the center (electrode shaft part 412) toward the outside in the radial direction. Equipped with Each through hole 413 is spaced from the electrode shaft portion 412 by the same distance, and is arranged at equal intervals from each other. Each through hole 413 allows the processing liquid L discharged from the nozzle 31 to pass from the upper surface side of the opposing portion 411 to the processing space PS on the electrode surface 411a side. The processing liquid L supplied to the processing space PS is supplied to the entire substrate W in the radial direction by centrifugal force. Note that, of course, the number of through holes 413 is not particularly limited.
  • the first electrode 41 is not limited to having a plurality of through holes 413 near the center of the flat plate of the opposing portion 411, and may employ various forms of the opposing portion 411.
  • the opposing portion 411A may be formed by weaving a plurality of electrode wires 414 so as to have a mesh (holes) as a whole. Thereby, the facing part 411A can more easily guide the processing liquid L discharged from the nozzle 31 to the processing space PS below the facing part 411A.
  • the electrode shaft portion 412 is made of a conductive material and has a rod shape.
  • the upper end portion of the electrode shaft portion 412 is connected to the electrode rotating portion 44 and the electrode moving portion 45 inside the processing container 10 .
  • the lower end of the electrode shaft portion 412 is fixed to the center of the opposing portion 411.
  • the opposing portion 411 and the electrode shaft portion 412 may be made of different materials and connected by appropriate joining means, or may be integrally molded from the same material.
  • the electrode rotating section 44 is constituted by a motor and a drive transmission mechanism (not shown), and is connected to the control section 90.
  • the electrode rotating section 44 rotates the electrode shaft section 412 and the opposing section 411 at a target rotation speed under the control of the control section 90.
  • the rotation direction of the first electrode 41 may be set, for example, to be opposite to the rotation direction of the substrate W by the substrate rotation unit 61.
  • the first electrode 41 and the substrate W each face the discharge port 31a of the nozzle 31 at different timings, and the processing liquid L discharged from the discharge port 31a can be smoothly spread over the entire surface of the substrate W. Can be done.
  • the rotating unit 60 adjusts the relative position between the first electrode 41 and the substrate W by making the rotation direction of the first electrode 41 and the rotation direction of the second electrode 42 the same, and by shifting their target rotation speeds. It may be changed.
  • the electrode moving unit 45 is composed of a motor and a drive transmission mechanism (not shown), and is connected to the control unit 90.
  • the electrode rotating section 44 moves the electrode shaft section 412 and the opposing section 411 in the horizontal and vertical directions under the control of the control section 90, and arranges the first electrode 41 at the processing position and the electrode retraction position as described above. do.
  • the power feeding section 40 may include a mechanical section that integrates the electrode rotating section 44 and the electrode moving section 45.
  • the second electrode 42 is provided in the middle of the nozzle 31 and within the flow path, so that it can constantly 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.
  • the power source 43 is connected to the first electrode 41 via a wiring 46 and to the second electrode 42 via a wiring 47.
  • the wiring form of the power source 43 may be arbitrarily set depending on the polarity of the first electrode 41 facing the substrate W. Below, as shown in FIG. 1, a case will be described in which the first electrode 41 is used as an anode and the second electrode 42 is used as a cathode.
  • the power source 43 is communicatively connected to 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 source 43 is preferably in the range of 1.8V to 2.2V, for example.
  • oxygen will be generated as the anode voltage is increased, but with the first electrode 41 to which BDD is applied, oxygen overvoltage is large and oxygen is difficult to generate. . Therefore, the power source 43 can apply a high voltage, and can satisfactorily generate active oxygen such as OH radicals around the first electrode 41.
  • the first electrode 41 and the second electrode 42 configured as described above are electrically connected through the processing liquid L during the etching process.
  • the processing liquid L for example, TMAH
  • the processing space PS is applied to the electrode surface 411a of the facing portion 411 of the first electrode 41 and the second electrode 42. is in contact with.
  • 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.
  • a predetermined output value for example, 2V
  • the lifetime of the OH radicals generated by the above reaction is as short as 200 ⁇ s or less.
  • the electrode surface 411a at a position sufficiently close to the surface of the substrate W (the width of the processing space PS is 5 mm or less)
  • OH radicals can be easily guided to the resist film that is the removal target A.
  • OH radicals have strong oxidizing power and oxidize the resist film that comes into contact with them. As a result, the resist film can be smoothly peeled off from the surface of the substrate W.
  • the cup 50 provided inside the processing container 10 surrounds the outer periphery of the substrate W held by the holding part 20, and receives the processing liquid L scattered from the outer periphery of the substrate W.
  • the cup 50 does not rotate in this embodiment, it may be configured to rotate together with the holding shaft portion 62.
  • a drain pipe 51 for discharging the liquid accumulated inside the cup 50 and an exhaust pipe 52 for discharging the gas accumulated inside the cup 50 are provided on the bottom wall of the cup 50.
  • the substrate processing apparatus 1 includes a detection unit 80 that detects OH radicals generated by applying a voltage to the processing liquid L at a position different from the processing container 10 (outside the processing container 10).
  • the detection unit 80 includes an extraction path 81 that branches from the processing liquid supply path 71, a reaction liquid source 82 that supplies a reaction liquid that reacts with OH radicals, and a reaction liquid supply path 83 through which the reaction liquid from the reaction liquid source 82 flows. , and a reactor 84 into which a mixed liquid of the processing liquid L and the reaction liquid flows.
  • the extraction path 81 and the reaction liquid supply path 83 merge in a merging path 85 on the upstream side of the reactor 84 to form a mixed liquid.
  • a detection mechanism 86 is provided on the downstream side of the reactor 84 to detect the amount of OH radicals generated within the mixed liquid.
  • the extraction path 81 is constituted by a tube that has a flow path inside thereof through which the processing liquid L can flow, and is provided with a valve 81v that opens and closes the flow path at an intermediate position.
  • the reaction liquid supply path 83 is constituted by a tube having a flow path through which the reaction liquid can flow, the reaction liquid source 82 is connected to the upstream end of the tube, and a valve 83v for opening and closing the flow path is provided at an intermediate position. Be prepared.
  • terephthalic acid which is a scavenger of OH radicals and does not react with other radicals (O 2 radical, HO 2 radical, H 2 O 2 radical).
  • TA terephthalic acid
  • HTA 2-hydroxyterephthalic acid
  • the detection mechanism 86 can detect the amount of OH radicals by irradiating the liquid mixture discharged from the reactor 84 with excitation light of a predetermined wavelength and receiving the fluorescence of HTA.
  • the reactor 84 into which the mixed liquid flows has a structure that can temporarily store the mixed liquid and apply a voltage to the mixed liquid.
  • 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 first detection electrode 842 connected to the power source 43 and the second electrode 42. and a second detection electrode 843 connected to the wiring 47 between them.
  • the container 841 has a confluence path 85 connected to one end in the axial direction, and a detection mechanism 86 to the other end in the axial direction.
  • the first detection electrode 842 and the second detection electrode 843 are exposed inside the container 841 and come into contact with the liquid mixture that has flowed 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 approximately equal to the distance between the first electrode 41 and the second electrode 42 of the processing container 10.
  • the detection unit 80 determines the conditions for electrolyzing the mixed solution by applying a voltage to the first detection electrode 842 and the second detection electrode 843 in the reactor 84 and the conditions for electrolyzing the mixed liquid by applying a voltage to the first detection electrode 842 and the second detection electrode 843 in the processing container 10.
  • the conditions for electrolyzing the treatment liquid L by applying a voltage to the two electrodes 42 can be made equal.
  • the detection mechanism 86 optically detects the fluorescent substance generated in the reactor.
  • the detection mechanism 86 includes a sample tube 861 connected to the reactor 84, an irradiation section 862 that irradiates excitation light to the detected section 861a of the sample tube 861, and a light receiving section 863 that receives fluorescence generated in the detected section 861a. has.
  • the irradiation section 862 is connected to the control section 90, and under the control of the control section 90 projects excitation light having a wavelength of, for example, 310 nm onto the detected section 861a.
  • the light receiving section 863 is connected to the control section 90 and transmits an electric signal to the control section 90 according to the amount of received fluorescence.
  • the control unit 90 calculates the amount of OH radicals generated in the mixed liquid based on this electrical signal.
  • the control unit 90 of the substrate processing apparatus 1 is a control computer that includes a processor 91, a memory 92, an input/output interface (not shown), an electronic circuit, etc.
  • the processor 91 includes 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), a circuit made of a plurality of discrete semiconductors, etc. It is a combination.
  • the memory 92 includes a nonvolatile memory (for example, a compact disk, a DVD, a hard disk, a flash memory, etc.) and a volatile memory, and forms the storage section of the control unit 90.
  • the control unit 90 controls the overall operation of the substrate processing apparatus 1 by having the processor 91 execute a program stored in the memory 92.
  • 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 rotation unit 60, and the detection unit 80 to interlock with each other to sequentially perform predetermined steps.
  • the substrate processing apparatus 1 may have a configuration in which the control unit 90 directly controls a plurality of configurations, and is provided with a control board for each of the plurality of configurations, and the control unit 90 transmits commands to each control board so that each control board can control the control board.
  • a configuration that controls the operation may also be used.
  • the substrate processing apparatus 1 is basically configured as described above, and its operation (substrate processing method) will be described below with reference to the flowchart in FIG. 4.
  • the control unit 90 of the substrate processing apparatus 1 first carries the substrate W into the processing container 10 (step S1). At this time, the control section 90 opens the gate valve 12, causes the transfer device 2 to move the substrate W above the holding section 20, and performs an operation to transfer the substrate W to the plurality of lifted lift pins. After the transport device 2 retreats, the control section 90 lowers each lift pin and further operates the chuck mechanism 22 to hold the substrate W horizontally by the holding section 20. Further, the processing container 10 is sealed by a gate valve 12 .
  • control unit 90 operates the detection unit 80 installed outside the processing container 10 to perform a voltage adjustment step (step S2). Note that the voltage adjustment step may be performed before loading the substrate W into the processing container 10.
  • the control unit 90 opens the valves 81v and 83v while closing the valves 71v and 73v.
  • the processing liquid L (TMAH) flows from the processing liquid source 72 into the extraction path 81
  • the reaction liquid (TA) flows from the reaction liquid source 82 into the reaction liquid supply path 83
  • the processing liquid L and the reaction solution merge.
  • the mixed liquid of the processing liquid L and the reaction liquid flows into the reactor 84 from the confluence path 85.
  • the control unit 90 starts electrolyzing the mixed liquid in the reactor 84.
  • the control unit 90 applies a predetermined voltage to the first detection electrode 842 and the second detection electrode 843 to generate OH radicals in the mixed liquid in the reactor 84 .
  • This OH radical reacts with the mixed reaction solution to become fluorescent 2-hydroxyterephthalic acid (HTA).
  • a mixed liquid containing HTA depending on the reaction state of the reactor 84 flows into the sample tube 861 of the detection mechanism 86 .
  • the detection mechanism 86 irradiates excitation light from the irradiation section 862 to the detected section 861a of the sample tube 861, and when the light receiving section 863 receives the fluorescence of HTA, transmits an electric signal corresponding to the amount of fluorescence to the control section 90. .
  • the control unit 90 calculates the amount of OH radicals based on this electrical signal, and determines whether the calculated amount of OH radicals is within the target range. If it is outside the target range, the voltage applied from the power source 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 adjusted to be increased, and when the calculated amount of OH radicals is more than the target range, the voltage is adjusted to be lowered. Thereby, the substrate processing apparatus 1 can optimize in advance the voltage that the power supply 43 actually applies to the first electrode 41 and the second electrode 42 in the processing container 10.
  • the voltage adjustment step is not limited to being performed every time one substrate W is processed, but may be performed as necessary.
  • the control unit 90 may be configured to perform the voltage adjustment step first after startup or maintenance of the substrate processing apparatus 1, and not perform the voltage adjustment step during subsequent substrate processing.
  • the control unit 90 may be configured to perform the voltage adjustment step when the processing liquid source 72 is filled with the processing liquid L.
  • the control unit 90 After adjusting the voltage scheduled to be applied in the voltage adjustment step, the control unit 90 closes the valves 81v and 83v, ends the voltage adjustment step, and moves to etching processing (steps S3 to S7), which is substrate processing.
  • the control unit 90 first operates the rotating unit 60 to rotate the substrate W and the first electrode 41 (step S3).
  • the substrate rotation unit 61 rotates the substrate W in a predetermined rotation direction and at a set target rotation speed for the substrate.
  • the electrode rotation unit 44 rotates the first electrode 41 in the opposite direction to the rotation direction of the substrate W and at a set target rotation speed for the electrode.
  • control unit 90 opens the valve 71v of the processing liquid supply path 71 to cause the processing liquid L from the processing liquid source 72 to flow into the nozzle 31, and supplies the processing liquid L 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 passes through each through hole 413 of the first electrode 41 and hits the surface of the substrate W.
  • the processing liquid L wets and spreads toward the outside in the radial direction of the substrate W due to the centrifugal force accompanying the rotation of the substrate W and the opposing portion 411. Thereby, the entire electrode surface 411a of the first electrode 41 and the entire surface of the substrate W come into contact with the processing liquid L in the processing space PS.
  • the control unit 90 operates the power supply unit 40 to apply a voltage of a predetermined output value (for example, 2V) from the power supply 43 to the first electrode 41 and the second electrode 42 that are in contact with the processing liquid L. (Step S5). Thereby, the first electrode 41 and the second electrode 42 are electrically connected through the processing liquid L, and the processing liquid L is electrolyzed. Due to electrolysis, OH radicals are generated in the processing liquid L near the electrode surface 411a of the first electrode 41. The OH radicals separate the resist film from the substrate W by reacting with the resist film that is the removal target A of the substrate W.
  • the substrate processing apparatus 1 can uniformly remove the resist film on the entire surface of the substrate W by the opposing portion 411 facing the entire surface of the substrate W.
  • the control unit 90 measures the period during which the etching process is performed upon the start of electrolysis of the treatment liquid L, and determines whether a predetermined set period has elapsed (step S6).
  • the set period is a period during which the resist film of the substrate W is removed by OH radicals, which is determined through experiments, simulations, and the like.
  • the substrate processing apparatus 1 continues the relative rotation of the substrate W and the first electrode 41, the supply of the processing liquid L, and the supply of power (electrolysis) to the processing liquid L until the etching processing period passes the set period. By doing so, the resist film can be reliably removed.
  • control unit 90 ends the etching process (step S7). At this time, the control unit 90 stops the power supply to the first electrode 41 and the second electrode 42, and also stops the supply of the processing liquid L to the nozzle 31 by closing the valve 71v.
  • control unit 90 performs a rinsing process for the substrate W as substrate processing in order to drain the processing liquid L remaining on the surface of the substrate W (step S8).
  • the valve 73v is opened, and the rinsing liquid from the rinsing liquid source 74 is allowed to flow into the nozzle 31 while the substrate W is rotated by the rotation unit 60, and the rinsing liquid is applied to the substrate W from the discharge port 31a of the nozzle 31. supply The rinsing liquid spreads on the surface of the substrate W due to the centrifugal force of rotation, and the processing liquid L is discharged from the surface of the substrate W.
  • the control unit 90 After the rinsing process, the control unit 90 performs a spin drying process as substrate processing in order to dry the rinsing liquid on the surface of the substrate W (step S9).
  • the spin drying process the rinsing liquid on the surface of the substrate W is dried by rotating the substrate W by the rotation unit 60.
  • a drying liquid which is the processing liquid L, may be supplied from the liquid supply unit 30 to the surface of the substrate W to replace the rinsing liquid with the drying liquid.
  • control unit 90 releases the holding of the substrate W by the holding unit 20, opens the gate valve 12, causes the transfer device 2 to enter the processing container 10, and transfers the substrate W to the transfer device 2. , the substrate W is carried out from inside the processing container 10 (step S10). Thereby, the substrate processing apparatus 1 can satisfactorily obtain the substrate W from which the resist film has been removed.
  • the substrate processing apparatus 1 and the substrate processing method voltage is applied to the first electrode 41 and the second electrode 42 while the first electrode 41 and the substrate W are in contact with the processing liquid L supplied from the liquid supply section 30. Apply. Therefore, OH radicals are generated in the processing liquid L near the first electrode 41, and the OH radicals can be smoothly applied to the removal target A of the substrate W. Thereby, the substrate processing apparatus 1 and the substrate processing method can efficiently remove the removal target A on the surface of the substrate W. Further, since the substrate processing apparatus 1 does not use sulfuric acid, it is possible to eliminate the treatment necessary for disposing of sulfuric acid, and as a result, reduce the environmental load.
  • the substrate processing apparatus 1 can easily spread the processing liquid L supplied to the surface of the substrate W over the entire surface by rotating at least one of the first electrode 41 and the substrate W using the rotating section 60.
  • the first electrode 41 has at least one layer of gold, palladium, carbon, and boron-doped diamond (BDD) on the electrode surface 411a to increase oxygen overvoltage and direct OH radicals into the processing liquid L. can be easily generated.
  • BDD boron-doped diamond
  • the opposing parts 411 and 411A of the first electrode 41 have holes (through holes 413, mesh) through which the processing liquid L discharged from the upper nozzle 31 passes, so that the surface of the substrate W can be stably processed. Liquid L can be continuously supplied.
  • the substrate processing apparatus 1 and the substrate processing method by using an aqueous solution containing an electrolyte as the processing liquid L, it becomes possible to promote electrolysis of the processing liquid L.
  • the aqueous solution contains at least one of HF, HCl, NH 4 OH, TMAH, H 2 O 2 , H 2 SO 4 , H 3 PO 4 , and HNO 3 to sufficiently generate OH radicals. Can be done.
  • the substrate processing apparatus 1 by detecting OH radicals generated in the processing liquid L separately from the processing container 10 using the detection unit 80, it is possible to accurately adjust the voltage applied by the power supply unit 40. can.
  • the substrate processing apparatus 1 easily detects the amount of OH radicals by optically detecting a fluorescent substance generated by reacting with OH radicals in the reactor 84. becomes possible.
  • the substrate processing apparatus 1 reacts with OH radicals, becomes fluorescent, and can stably detect the amount of OH radicals.
  • the substrate processing apparatus 1 and substrate processing method of the present disclosure are not limited to the above embodiments, and may take various modifications.
  • the substrate processing apparatus 1 uses the resist film as the removal target A, but the same substrate processing can also be performed on the metal film, metal nitride film, and polymer residue on the surface of the substrate W.
  • the metal film is at least one of W, TiN, Co, Ni, Ru, Mo, and Al, the metal film can be effectively removed by the OH radicals generated in the treatment liquid L.
  • the first electrode 41 has a facing portion 411B that partially covers the surface of the substrate W, and the facing portion 411B is rotated by the electrode rotating portion 44 (see FIG. 1).
  • a configuration may also be adopted in which the rotation is performed.
  • the opposing portion 411B is formed, for example, into an elongated rectangular flat plate extending beyond the diameter of the substrate W, and can face the entire surface of the substrate W as it rotates.
  • the processing liquid L discharged from the nozzle 31 is supplied to the surface of the substrate W when the opposing portion 411B is not opposed to the discharge port 31a. Even in this case, the power supply section 40 can satisfactorily remove the removal target A of the substrate W by generating OH radicals near the opposing section 411B by power supply.
  • the first electrode 41 has a fan-shaped facing part 411C with a narrow center and a wide outer peripheral edge, and the facing part 411C is rotated by the electrode rotating part 44.
  • a configuration may also be adopted in which the By applying the facing part 411C in this way, the facing part 411C can face the surface near the outer periphery of the substrate W for a longer time, and the removal target A near the outer periphery of the substrate W can be more stably removed. Can be removed.
  • the rotating section 60 may be configured to include a fixing structure 48 for fixing the first electrode 41 without including the electrode rotating section 44 (see FIG. 1).
  • the rotating unit 60 causes the substrate rotating unit 61 to rotate the substrate W, and spreads the processing liquid L supplied to the surface of the substrate W over the entire surface of the substrate W.
  • 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 .
  • the means for supplying the processing liquid L to the entire surface of the substrate W in the substrate processing apparatus 1 is not particularly limited as long as it can generate OH radicals over the entire surface of the substrate W.
  • the rotating unit 60 includes the electrode rotating unit 44 but does not include the substrate rotating unit 61 (does not rotate the substrate W), as the first electrode 41 rotates, the surface of the substrate W may be rotated.
  • the processing liquid L can be spread over the entire area.
  • the first electrode 41A according to the fifth modification does not have a configuration in which the removal target A is removed from the entire surface of the substrate W as in the above-described embodiment.
  • the configuration is such that the removal target A near the periphery is removed.
  • the first electrode 41A includes a connecting portion 415 fixed to the fixing structure 48, and a protruding portion 416 that is supported by the connecting portion 415 and protrudes briefly above the surface of the substrate W.
  • the protrusion 416 is set to a length such that it can face only the outer peripheral edge of the substrate W, and is close to a portion of the outer peripheral edge of the substrate W in the circumferential direction.
  • the substrate processing apparatus 1 supplies the processing liquid L to the surface of the substrate W from the nozzle 31 while rotating the substrate W using the rotating section 60 (substrate rotating section 61), and supplies the processing liquid L to the surface of the substrate W from the nozzle 31, and also supplies the first electrode 41A and the second electrode using the power supply section 40.
  • a voltage is applied to the electrode 42.
  • the protrusion 416 of the first electrode 41A generates OH radicals in the processing liquid L near the outer periphery of the substrate W, and the object to be removed near the outer periphery can be favorably removed by the OH radicals.
  • the first electrode 41B according to the sixth modification rotates around the outer periphery of the substrate instead of the protrusion 416 in order to remove the removal target A near the outer periphery of the substrate W. It has a ring part 417. Even in this case, the substrate processing apparatus 1 can effectively remove the object to be removed near the outer peripheral edge of the substrate W.
  • the substrate processing apparatus 1 has a flow path 412a formed inside the electrode shaft portion 412 of the first electrode 41C, and the protruding end of the nozzle 31 inserted into the flow path 412a. It is inserted.
  • the flow path 412a communicates with an opening formed at 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 cause the processing liquid L discharged from the discharge port 31a of the nozzle 31 to flow into the processing space PS from the opening.
  • the electrode moving unit 45 is configured to move the nozzle 31 and the first electrode 41 together.
  • the substrate processing apparatus 1A is configured to apply a voltage to the first electrode 41 and the second electrode 42 while the substrate W is immersed in the processing liquid L.
  • the holding part 20 has a chuck mechanism 22 that vacuum-chucks the substrate W, and also has a frame part 23 that protrudes outward in the radial direction of the substrate W and above the substrate W, and that circulates annularly in the circumferential direction.
  • the liquid supply unit 30 has a nozzle 31 that supplies the processing liquid L above the storage space 24.
  • the nozzle 31 retreats from the cup 50 after supplying the processing liquid L.
  • the nozzle 31 may be configured to stand by 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 decreases.
  • the power feeding 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 on the horizontal outer side of the first electrode 41.
  • the first electrode 41 is connected to an electrode moving section 45 . Note that although this modification does not include the rotating section 60 (the substrate rotating section 61 and the electrode rotating section 44), the substrate processing apparatus 1A is equipped with the rotating section 60 that rotates the substrate W and the first electrode 41. It can also be a configuration.
  • this substrate processing apparatus 1A when a voltage is applied to the first electrode 41 and the second electrode 42 by the power source 43 with the processing liquid L stored in the storage space 24, the electrode surface of the first electrode 41 OH radicals are generated near 411a. Therefore, this substrate processing apparatus 1A can also remove the removal target A on the surface of the substrate W using the generated OH radicals. In particular, the substrate processing apparatus 1A can more uniformly remove the removal target A by suppressing the turbulent flow of the processing liquid L during electrolysis.
  • the substrate processing apparatus 1B is configured to simultaneously clean the first electrode 41 that has been subjected to the etching process during the rinsing process of the substrate W.
  • the substrate processing apparatus 1B includes a support arm 45a that supports the first electrode 41 as an electrode moving section 45, and an arm rotation section 45b that rotates the support arm 45a.
  • the substrate processing apparatus 1B disposes the first electrode 41 above the substrate W in the vertical direction and in the vicinity of the substrate W, and generates OH radicals in the processing liquid L during the etching process. By generating, the removal target A of the substrate W is removed.
  • the substrate processing apparatus 1B rotates the support arm 45a using the arm rotating section 45b to move the first electrode 41 to the electrode retracted position. As a result, the surface of the substrate W is exposed, and the first electrode 41 can perform another process at the electrode retracted position.
  • the substrate processing apparatus 1B performs the above-mentioned rinsing process and spin drying process on the exposed substrate W (see also FIG. 4). For example, in the rinsing process, the substrate processing apparatus 1B moves the cleaning nozzle 33 that discharges a rinsing liquid (DIW) above the substrate W, and rotates the substrate W while supplying the rinsing liquid.
  • DIW rinsing liquid
  • the first electrode 41 placed in the electrode retracted position is subjected to an electrode rinsing process and an air blow drying process in this order.
  • the substrate processing apparatus 1B moves the bar nozzle 34 that discharges the rinsing liquid (DIW) above (or below) the first electrode 41, and slides the bar nozzle 34 while supplying the rinsing liquid. let Thereby, the first electrode 41 used for electrolysis can be cleaned.
  • the substrate processing apparatus 1B moves a blower (not shown) above (or below) the first electrode 41 to remove the rinse liquid adhering to the first electrode 41. In this way, by cleaning the first electrode 41, the substrate processing apparatus 1B can increase the durability of the first electrode 41 and use the first electrode 41 for a long period of time.
  • the substrate processing apparatus 1C may be configured as a batch-type apparatus that simultaneously processes a plurality of substrates W.
  • the batch-type substrate processing apparatus 1C has a processing tank 15 (processing container) that stores processing liquid L and can accommodate a plurality of substrates W. are immersed in one batch. For example, each substrate W is held by a holding section (not shown) so as to extend along the vertical direction.
  • the substrate processing apparatus 1C has a liquid supply section (not shown) that supplies the processing liquid L into the processing tank 15.
  • the substrate processing apparatus 1C arranges the first electrodes 41 at positions near each substrate W in the held state. Further, the second electrode 42 is arranged at an appropriate position within the processing tank 15. Thereby, 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 source 43 to the first electrode 41 and the second electrode 42. In the substrate W disposed adjacent to each first electrode 41, the removal target A is successfully removed by the OH radicals.
  • the substrate processing apparatus 1 and substrate processing method according to the embodiment disclosed herein are illustrative in all respects and are not restrictive.
  • the embodiments can be modified and improved in various ways without departing from the scope and spirit of the appended claims.
  • the matters described in the plurality of embodiments described above may be configured in other ways without being inconsistent, and may be combined without being inconsistent.

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Abstract

This substrate treatment device removes an object to be removed from a substrate using a treatment solution. The substrate treatment device comprises: a holding unit that holds the substrate; a solution supply unit that supplies treatment solution to the substrate that is held by the holding unit; an electrode that is disposed so as not to be in contact with the substrate that is held by the holding unit, and makes contact with the treatment solution that is supplied from the solution supply unit; an electric power source that applies a voltage to the electrode; and a control unit that controls the solution supply unit and the electric power source. The control unit generates OH radicals in the treatment solution that is supplied from the solution supply unit, by applying a voltage to the electrode with the electrode and the substrate in contact with the treatment solution, and provides the OH radicals to the object to be removed.

Description

基板処理装置、および基板処理方法Substrate processing equipment and substrate processing method
　本開示は、基板処理装置、および基板処理方法に関する。 The present disclosure relates to a substrate processing apparatus and a substrate processing method.
　従来、基板の表面のレジスト膜、金属膜、窒化金属膜、ポリマの残渣（以下、まとめて除去対象という）をエッチングする基板処理方法では、硫酸と過酸化水素水とを基板の表面の除去対象に供給している。基板の表面に供給された硫酸および過酸化水素水は、その酸化力によって除去対象を基板から剥離することができる。 Conventionally, in the substrate processing method that etches the resist film, metal film, metal nitride film, and polymer residue (hereinafter collectively referred to as the removal target) on the surface of the substrate, sulfuric acid and hydrogen peroxide solution are used as the removal target on the surface of the substrate. is supplied to. The sulfuric acid and hydrogen peroxide solution supplied to the surface of the substrate can peel off the object to be removed from the substrate by their oxidizing power.
　また、特許文献１には、環境負荷を軽減するために硫酸を用いずに、酸素ガスと、オゾン水とを混合させた液滴に対してＵＶ光を照射し、この液滴をレジスト膜に供給することで、レジスト膜を除去する基板処理装置が開示されている。 Furthermore, in order to reduce the environmental impact, UV light is irradiated onto droplets of a mixture of oxygen gas and ozone water without using sulfuric acid, and the droplets are applied to a resist film. A substrate processing apparatus is disclosed that removes a resist film by supplying a resist film.
特開２０２１－１４８９５５号公報Japanese Patent Application Publication No. 2021-148955
　本開示は、基板の表面の除去対象を効率的に除去することができる技術を提供する。 The present disclosure provides a technique that can efficiently remove a target to be removed from the surface of a substrate.
　本開示の一態様によれば、基板の除去対象を処理液で除去する基板処理装置であって、前記基板を保持する保持部と、前記保持部に保持された前記基板に前記処理液を供給する液供給部と、前記保持部に保持された前記基板に対して間隔をおいて配置され、かつ前記液供給部から供給される前記処理液に接触する電極と、前記電極に電圧を印加する電源と、前記液供給部および前記電源を制御する制御部と、を備え、前記制御部は、前記液供給部から供給した前記処理液に前記電極および前記基板を接触させた状態として前記電極に電圧を印加することで、前記処理液にＯＨラジカルを生成して、前記ＯＨラジカルを前記除去対象に付与する、基板処理装置が提供される。 According to one aspect of the present disclosure, there is provided a substrate processing apparatus that removes a target to be removed from a substrate using a processing liquid, the apparatus comprising: a holding part that holds the substrate; and a holding part that supplies the processing liquid to the substrate held by the holding part. a liquid supply unit for applying a voltage to the electrode, an electrode arranged at a distance from the substrate held by the holding unit and in contact with the processing liquid supplied from the liquid supply unit; a power supply; a control unit that controls the liquid supply unit and the power supply; A substrate processing apparatus is provided that generates OH radicals in the processing liquid and applies the OH radicals to the object to be removed by applying a voltage.
　一態様によれば、基板の表面の除去対象を効率的に除去することができる。 According to one embodiment, the target to be removed on the surface of the substrate can be efficiently removed.
一実施形態に係る基板処理装置の全体構成を示す概略説明図である。1 is a schematic explanatory diagram showing the overall configuration of a substrate processing apparatus according to an embodiment. 図２（Ａ）は、一実施形態に係る第１電極の対向部を示す概略平面図である。図２（Ｂ）は、第１変形例に係る対向部を示す概略平面図である。FIG. 2(A) is a schematic plan view showing the facing portion of the first electrode according to one embodiment. FIG. 2(B) is a schematic plan view showing the facing portion according to the first modification. 基板処理装置の電解によるＯＨラジカルの生成を拡大して示す断面図である。FIG. 3 is an enlarged cross-sectional view showing the generation of OH radicals due to electrolysis in the substrate processing apparatus. 一実施形態に係る基板処理方法のフローチャートである。3 is a flowchart of a substrate processing method according to one embodiment. 図５（Ａ）は、第２変形例に係る対向部を示す概略平面図である。図５（Ｂ）は、第３変形例に係る対向部を示す概略平面図である。FIG. 5(A) is a schematic plan view showing the facing portion according to the second modification. FIG. 5(B) is a schematic plan view showing the facing portion according to the third modification. 第４変形例に係る基板処理装置を部分的に示す概略説明図である。FIG. 7 is a schematic explanatory diagram partially showing a substrate processing apparatus according to a fourth modification. 図７（Ａ）は、第５変形例に係る第１電極を示す概略平面図である。図７（Ｂ）は、第６変形例に係る第１電極を示す概略平面図である。FIG. 7(A) is a schematic plan view showing a first electrode according to a fifth modification. FIG. 7(B) is a schematic plan view showing the first electrode according to the sixth modification. 第７変形例に係る基板処理装置を部分的に示す概略説明図である。FIG. 7 is a schematic explanatory diagram partially showing a substrate processing apparatus according to a seventh modification. 第８変形例に係る基板処理装置を部分的に示す概略説明図である。It is a schematic explanatory view partially showing a substrate processing apparatus according to an eighth modification. 第９変形例に係る基板処理装置を部分的に示す概略平面図である。FIG. 12 is a schematic plan view partially showing a substrate processing apparatus according to a ninth modification. 第１０変形例に係る基板処理装置を部分的に示す概略平面図である。FIG. 7 is a schematic plan view partially showing a substrate processing apparatus according to a tenth modification.
　以下、図面を参照して本開示を実施するための形態について説明する。各図面において、同一構成部分には同一符号を付し、重複した説明を省略する場合がある。 Hereinafter, embodiments for implementing the present disclosure will be described with reference to the drawings. In each drawing, the same components are given the same reference numerals, and redundant explanations may be omitted.
　一実施形態に係る基板処理装置１は、図１に示すように、基板処理として、基板Ｗの表面の除去対象Ａに処理液Ｌを供給して、除去対象Ａを除去するエッチング処理を行う。また、図１に示す基板処理装置１は、基板Ｗを一枚ずつ処理する枚葉式の装置に構成されている。 As shown in FIG. 1, the substrate processing apparatus 1 according to one embodiment performs an etching process to remove the removal target A by supplying a processing liquid L to the removal target A on the surface of the substrate W as substrate processing. Further, the substrate processing apparatus 1 shown in FIG. 1 is configured as a single-wafer type apparatus that processes the substrates W one by one.
　基板Ｗの表面から除去する除去対象Ａとしては、例えば、レジスト膜、金属膜または窒化金属膜、もしくは基板Ｗに残存するポリマ（樹脂）残渣があげられる。レジスト膜は、樹脂（ポリマ）と感光剤を含む。なお、レジスト膜は、イオン線を露光することにより硬化されたものでもよい。金属膜は、タングステン（Ｗ）、窒化チタン（ＴｉＮ）、コバルト（Ｃｏ）、ニッケル（Ｎｉ）、ルテニウム（Ｒｕ）、モリブデン（Ｍｏ）、アルミ（Ａｌ）のうち少なくとも１つを含むものがあげられる。金属膜は、単金属でも合金でもよい。窒化金属膜としては、例えば、窒化チタン（ＴｉＮ）があげられる。また、ポリマ残渣は、本実施形態とは別の基板処理によって、基板Ｗの表面に意図せずに残ったポリマの異物である。以下では、除去対象Ａとしてレジスト膜を有する基板Ｗにおいて、当該レジスト膜を除去する例を説明していく。 The removal target A to be removed from the surface of the substrate W includes, for example, a resist film, a metal film, a metal nitride film, or a polymer (resin) residue remaining on the substrate W. The resist film includes a resin (polymer) and a photosensitizer. Note that the resist film may be cured by exposure to ion beams. The metal film includes at least one of tungsten (W), titanium nitride (TiN), cobalt (Co), nickel (Ni), ruthenium (Ru), molybdenum (Mo), and aluminum (Al). . The metal film may be a single metal or an alloy. Examples of the metal nitride film include titanium nitride (TiN). Further, the polymer residue is a polymer foreign substance that remains unintentionally on the surface of the substrate W due to substrate processing different from this embodiment. In the following, an example of removing a resist film on a substrate W having a resist film as a removal target A will be described.
　基板処理装置１は、処理容器１０と、処理容器１０内で基板Ｗを保持する保持部２０と、処理容器１０内の基板Ｗに処理液Ｌを供給する液供給部３０と、処理液Ｌに電力を給電する給電部４０と、使用した処理液Ｌを回収するカップ５０と、を含む。また、基板処理装置１は、この基板処理装置１の各構成を制御する制御部９０を備える。 The substrate processing apparatus 1 includes a processing container 10, a holding section 20 that holds the substrate W within the processing container 10, a liquid supply section 30 that supplies the processing liquid L to the substrate W within the processing container 10, and a It includes a power supply unit 40 that supplies power, and a cup 50 that collects the used processing liquid L. Further, the substrate processing apparatus 1 includes a control section 90 that controls each component of the substrate processing apparatus 1.
　処理容器１０は、保持部２０およびカップ５０を内部に収容する箱状に形成されている。処理容器１０は、ゲート１１と、ゲート１１を開閉するゲートバルブ１２と、を有する。基板Ｗは、搬送装置２により搬送され、ゲートバルブ１２の開放状態で、ゲート１１を介して処理容器１０の内部に搬入される。その後、ゲートバルブ１２がゲート１１を気密に閉塞すると、基板Ｗは、処理容器１０の内部にてエッチング処理が施される。基板処理後にゲートバルブ１２が開放すると、基板Ｗは、処理容器１０の内部に進入した搬送装置２に受け渡され、ゲート１１を介して処理容器１０の外部に搬出される。 The processing container 10 is formed into a box shape that accommodates the holding portion 20 and the cup 50 therein. The processing container 10 has a gate 11 and a gate valve 12 that opens and closes the gate 11. The substrate W is transported by the transport device 2 and loaded into the processing container 10 via the gate 11 with the gate valve 12 in an open state. Thereafter, when the gate valve 12 hermetically closes the gate 11, the substrate W is subjected to an etching process inside the processing container 10. When the gate valve 12 is opened after substrate processing, the substrate W is transferred to the transport device 2 that has entered the processing container 10 and is carried out to the outside of the processing container 10 via the gate 11.
　保持部２０は、基板処理時に、処理容器１０の内部において基板Ｗを水平に保持する。保持部２０は、円盤状のベース２１と、基板Ｗの表面（除去対象Ａ）を鉛直方向上側に向けた状態で保持するチャック機構２２と、を有する。チャック機構２２は、図１において基板Ｗの外周縁を把持するメカニカルチャックを適用しているが、これに限定されるものではなく、例えば、真空吸着チャック、静電チャック等でもよい。また、保持部２０には、チャック機構２２から基板Ｗを浮上させて、搬送装置２との間で基板Ｗの受け取りおよび受け渡しを行う図示しない複数のリフトピンが設けられている。 The holding unit 20 holds the substrate W horizontally inside the processing container 10 during substrate processing. The holding unit 20 includes a disk-shaped base 21 and a chuck mechanism 22 that holds the surface of the substrate W (removal target A) in a state facing upward in the vertical direction. Although the chuck mechanism 22 is a mechanical chuck that grips the outer peripheral edge of the substrate W in FIG. 1, it is not limited to this, and may be, for example, a vacuum chuck, an electrostatic chuck, or the like. Further, the holding unit 20 is provided with a plurality of lift pins (not shown) that levitate the substrate W from the chuck mechanism 22 and receive and transfer the substrate W to and from the transport device 2 .
　保持部２０は、基板処理装置１の回転部６０の一方である基板回転部６１に支持されている。回転部６０は、基板Ｗおよび給電部４０の第１電極４１のうち少なくとも一方を、他方に対して相対的に回転させる。なお、本実施形態に係る回転部６０は、基板Ｗおよび第１電極４１の両方を回転させる構成としている。 The holding section 20 is supported by a substrate rotating section 61, which is one of the rotating sections 60 of the substrate processing apparatus 1. The rotating section 60 rotates at least one of the substrate W and the first electrode 41 of the power feeding section 40 relative to the other. Note that the rotating section 60 according to this embodiment is configured to rotate both the substrate W and the first electrode 41.
　基板回転部６１は、上端部において保持部２０のベース２１を固定する保持軸部６２と、保持軸部６２の下端部を支持してこの保持軸部６２を回転させる回転ユニット６３と、を含む。回転ユニット６３は、図示しないモータおよび駆動伝達機構を有し、また制御部９０に通信可能に接続されている。回転ユニット６３は、制御部９０の制御下にモータを駆動させることで、保持軸部６２を介して保持部２０に保持された基板Ｗを目標回転速度で回転させる。 The substrate rotating section 61 includes a holding shaft section 62 that fixes the base 21 of the holding section 20 at its upper end, and a rotation unit 63 that supports the lower end of the holding shaft section 62 and rotates the holding shaft section 62. . The rotation unit 63 has a motor and a drive transmission mechanism (not shown), and is communicably connected to the control section 90. The rotation unit 63 rotates the substrate W held by the holding part 20 via the holding shaft part 62 at a target rotation speed by driving a motor under the control of the control part 90.
　液供給部３０は、保持部２０に保持された基板Ｗの表面に液体を吐出する。液供給部３０は、例えば、液体の流路を内部に有する管状のノズル３１と、処理容器１０の内部においてノズル３１を移動させるノズル移動部３２と、を含む。また、液供給部３０は、処理容器１０の外部からノズル３１に液体を供給する外部供給部７０を有する。 The liquid supply unit 30 discharges a 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 inside the processing container 10. The liquid supply unit 30 also includes an external supply unit 70 that supplies liquid to the nozzle 31 from outside the processing container 10 .
　ノズル３１は、保持部２０に保持された基板Ｗよりも上方に配置されている。ノズル３１は、側面視でＬ字状を呈し、処理容器１０の側壁から保持部２０の中心付近に向かって水平に延在し、保持部２０の中心付近において下方に屈曲する突出端部を有している。突出端部の下端には、ノズル３１の流路に連通して、基板Ｗの表面に液体を吐出する吐出口３１ａが設けられている。 The nozzle 31 is arranged above the substrate W held by the holding part 20. The nozzle 31 has an L-shape in side view, extends horizontally from the side wall of the processing container 10 toward the vicinity of the center of the holding part 20 , and has a protruding end portion bent downward near the center of the holding part 20 . are doing. A discharge port 31a that communicates with 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.
　ノズル移動部３２は、ノズル３１を水平方向および鉛直方向に移動させる。ノズル移動部３２は、図示しないモータおよび駆動伝達機構を有し、また制御部９０に通信可能に接続されている。ノズル移動部３２は、制御部９０の制御下に動作することで、カップ５０から退避させたノズル退避位置と、吐出口３１ａが基板Ｗの略中心に位置する吐出位置と、にノズル３１を配置させる。 The nozzle moving unit 32 moves the nozzle 31 in the horizontal and vertical directions. The nozzle moving section 32 has a motor and a drive transmission mechanism (not shown), and is communicably connected to the control section 90. The nozzle moving unit 32 operates under the control of the control unit 90 to arrange the nozzle 31 at a nozzle retracted position where the nozzle is retracted from the cup 50 and at an ejection position where the ejection port 31a is located approximately at the center of the substrate W. let
　外部供給部７０は、基板処理時に、処理容器１０の外部からノズル３１に液体を供給する。基板処理に使用する液体としては、例えば、エッチング処理に用いる処理液Ｌ（薬液）と、エッチング処理後に処理液Ｌと置換するためのリンス液と、があげられる。図１では、１つのノズル３１が処理液Ｌとリンス液を順番に吐出する構成を例示しているが、基板処理装置１は、複数のノズル３１により異なる種類の処理液Ｌを吐出する構成でもよい。なお、外部供給部７０は、リンス液の吐出後に、当該リンス液よりも揮発性が高い乾燥液（例えば、イソプロピレンアルコール等の有機溶剤）をさらに吐出して、リンス液を乾燥液に置換する構成でもよい。 The external supply unit 70 supplies liquid to the nozzle 31 from outside the processing container 10 during substrate processing. Examples of the liquid used for substrate processing include a processing liquid L (chemical liquid) used for etching processing and a rinsing liquid for replacing processing liquid L after etching processing. Although FIG. 1 illustrates a configuration in which one nozzle 31 sequentially discharges a processing liquid L and a rinsing liquid, the substrate processing apparatus 1 may also have a configuration in which a plurality of nozzles 31 discharge different types of processing liquid L. good. Note that, after discharging the rinsing liquid, the external supply unit 70 further discharges a drying liquid (for example, an organic solvent such as isopropylene alcohol) that is more volatile than the rinsing liquid to replace the rinsing liquid with the drying liquid. It can also be a configuration.
　処理液Ｌは、基板Ｗに対向する給電部４０の第１電極４１の種類（陽極、陰極）等に応じて、適切な電解質を含む水溶液を選択することが好ましい。例えば、第１電極４１が陽極の場合には、ＨＦ、ＨＣｌ、ＮＨ４ＯＨ、ＴＭＡＨ（水酸化テトラメチルアンモニウム：Ｍｅ４ＮＯＨ）、Ｈ２ＳＯ４、Ｈ３ＰＯ４、ＨＮＯ３等のうち少なくとも１つを含む水溶液を用いるとよい。特に、除去対象Ａがレジスト膜である場合には、溶解を促進するために、アルカリ水溶液がより好ましい。また、第１電極４１が陰極の場合には、Ｈ２Ｏ２を含む水溶液を用いるとよく、例えば、ＳＣ１（ＮＨ４ＯＨ＋Ｈ２Ｏ２）、ＳＣ２（ＨＣｌ＋Ｈ２Ｏ２）等があげられる。一方、リンス液は、例えば、ＤＩＷ（脱イオン水）である。 As the processing liquid L, it is preferable to select an aqueous solution containing an appropriate electrolyte depending on the type (anode, cathode) of the first electrode 41 of the power supply section 40 facing the substrate W, and the like. For example, when the first electrode 41 is an anode, at least one of HF, HCl, NH4OH , TMAH (tetramethylammonium hydroxide: Me4NOH ), H2SO4 , H3PO4 , HNO3, etc. It is preferable to use an aqueous solution containing one of them. In particular, when the object A to be removed is a resist film, an alkaline aqueous solution is more preferable in order to promote dissolution. Furthermore, when the first electrode 41 is a cathode, an aqueous solution containing H 2 O 2 may be used, such as SC1 (NH 4 OH+H 2 O 2 ), SC2 (HCl+H 2 O 2 ), and the like. On the other hand, the rinsing liquid is, for example, DIW (deionized water).
　外部供給部７０は、ノズル３１に処理液Ｌを供給する処理液供給経路７１と、処理液供給経路７１の上流に設けられる処理液源７２と、ノズル３１にリンス液を供給するリンス液供給経路７３と、リンス液供給経路７３の上流に設けられるリンス液源７４と、を含む。処理液供給経路７１およびリンス液供給経路７３は、液体を流通可能な流路を内側に有するチューブによって構成され、途中位置に流路を開閉するバルブ７１ｖ、７３ｖを備える。さらに、処理液供給経路７１およびリンス液供給経路７３には、処理液Ｌを圧送するポンプ、処理液Ｌの流量を調整する流量調整器、処理液Ｌの温度を調整する温度調整器等が設けられる（共に不図示）。また、リンス液供給経路７３は、処理液供給経路７１の途中位置で合流している。これにより、外部供給部７０は、制御部９０の制御下に、処理液Ｌおよびリンス液を選択的にノズル３１に供給できる。 The external supply unit 70 includes a processing liquid supply path 71 that supplies the processing liquid L to the nozzle 31, a processing liquid source 72 provided upstream of the processing liquid supply path 71, and a rinsing liquid supply path that supplies the rinsing liquid to the nozzle 31. 73 and a rinsing liquid source 74 provided upstream of the rinsing liquid supply path 73. The processing liquid supply path 71 and the rinsing liquid supply path 73 are constituted by tubes each having a flow path through which a liquid can flow, and are provided with valves 71v and 73v at intermediate positions to open and close the flow path. Furthermore, the processing liquid supply path 71 and the rinsing liquid supply path 73 are provided with a pump that pumps the processing liquid L, a flow rate regulator that adjusts the flow rate of the processing liquid L, a temperature regulator that adjusts the temperature of the processing liquid L, and the like. (both not shown). Further, the rinsing liquid supply path 73 joins the processing liquid supply path 71 at an intermediate position. Thereby, the external supply unit 70 can selectively supply the processing liquid L and the rinsing liquid to the nozzle 31 under the control of the control unit 90.
　給電部４０は、エッチング処理時に吐出する処理液Ｌに電圧を印加する一対の電極を有し、一対の電極による処理液Ｌの電解により、処理液ＬにＯＨラジカル（ヒドロキシルラジカル）を生成する。給電部４０は、一対の電極である第１電極４１および第２電極４２と、一対の電極に電圧を印加する電源４３と、第１電極４１を回転させる電極回転部４４と、第１電極４１を移動させる電極移動部４５と、を含む。すなわち、電極回転部４４は、基板Ｗと相対的に第１電極４１を回転させる回転部６０の一部を構成している。また、電極移動部４５は、第１電極４１を移動させて、保持部２０に保持された基板Ｗに対向する処理位置と、カップ５０の外側に退避した電極退避位置と、に第１電極４１を配置する。 The power supply unit 40 has a pair of electrodes that apply a voltage to the processing liquid L discharged during the etching process, and generates OH radicals (hydroxyl radicals) in the processing liquid L by electrolysis of the processing liquid L by the pair of electrodes. The power supply unit 40 includes a pair of electrodes, a first electrode 41 and a second electrode 42 , a power source 43 that applies voltage to the pair of electrodes, an electrode rotation unit 44 that rotates the first electrode 41 , and a first electrode 41 . an electrode moving section 45 that moves the electrode. That is, the electrode rotating section 44 constitutes a part of the rotating section 60 that rotates the first electrode 41 relative to the substrate W. Further, the electrode moving unit 45 moves the first electrode 41 between a processing position facing the substrate W held by the holding unit 20 and an electrode retraction position where the first electrode 41 is retracted to the outside of the cup 50. Place.
　第１電極４１は、保持部２０に保持された基板Ｗに隣接する位置において間隔をおいて配置され、接触した処理液Ｌ内にＯＨラジカルを生成する電極である。第１電極４１は、電源４３との接続形態に応じて、陽極および陰極のうちいずれを採用してもよい。ただし、陽極を採った場合には、陽極に応じた処理液Ｌ（電解質水溶液）および電極の材料を適用し、陰極を採った場合には、陰極に応じた処理液Ｌおよび電極の材料を適用する。 The first electrode 41 is an electrode that is arranged at a distance from the substrate W held by the holding unit 20 and generates OH radicals in the processing liquid L that comes into contact with it. The first electrode 41 may be either an anode or a cathode depending on the connection form with the power source 43. However, if an anode is used, the treatment liquid L (electrolyte aqueous solution) and electrode material will be applied depending on the anode, and if a cathode is used, the treatment liquid L and electrode material will be applied according to the cathode. do.
　第１電極４１は、保持部２０に対向可能に配置される対向部４１１と、対向部４１１の中心を支持する電極軸部４１２と、を備える。対向部４１１は、平面視で、基板Ｗと略同程度の直径を有する正円状に形成され、基板Ｗの表面全体に対向する電極面４１１ａを有する。対向部４１１は、処理位置に配置された状態で、その中心が基板Ｗの中心に一致し、かつ保持部２０に保持された基板Ｗの表面に対して平行にとなるように電極軸部４１２に支持される。電極面４１１ａと基板Ｗの表面との間には、エッチング処理において処理液Ｌを流通可能な処理空間ＰＳが形成される。 The first electrode 41 includes a facing part 411 that is arranged to face the holding part 20 and an electrode shaft part 412 that supports the center of the facing part 411. The opposing portion 411 is formed in a perfect circular shape having approximately the same diameter as the substrate W in plan view, and has an electrode surface 411a facing the entire surface of the substrate W. When the opposing part 411 is placed at the processing position, the electrode shaft part 411 is arranged so that its center coincides with the center of the substrate W and is parallel to the surface of the substrate W held by the holding part 20. Supported by 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 etching processing.
　処理空間ＰＳの幅（対向部４１１の電極面４１１ａと基板Ｗの表面との間隔Ｄ：図３参照）は、例えば、０．５ｍｍ～５ｍｍの範囲に設定されることが好ましい。これにより、生成された処理液ＬのＯＨラジカルが、除去対象Ａであるレジスト膜とスムーズに付与されるようになる。仮に、処理空間ＰＳの幅が０．５ｍｍ未満の場合には、ノズル３１から吐出された処理液Ｌが処理空間ＰＳに入り込み難くなる可能性がある。また、処理空間ＰＳの幅が５ｍｍを超える場合には、第１電極４１で生成したＯＨラジカルが基板Ｗに届かずに消失する可能性が高くなり、処理効率が低下するおそれがある。 The width of the processing space PS (distance D between the electrode surface 411a of the opposing portion 411 and the surface of the substrate W: see FIG. 3) is preferably set in a range of 0.5 mm to 5 mm, for example. Thereby, the OH radicals of the generated processing liquid L are smoothly applied to the resist film that is the removal target A. If the width of the processing space PS is less than 0.5 mm, it may be difficult for the processing liquid L discharged from the nozzle 31 to enter the processing space PS. Furthermore, if the width of the processing space PS exceeds 5 mm, there is a high possibility that the OH radicals generated at the first electrode 41 will disappear without reaching the substrate W, and there is a possibility that the processing efficiency will decrease.
　対向部４１１を構成する材料は、上記したように電極の種類（陽極、陰極）等に応じて適切なものを選択することが好ましい。例えば、第１電極４１が陽極の場合には、ボロンドープダイアモンド（以下、ＢＤＤという）を適用するとよい。第１電極４１として用いるＢＤＤのボロンドープ濃度としては、１０００ｐｐｍ～２００００ｐｐｍの範囲の質量に設定されることが好ましい。このＢＤＤを適用することにより、第１電極４１は、処理液Ｌに印加する電圧を増やした場合でも、酸素過電圧を大きくして、処理液Ｌから酸素を発生させ難くすることができる。そのため、給電部４０は、高電圧をかけることができ、酸素の代わりにＯＨラジカル等の活性酸素を効率的に生成することが可能となる。 As described above, it is preferable to select an appropriate material for the facing portion 411 depending on the type of electrode (anode, cathode), etc. For example, when the first electrode 41 is an anode, boron-doped diamond (hereinafter referred to as BDD) may be used. The boron doping concentration of the BDD used as the first electrode 41 is preferably set to a mass in the range of 1000 ppm to 20000 ppm. By applying this BDD, the first electrode 41 can increase the oxygen overvoltage and make it difficult to generate oxygen from the processing liquid L even when the voltage applied to the processing liquid L is increased. Therefore, the power supply unit 40 can apply a high voltage and can efficiently generate active oxygen such as OH radicals instead of oxygen.
　一方、第１電極４１が陰極の場合には、耐薬性のある貴金属、もしくはカーボンやＢＤＤを適用するとよい。耐薬性がある貴金属の種類としては、金（Ａｕ）、パラジウム（Ｐｄ）があげられる。ただし、貴金属の１つであるプラチナ（Ｐｔ）については、第１電極４１に適用しないことが好ましい。プラチナは、触媒となって水溶液であるＨ２Ｏ２を分解してしまうからである。なお、第１電極４１は、円盤状のベース部分を別の導電性を有する材料によって構成し、電極面４１１ａのみを上記の材料（金、パラジウム、カーボン、ＢＤＤ）によってコーティングしてもよい。 On the other hand, when the first electrode 41 is a cathode, chemically resistant noble metal, carbon, or BDD may be used. Examples of chemically resistant noble metals include gold (Au) and palladium (Pd). However, platinum (Pt), which is one of the noble metals, is preferably not applied to the first electrode 41. This is because platinum acts as a catalyst and decomposes H 2 O 2 in an aqueous solution. Note that the first electrode 41 may have a disk-shaped base portion made of another conductive material, and only the electrode surface 411a may be coated with the above-mentioned material (gold, palladium, carbon, BDD).
　図２（Ａ）に示すように、第１電極４１の対向部４１１は、中心（電極軸部４１２）から径方向外側に向かって短く離れた位置に、複数の孔（４つの貫通孔４１３）を備える。各貫通孔４１３は、電極軸部４１２から同じ距離だけ離れ、また相互に等間隔に配置されている。各貫通孔４１３は、ノズル３１から吐出された処理液Ｌを、対向部４１１の上面側から電極面４１１ａ側の処理空間ＰＳに通過させる。処理空間ＰＳに供給された処理液Ｌは遠心力によって基板Ｗの径方向全体に供給される。なお、貫通孔４１３の数は、特に限定されないことは勿論である。 As shown in FIG. 2(A), the facing part 411 of the first electrode 41 has a plurality of holes (four through holes 413) at a short distance from the center (electrode shaft part 412) toward the outside in the radial direction. Equipped with Each through hole 413 is spaced from the electrode shaft portion 412 by the same distance, and is arranged at equal intervals from each other. Each through hole 413 allows the processing liquid L discharged from the nozzle 31 to pass from the upper surface side of the opposing portion 411 to the processing space PS on the electrode surface 411a side. The processing liquid L supplied to the processing space PS is supplied to the entire substrate W in the radial direction by centrifugal force. Note that, of course, the number of through holes 413 is not particularly limited.
　あるいは、第１電極４１は、対向部４１１の平板状の中心付近に複数の貫通孔４１３を備える構成に限定されず、種々の形態の対向部４１１を採用してよい。例えば図３Ｂに示す第１変形例のように、対向部４１１Ａは、複数の電極線４１４を編み込むことによって全体としてメッシュ（網目：孔）を有するように形成されたものを適用できる。これにより、対向部４１１Ａは、ノズル３１から吐出された処理液Ｌを、対向部４１１Ａの下方の処理空間ＰＳに一層容易に導くことができる。 Alternatively, the first electrode 41 is not limited to having a plurality of through holes 413 near the center of the flat plate of the opposing portion 411, and may employ various forms of the opposing portion 411. For example, as in the first modification shown in FIG. 3B, the opposing portion 411A may be formed by weaving a plurality of electrode wires 414 so as to have a mesh (holes) as a whole. Thereby, the facing part 411A can more easily guide the processing liquid L discharged from the nozzle 31 to the processing space PS below the facing part 411A.
　電極軸部４１２は、導電性を有する材料により棒状により形成されている。電極軸部４１２の上端部は、処理容器１０の内部において電極回転部４４および電極移動部４５に接続されている。電極軸部４１２の下端部は、対向部４１１の中心に固定されている。対向部４１１および電極軸部４１２は、異なる材料により構成されて適宜の接合手段によって連結したものでもよく、同じ材料により一体成形されたものでもよい。 The electrode shaft portion 412 is made of a conductive material and has a rod shape. The upper end portion of the electrode shaft portion 412 is connected to the electrode rotating portion 44 and the electrode moving portion 45 inside the processing container 10 . The lower end of the electrode shaft portion 412 is fixed to the center of the opposing portion 411. The opposing portion 411 and the electrode shaft portion 412 may be made of different materials and connected by appropriate joining means, or may be integrally molded from the same material.
　電極回転部４４は、図示しないモータおよび駆動伝達機構により構成され、かつ制御部９０に接続されている。電極回転部４４は、制御部９０の制御下に、電極軸部４１２および対向部４１１を目標回転速度で回転させる。第１電極４１の回転方向は、例えば、基板回転部６１による基板Ｗの回転方向と逆回りに設定されるとよい。これにより、ノズル３１の吐出口３１ａに対して第１電極４１および基板Ｗの各々が別タイミングで対向することになり、吐出口３１ａから吐出した処理液Ｌを基板Ｗの全面にスムーズに広げることができる。なお、回転部６０は、第１電極４１の回転方向と第２電極４２の回転方向とを同じ向きとし、相互の目標回転速度をずらすことで、第１電極４１と基板Ｗとの相対位置を変化させてもよい。 The electrode rotating section 44 is constituted by a motor and a drive transmission mechanism (not shown), and is connected to the control section 90. The electrode rotating section 44 rotates the electrode shaft section 412 and the opposing section 411 at a target rotation speed under the control of the control section 90. The rotation direction of the first electrode 41 may be set, for example, to be opposite to the rotation direction of the substrate W by the substrate rotation unit 61. As a result, the first electrode 41 and the substrate W each face the discharge port 31a of the nozzle 31 at different timings, and the processing liquid L discharged from the discharge port 31a can be smoothly spread over the entire surface of the substrate W. Can be done. Note that the rotating unit 60 adjusts the relative position between the first electrode 41 and the substrate W by making the rotation direction of the first electrode 41 and the rotation direction of the second electrode 42 the same, and by shifting their target rotation speeds. It may be changed.
　電極移動部４５は、図示しないモータおよび駆動伝達機構により構成され、かつ制御部９０に接続されている。電極回転部４４は、制御部９０の制御下に、電極軸部４１２および対向部４１１を水平方向かつ鉛直方向に移動させ、上記したように処理位置と電極退避位置とに第１電極４１を配置する。なお、給電部４０は、電極回転部４４と、電極移動部４５とを一体にした機構部を備えてもよい。 The electrode moving unit 45 is composed of a motor and a drive transmission mechanism (not shown), and is connected to the control unit 90. The electrode rotating section 44 moves the electrode shaft section 412 and the opposing section 411 in the horizontal and vertical directions under the control of the control section 90, and arranges the first electrode 41 at the processing position and the electrode retraction position as described above. do. Note that the power feeding section 40 may include a mechanical section that integrates the electrode rotating section 44 and the electrode moving section 45.
　第２電極４２は、ノズル３１の途中位置かつ流路内に設けられることで、ノズル３１を流通する処理液Ｌに定常的に接触することができる。この第２電極４２は、導電性および耐薬性を有していれば、その材料については特に限定されない。 The second electrode 42 is provided in the middle of the nozzle 31 and within the flow path, so that it can constantly 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.
　電源４３は、配線４６を介して第１電極４１に接続され、配線４７を介して第２電極４２に接続されている。電源４３の配線形態は、基板Ｗと対向する第１電極４１の極性に応じて任意に設定してよい。以下では、図１に示すように、第１電極４１を陽極とし、第２電極４２を陰極した場合について説明していく。 The power source 43 is connected to the first electrode 41 via a wiring 46 and to the second electrode 42 via a wiring 47. The wiring form of the power source 43 may be arbitrarily set depending on the polarity of the first electrode 41 facing the substrate W. Below, as shown in FIG. 1, a case will be described in which the first electrode 41 is used as an anode and the second electrode 42 is used as a cathode.
　電源４３は、制御部９０に通信可能に接続されており、制御部９０の制御下に第１電極４１および第２電極４２に直流電圧を印加する。電源４３が印加する電圧の出力値としては、例えば１．８Ｖ～２．２Ｖの範囲であるとよい。ここで、ガラス状カーボン等の一般的な電極は、陽極の電圧を上げていくと酸素が発生することになるが、ＢＤＤを適用した第１電極４１は、酸素過電圧が大きく酸素が発生し難い。このため、電源４３は、高電圧を印加することが可能となり、第１電極４１の周辺にＯＨラジカル等の活性酸素を良好に生成できる。 The power source 43 is communicatively connected to 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 source 43 is preferably in the range of 1.8V to 2.2V, for example. Here, with general electrodes such as glassy carbon, oxygen will be generated as the anode voltage is increased, but with the first electrode 41 to which BDD is applied, oxygen overvoltage is large and oxygen is difficult to generate. . Therefore, the power source 43 can apply a high voltage, and can satisfactorily generate active oxygen such as OH radicals around the first electrode 41.
　以上のように構成された第１電極４１および第２電極４２は、エッチング処理時に、処理液Ｌを通して電気的に導通する。具体的には、図３に示すように、ノズル３１および処理空間ＰＳに存在する処理液Ｌ（例えば、ＴＭＡＨ）は、第１電極４１の対向部４１１の電極面４１１ａと、第２電極４２とに接触している。この状態で、給電部４０は、第１電極４１および第２電極４２に所定の出力値（例えば、２Ｖ）の電圧を印加する。これにより、電極面４１１ａの周辺では、以下の［１］および［２］の反応が生じる。
［１］２Ｈ２Ｏ＝Ｏ２＋４Ｈ＋＋４ｅ－
［２］Ｈ２Ｏ＝・ＯＨ＋Ｈ＋＋ｅ－ The first electrode 41 and the second electrode 42 configured as described above are electrically connected through the processing liquid L during the etching process. Specifically, as shown in FIG. 3, the processing liquid L (for example, TMAH) present in the nozzle 31 and the processing space PS is applied to the electrode surface 411a of the facing portion 411 of the first electrode 41 and the second electrode 42. is in contact with. 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.
[1]2H 2 O=O 2 +4H + +4e -
[2] H 2 O=・OH+H + +e −
　すなわち、［２］の反応により直接的にＯＨラジカル（・ＯＨ）が生成される。さらに、電極面４１１ａ付近では、高電圧が印加されることにより、オゾン（Ｏ３）および過酸化水素水（Ｈ２Ｏ２）を生成する以下の［３］および［４］の反応が生じる。そして、反応により生成されたオゾン（Ｏ３）および過酸化水素水（Ｈ２Ｏ２）によって、以下の［５］の反応がさらに生じて、間接的にＯＨラジカルが生成される。
［３］２Ｈ２Ｏ＝Ｈ２Ｏ２＋２Ｈ＋＋２ｅ－
［４］３Ｈ２Ｏ＝Ｏ３＋６Ｈ＋＋６ｅ－
［５］Ｏ３＋Ｈ２Ｏ２＝・ＯＨ＋ＨＯ２＋Ｏ２ That is, OH radicals (.OH) are directly generated by the reaction [2]. Further, near the electrode surface 411a, by applying a high voltage, the following reactions [3] and [4] that generate ozone (O 3 ) and hydrogen peroxide (H 2 O 2 ) occur. Then, the following reaction [5] further occurs due to ozone (O 3 ) and hydrogen peroxide solution (H 2 O 2 ) generated by the reaction, and OH radicals are indirectly generated.
[3]2H 2 O=H 2 O 2 +2H + +2e -
[4]3H 2 O=O 3 +6H + +6e -
[5] O 3 +H 2 O 2 =・OH+HO 2 +O 2
　上記の反応によって生成されたＯＨラジカルの寿命は、２００μｓ以下と短い。しかしながら、電極面４１１ａが基板Ｗの表面に充分に近い位置（処理空間ＰＳの幅が５ｍｍ以下）に配置されていることで、除去対象Ａであるレジスト膜にＯＨラジカルを容易に導くことができる。ＯＨラジカルは、強い酸化力を有しており、接触したレジスト膜を酸化させる。その結果、基板Ｗの表面からレジスト膜を円滑に剥離することが可能となる。 The lifetime of the OH radicals generated by the above reaction is as short as 200 μs or less. However, by arranging the electrode surface 411a at a position sufficiently close to the surface of the substrate W (the width of the processing space PS is 5 mm or less), OH radicals can be easily guided to the resist film that is the removal target A. . OH radicals have strong oxidizing power and oxidize the resist film that comes into contact with them. As a result, the resist film can be smoothly peeled off from the surface of the substrate W.
　図１に戻り、処理容器１０の内部に設けられるカップ５０は、保持部２０に保持されている基板Ｗの外周縁を囲み、基板Ｗの外周縁から飛散する処理液Ｌを受ける。カップ５０は、本実施形態において非回転であるが、保持軸部６２と共に回転する構成でもよい。カップ５０の底壁には、カップ５０の内部に溜まった液体を排出する排液管５１と、カップ５０の内部に溜まった気体を排出する排気管５２とが設けられる。 Returning to FIG. 1, the cup 50 provided inside the processing container 10 surrounds the outer periphery of the substrate W held by the holding part 20, and receives the processing liquid L scattered from the outer periphery of the substrate W. Although the cup 50 does not rotate in this embodiment, it may be configured to rotate together with the holding shaft portion 62. A drain pipe 51 for discharging the liquid accumulated inside the cup 50 and an exhaust pipe 52 for discharging the gas accumulated inside the cup 50 are provided on the bottom wall of the cup 50.
　また、基板処理装置１は、処理容器１０と異なる位置（処理容器１０の外部）に、処理液Ｌに電圧を印加することにより生成されるＯＨラジカルを検出する検出ユニット８０を備える。検出ユニット８０は、処理液供給経路７１から分岐する抽出経路８１と、ＯＨラジカルと反応する反応液を供給する反応液源８２と、反応液源８２の反応液が流通する反応液供給経路８３と、処理液Ｌおよび反応液の混合液が流入するリアクタ８４と、を有する。抽出経路８１および反応液供給経路８３は、リアクタ８４の上流側の合流経路８５において合流して混合液となる。また、リアクタ８４の下流側には、混合液内で生成されたＯＨラジカルの量を検出する検出機構８６が設けられている。 Further, the substrate processing apparatus 1 includes a detection unit 80 that detects OH radicals generated by applying a voltage to the processing liquid L at a position different from the processing container 10 (outside the processing container 10). The detection unit 80 includes an extraction path 81 that branches from the processing liquid supply path 71, a reaction liquid source 82 that supplies a reaction liquid that reacts with OH radicals, and a reaction liquid supply path 83 through which the reaction liquid from the reaction liquid source 82 flows. , and a reactor 84 into which a mixed liquid of the processing liquid L and the reaction liquid flows. The extraction path 81 and the reaction liquid supply path 83 merge in a merging path 85 on the upstream side of the reactor 84 to form a mixed liquid. Furthermore, a detection mechanism 86 is provided on the downstream side of the reactor 84 to detect the amount of OH radicals generated within the mixed liquid.
　抽出経路８１は、処理液Ｌを流通可能な流路を内側に有するチューブによって構成され、途中位置に流路を開閉するバルブ８１ｖを備える。同様に、反応液供給経路８３は、反応液を流通可能な流路を内側に有するチューブによって構成され、その上流端に反応液源８２が接続され、途中位置に流路を開閉するバルブ８３ｖを備える。 The extraction path 81 is constituted by a tube that has a flow path inside thereof through which the processing liquid L can flow, and is provided with a valve 81v that opens and closes the flow path at an intermediate position. Similarly, the reaction liquid supply path 83 is constituted by a tube having a flow path through which the reaction liquid can flow, the reaction liquid source 82 is connected to the upstream end of the tube, and a valve 83v for opening and closing the flow path is provided at an intermediate position. Be prepared.
　反応液源８２が供給する反応液としては、ＯＨラジカルのスカベンジャーであり、他のラジカル（Ｏ２ラジカル、ＨＯ２ラジカル、Ｈ２Ｏ２ラジカル）と反応しないテレフタル酸（ＴＡ）を適用することがあげられる。テレフタル酸は、ＯＨラジカルと反応する前は非蛍光性を有するが、ＯＨラジカルと反応すると２－ヒドロキシテレフタル酸（ＨＴＡ）となって蛍光性をもつようになる。したがって、検出機構８６は、リアクタ８４から排出された混合液に所定波長の励起光を照射して、ＨＴＡの蛍光を受光することで、ＯＨラジカルの量を検出することができる。 As the reaction liquid supplied by the reaction liquid source 82, terephthalic acid (TA), which is a scavenger of OH radicals and does not react with other radicals (O 2 radical, HO 2 radical, H 2 O 2 radical), can be used. can give. Terephthalic acid has non-fluorescence before reacting with OH radicals, but when it reacts with OH radicals, it becomes 2-hydroxyterephthalic acid (HTA) and becomes fluorescent. Therefore, the detection mechanism 86 can detect the amount of OH radicals by irradiating the liquid mixture discharged from the reactor 84 with excitation light of a predetermined wavelength and receiving the fluorescence of HTA.
　混合液が流入するリアクタ８４は、この混合液を一時的に貯留可能かつ混合液に電圧を印加可能な構造を呈している。具体的には、リアクタ８４は、円筒状の容器８４１と、電源４３と第１電極４１との間の配線４６に接続される第１検出用電極８４２と、電源４３と第２電極４２との間の配線４７に接続される第２検出用電極８４３と、を含む。容器８４１は、軸方向一端部に合流経路８５が連結されており、軸方向他端部に検出機構８６が連結されている。 The reactor 84 into which the mixed liquid flows has a structure that can temporarily store the mixed liquid and apply 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 first detection electrode 842 connected to the power source 43 and the second electrode 42. and a second detection electrode 843 connected to the wiring 47 between them. The container 841 has a confluence path 85 connected to one end in the axial direction, and a detection mechanism 86 to the other end in the axial direction.
　第１検出用電極８４２と第２検出用電極８４３は、容器８４１内に露出していることで、合流経路８５から容器８４１内に流入した混合液に接触する。第１検出用電極８４２と、第２検出用電極８４３との間の距離は、処理容器１０の第１電極４１と第２電極４２の距離と略等しく設定されることが好ましい。これにより、検出ユニット８０は、リアクタ８４内で第１検出用電極８４２および第２検出用電極８４３に電圧を印加して混合液を電解する条件と、処理容器１０内で第１電極４１および第２電極４２に電圧を印加して処理液Ｌを電解する条件とを等しくできる。 The first detection electrode 842 and the second detection electrode 843 are exposed inside the container 841 and come into contact with the liquid mixture that has flowed 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 approximately equal to the distance between the first electrode 41 and the second electrode 42 of the processing container 10. Thereby, the detection unit 80 determines the conditions for electrolyzing the mixed solution by applying a voltage to the first detection electrode 842 and the second detection electrode 843 in the reactor 84 and the conditions for electrolyzing the mixed liquid by applying a voltage to the first detection electrode 842 and the second detection electrode 843 in the processing container 10. The conditions for electrolyzing the treatment liquid L by applying a voltage to the two electrodes 42 can be made equal.
　検出機構８６は、リアクタにおいて生成された蛍光性を持つ物質を光学的に検出する。検出機構８６は、リアクタ８４に接続されるサンプルチューブ８６１と、サンプルチューブ８６１の被検出部８６１ａに励起光を照射する照射部８６２と、被検出部８６１ａで生じる蛍光を受光する受光部８６３と、を有する。照射部８６２は、制御部９０に接続され、制御部９０の制御下に、例えば３１０ｎｍの波長を有する励起光を被検出部８６１ａに投光する。受光部８６３は、制御部９０に接続され、受光した蛍光量に応じた電気信号を制御部９０に送信する。制御部９０は、この電気信号に基づき混合液内で生成されたＯＨラジカルの量を算出する。 The detection mechanism 86 optically detects the fluorescent substance generated in the reactor. The detection mechanism 86 includes a sample tube 861 connected to the reactor 84, an irradiation section 862 that irradiates excitation light to the detected section 861a of the sample tube 861, and a light receiving section 863 that receives fluorescence generated in the detected section 861a. has. The irradiation section 862 is connected to the control section 90, and under the control of the control section 90 projects excitation light having a wavelength of, for example, 310 nm onto the detected section 861a. The light receiving section 863 is connected to the control section 90 and transmits an electric signal to the control section 90 according to the amount of received fluorescence. The control unit 90 calculates the amount of OH radicals generated in the mixed liquid based on this electrical signal.
　基板処理装置１の制御部９０は、プロセッサ９１、メモリ９２、図示しない入出力インタフェースおよび電子回路等を有する制御用コンピュータである。プロセッサ９１は、ＣＰＵ（Central Processing Unit）、ＧＰＵ（Graphics Processing Unit）、ＡＳＩＣ（Application Specific Integrated Circuit）、ＦＰＧＡ（Field-Programmable Gate Array）、複数のディスクリート半導体からなる回路等のうち１つまたは複数を組み合わせたものである。メモリ９２は、不揮発性メモリ（例えば、コンパクトディスク、ＤＶＤ、ハードディスク、フラッシュメモリなど）および揮発性メモリを含み、制御部９０の記憶部を形成している。 The control unit 90 of the substrate processing apparatus 1 is a control computer that includes a processor 91, a memory 92, an input/output interface (not shown), an electronic circuit, etc. The processor 91 includes 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), a circuit made of a plurality of discrete semiconductors, etc. It is a combination. The memory 92 includes a nonvolatile memory (for example, a compact disk, a DVD, a hard disk, a flash memory, etc.) and a volatile memory, and forms the storage section of the control unit 90.
　制御部９０は、メモリ９２に記憶されたプログラムをプロセッサ９１が実行することにより、基板処理装置１全体の動作を制御する。制御部９０は、基板処理において、保持部２０、液供給部３０（外部供給部７０を含む）、給電部４０、回転部６０、検出ユニット８０を相互に連動させて所定の工程を順次実施していく。なお、基板処理装置１は、複数の構成を制御部９０が直接制御する構成でもよく、複数の構成毎に制御基板を備え、制御部９０から各制御基板に指令を送信して各制御基板により動作を制御する構成でもよい。 The control unit 90 controls the overall operation of the substrate processing apparatus 1 by having the processor 91 execute a program stored in the memory 92. In 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 rotation unit 60, and the detection unit 80 to interlock with each other to sequentially perform predetermined steps. To go. Note that the substrate processing apparatus 1 may have a configuration in which the control unit 90 directly controls a plurality of configurations, and is provided with a control board for each of the plurality of configurations, and the control unit 90 transmits commands to each control board so that each control board can control the control board. A configuration that controls the operation may also be used.
　本実施形態に係る基板処理装置１は、基本的には以上のように構成されるものであり、以下その動作（基板処理方法）について、図４のフローチャートを参照しながら説明する。 The substrate processing apparatus 1 according to this embodiment is basically configured as described above, and its operation (substrate processing method) will be described below with reference to the flowchart in FIG. 4.
　基板処理装置１の制御部９０は、基板Ｗのレジスト膜（除去対象Ａ）を除去する基板処理において、まず処理容器１０内に基板Ｗを搬入させる（ステップＳ１）。この際、制御部９０は、ゲートバルブ１２を開放して、搬送装置２により保持部２０の上方に基板Ｗを移動させ、上昇した複数のリフトピンに基板Ｗを受け渡す動作を行う。そして搬送装置２の後退後に、制御部９０は、各リフトピンを下降し、さらにチャック機構２２を作動させることで、保持部２０により基板Ｗを水平に保持する。また処理容器１０は、ゲートバルブ１２により密閉される。 In substrate processing to remove the resist film (removal target A) of the substrate W, the control unit 90 of the substrate processing apparatus 1 first carries the substrate W into the processing container 10 (step S1). At this time, the control section 90 opens the gate valve 12, causes the transfer device 2 to move the substrate W above the holding section 20, and performs an operation to transfer the substrate W to the plurality of lifted lift pins. After the transport device 2 retreats, the control section 90 lowers each lift pin and further operates the chuck mechanism 22 to hold the substrate W horizontally by the holding section 20. Further, the processing container 10 is sealed by a gate valve 12 .
　次に、制御部９０は、処理液Ｌに印加する電圧を調整するために、処理容器１０の外部に設置した検出ユニット８０を動作させて電圧調整工程を行う（ステップＳ２）。なお、電圧調整工程は、処理容器１０内に基板Ｗを搬入する前に実施してもよい。 Next, in order to adjust the voltage applied to the processing liquid L, the control unit 90 operates the detection unit 80 installed outside the processing container 10 to perform a voltage adjustment step (step S2). Note that the voltage adjustment step may be performed before loading the substrate W into the processing container 10.
　電圧調整工程において、制御部９０は、バルブ７１ｖ、７３ｖを閉塞した状態で、バルブ８１ｖ、８３ｖを開放する。これにより、処理液源７２から抽出経路８１に処理液Ｌ（ＴＭＡＨ）が流入すると共に、反応液源８２から反応液供給経路８３に反応液（ＴＡ）が流入し、合流経路８５において処理液Ｌと反応液が合流する。そして、処理液Ｌと反応液の混合液は、合流経路８５からリアクタ８４に流入する。 In the voltage adjustment step, the control unit 90 opens the valves 81v and 83v while closing the valves 71v and 73v. As a result, the processing liquid L (TMAH) flows from the processing liquid source 72 into the extraction path 81 , the reaction liquid (TA) flows from the reaction liquid source 82 into the reaction liquid supply path 83 , and the processing liquid L and the reaction solution merge. Then, the mixed liquid of the processing liquid L and the reaction liquid flows into the reactor 84 from the confluence path 85.
　この状態で、制御部９０は、リアクタ８４内の混合液の電解を開始する。制御部９０は、第１検出用電極８４２および第２検出用電極８４３に所定の電圧を印加して、リアクタ８４内の混合液にＯＨラジカルを生じさせる。このＯＨラジカルは、混合している反応液と反応することで、蛍光性を有する２－ヒドロキシテレフタル酸（ＨＴＡ）となる。検出機構８６のサンプルチューブ８６１には、リアクタ８４の反応状態に応じたＨＴＡを含む混合液が流入するようになる。検出機構８６は、照射部８６２からサンプルチューブ８６１の被検出部８６１ａに励起光を照射し、受光部８６３においてＨＴＡの蛍光を受光すると、その蛍光量に応じた電気信号を制御部９０に送信する。 In this state, the control unit 90 starts electrolyzing the mixed liquid in the reactor 84. The control unit 90 applies a predetermined voltage to the first detection electrode 842 and the second detection electrode 843 to generate OH radicals in the mixed liquid in the reactor 84 . This OH radical reacts with the mixed reaction solution to become fluorescent 2-hydroxyterephthalic acid (HTA). A mixed liquid containing HTA depending on the reaction state of the reactor 84 flows into the sample tube 861 of the detection mechanism 86 . The detection mechanism 86 irradiates excitation light from the irradiation section 862 to the detected section 861a of the sample tube 861, and when the light receiving section 863 receives the fluorescence of HTA, transmits an electric signal corresponding to the amount of fluorescence to the control section 90. .
　制御部９０は、この電気信号に基づきＯＨラジカルの量を算出し、算出したＯＨラジカルの量が目標範囲内にあるか否かを判定する。目標範囲外にある場合には、電源４３から第１検出用電極８４２および第２検出用電極８４３に印加する電圧を調整する。例えば、算出したＯＨラジカルの量が目標範囲よりも少ない場合には、電圧を上げる調整を行い、算出したＯＨラジカルの量が目標範囲よりも多い場合には、電圧を下げる調整を行う。これにより、基板処理装置１は、実際に電源４３が処理容器１０内の第１電極４１および第２電極４２に印加する電圧を、事前に最適化することが可能となる。 The control unit 90 calculates the amount of OH radicals based on this electrical signal, and determines whether the calculated amount of OH radicals is within the target range. If it is outside the target range, the voltage applied from the power source 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 adjusted to be increased, and when the calculated amount of OH radicals is more than the target range, the voltage is adjusted to be lowered. Thereby, the substrate processing apparatus 1 can optimize in advance the voltage that the power supply 43 actually applies to the first electrode 41 and the second electrode 42 in the processing container 10.
　なお、電圧調整工程は、１枚の基板Ｗを基板処理する毎に実施することに限定されず、必要に応じて実施すればよい。例えば、制御部９０は、基板処理装置１の起動開始やメンテナンスを行った後の最初に電圧調整工程を実施し、その後の基板処理では電圧調整工程を行わない構成とすることができる。あるいは、制御部９０は、処理液源７２に対して処理液Ｌを充填した際に、電圧調整工程を行う構成でもよい。 Note that the voltage adjustment step is not limited to being performed every time one substrate W is processed, but may be performed as necessary. For example, the control unit 90 may be configured to perform the voltage adjustment step first after startup or maintenance of the substrate processing apparatus 1, and not perform the voltage adjustment step during subsequent substrate processing. Alternatively, the control unit 90 may be configured to perform the voltage adjustment step when the processing liquid source 72 is filled with the processing liquid L.
　電圧調整工程において印加予定の電圧の調整を行うと、制御部９０は、バルブ８１ｖ、８３ｖを閉塞して電圧調整工程を終了し、基板処理であるエッチング処理（ステップＳ３～Ｓ７）に移行する。エッチング処理において、制御部９０は、まず回転部６０を動作させて、基板Ｗおよび第１電極４１を回転させる（ステップＳ３）。この際、基板回転部６１は、所定の回転方向かつ設定した基板用の目標回転速度で基板Ｗを回転させる。また、電極回転部４４は、基板Ｗの回転方向と逆回りかつ設定した電極用の目標回転速度で第１電極４１を回転させる。 After adjusting the voltage scheduled to be applied in the voltage adjustment step, the control unit 90 closes the valves 81v and 83v, ends the voltage adjustment step, and moves to etching processing (steps S3 to S7), which is substrate processing. 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 rotation unit 61 rotates the substrate W in a predetermined rotation direction and at a set target rotation speed for the substrate. Further, the electrode rotation unit 44 rotates the first electrode 41 in the opposite direction to the rotation direction of the substrate W and at a set target rotation speed for the electrode.
　さらに、制御部９０は、処理液供給経路７１のバルブ７１ｖを開放して、処理液源７２の処理液Ｌをノズル３１に流入させ、ノズル３１の吐出口３１ａから基板Ｗに処理液Ｌを供給する（ステップＳ４）。吐出口３１ａから落下した処理液Ｌは、第１電極４１の各貫通孔４１３を通過して基板Ｗの表面に当たる。そして、処理液Ｌは、基板Ｗや対向部４１１の回転に伴う遠心力によって、基板Ｗの径方向外側に向かって濡れ広がる。これにより、第１電極４１の電極面４１１ａ全体と基板Ｗの表面全体とが、処理空間ＰＳの処理液Ｌに接触した状態となる。 Furthermore, the control unit 90 opens the valve 71v of the processing liquid supply path 71 to cause the processing liquid L from the processing liquid source 72 to flow into the nozzle 31, and supplies the processing liquid L 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 passes through each through hole 413 of the first electrode 41 and hits the surface of the substrate W. Then, the processing liquid L wets and spreads toward the outside in the radial direction of the substrate W due to the centrifugal force accompanying the rotation of the substrate W and the opposing portion 411. Thereby, the entire electrode surface 411a of the first electrode 41 and the entire surface of the substrate W come into contact with the processing liquid L in the processing space PS.
　制御部９０は、給電部４０を動作して処理液Ｌに接触している第１電極４１および第２電極４２に対して、電源４３から所定の出力値（例えば、２Ｖ）の電圧を印加する（ステップＳ５）。これにより、第１電極４１および第２電極４２は、処理液Ｌを通して導通し、この処理液Ｌを電解する。電解に伴い第１電極４１の電極面４１１ａ付近の処理液Ｌ内には、ＯＨラジカルが生成される。ＯＨラジカルは、基板Ｗの除去対象Ａであるレジスト膜と反応することで、レジスト膜を基板Ｗから分離させる。基板処理装置１は、基板Ｗの表面全体に対向した対向部４１１により、基板Ｗの表面全体のレジスト膜を均一的に除去することができる。 The control unit 90 operates the power supply unit 40 to apply a voltage of a predetermined output value (for example, 2V) from the power supply 43 to the first electrode 41 and the second electrode 42 that are in contact with the processing liquid L. (Step S5). Thereby, the first electrode 41 and the second electrode 42 are electrically connected through the processing liquid L, and the processing liquid L is electrolyzed. Due to electrolysis, OH radicals are generated in the processing liquid L near the electrode surface 411a of the first electrode 41. The OH radicals separate the resist film from the substrate W by reacting with the resist film that is the removal target A of the substrate W. The substrate processing apparatus 1 can uniformly remove the resist film on the entire surface of the substrate W by the opposing portion 411 facing the entire surface of the substrate W.
　制御部９０は、処理液Ｌの電解の開始に伴いエッチング処理の実施期間を計測し、予め定めた設定期間が経過したか否かを判定する（ステップＳ６）。設定期間は、ＯＨラジカルにより基板Ｗのレジスト膜が除去される期間を、実験やシミュレーション等を行って求めたものである。基板処理装置１は、エッチング処理の実施期間が設定期間を経過するまで、基板Ｗおよび第１電極４１の相対回転と、処理液Ｌの供給と、処理液Ｌへの給電（電解）とを継続することで、レジスト膜を確実に除去することができる。 The control unit 90 measures the period during which the etching process is performed upon the start of electrolysis of the treatment liquid L, and determines whether a predetermined set period has elapsed (step S6). The set period is a period during which the resist film of the substrate W is removed by OH radicals, which is determined through experiments, simulations, and the like. The substrate processing apparatus 1 continues the relative rotation of the substrate W and the first electrode 41, the supply of the processing liquid L, and the supply of power (electrolysis) to the processing liquid L until the etching processing period passes the set period. By doing so, the resist film can be reliably removed.
　エッチング処理の実施期間が設定期間を経過すると、制御部９０は、エッチング処理を終了する（ステップＳ７）。この際、制御部９０は、第１電極４１および第２電極４２への給電を停止すると共に、バルブ７１ｖを閉塞することでノズル３１への処理液Ｌの供給を停止する。 When the implementation period of the etching process has exceeded the set period, the control unit 90 ends the etching process (step S7). At this time, the control unit 90 stops the power supply to the first electrode 41 and the second electrode 42, and also stops the supply of the processing liquid L to the nozzle 31 by closing the valve 71v.
　その後、制御部９０は、基板Ｗの表面に残る処理液Ｌを排液するために、基板処理として基板Ｗのリンス洗浄工程を行う（ステップＳ８）。リンス洗浄工程では、バルブ７３ｖを開放し、回転部６０により基板Ｗを回転させながら、リンス液源７４のリンス液をノズル３１に流入させて、ノズル３１の吐出口３１ａから基板Ｗにリンス液を供給する。リンス液は、基板Ｗの表面において回転の遠心力により濡れ広がり、基板Ｗの表面から処理液Ｌを排出する。 Thereafter, the control unit 90 performs a rinsing process for the substrate W as substrate processing in order to drain the processing liquid L remaining on the surface of the substrate W (step S8). In the rinsing cleaning process, the valve 73v is opened, and the rinsing liquid from the rinsing liquid source 74 is allowed to flow into the nozzle 31 while the substrate W is rotated by the rotation unit 60, and the rinsing liquid is applied to the substrate W from the discharge port 31a of the nozzle 31. supply The rinsing liquid spreads on the surface of the substrate W due to the centrifugal force of rotation, and the processing liquid L is discharged from the surface of the substrate W.
　リンス洗浄工程後、制御部９０は、基板Ｗの表面のリンス液を乾燥させるために、基板処理としてスピン乾燥工程を行う（ステップＳ９）。スピン乾燥工程では、回転部６０により基板Ｗを回転させることで、基板Ｗの表面のリンス液を乾燥させる。なお、基板処理では、スピン乾燥工程の前に、液供給部３０から処理液Ｌである乾燥液を基板Ｗの表面に供給して、リンス液を乾燥液に置換するようにしてもよい。このスピン乾燥工程が終了すると、処理容器１０内に収容した基板Ｗに対する基板処理が完了する。 After the rinsing process, the control unit 90 performs a spin drying process as substrate processing in order to dry the rinsing liquid on the surface of the substrate W (step S9). In the spin drying process, the rinsing liquid on the surface of the substrate W is dried by rotating the substrate W by the rotation unit 60. Note that in the substrate processing, before the spin drying process, a drying liquid, which is the processing liquid L, may be supplied from the liquid supply unit 30 to the surface of the substrate W to replace the rinsing liquid with the drying liquid. When this spin drying step is completed, the substrate processing for the substrate W accommodated in the processing container 10 is completed.
　最後に、制御部９０は、保持部２０による基板Ｗの保持を解除し、ゲートバルブ１２を開放して搬送装置２を処理容器１０内に進入させ、搬送装置２に基板Ｗを受け渡すことで、処理容器１０の内部から基板Ｗを搬出する（ステップＳ１０）。これにより、基板処理装置１は、レジスト膜を除去した基板Ｗを良好に得ることができる。 Finally, the control unit 90 releases the holding of the substrate W by the holding unit 20, opens the gate valve 12, causes the transfer device 2 to enter the processing container 10, and transfers the substrate W to the transfer device 2. , the substrate W is carried out from inside the processing container 10 (step S10). Thereby, the substrate processing apparatus 1 can satisfactorily obtain the substrate W from which the resist film has been removed.
　以上のように、基板処理装置１および基板処理方法は、液供給部３０から供給した処理液Ｌに第１電極４１および基板Ｗを接触させた状態として第１電極４１および第２電極４２に電圧を印加する。そのため、第１電極４１付近の処理液Ｌ内には、ＯＨラジカルが生成され、このＯＨラジカルを基板Ｗの除去対象Ａにスムーズに付与することが可能となる。これにより、基板処理装置１および基板処理方法は、基板Ｗの表面の除去対象Ａを効率的に除去することができる。また、基板処理装置１は、硫酸を使用しないことで、硫酸の廃棄に必要な処理をなくし、結果的に環境負荷を軽減することができる。 As described above, in the substrate processing apparatus 1 and the substrate processing method, voltage is applied to the first electrode 41 and the second electrode 42 while the first electrode 41 and the substrate W are in contact with the processing liquid L supplied from the liquid supply section 30. Apply. Therefore, OH radicals are generated in the processing liquid L near the first electrode 41, and the OH radicals can be smoothly applied to the removal target A of the substrate W. Thereby, the substrate processing apparatus 1 and the substrate processing method can efficiently remove the removal target A on the surface of the substrate W. Further, since the substrate processing apparatus 1 does not use sulfuric acid, it is possible to eliminate the treatment necessary for disposing of sulfuric acid, and as a result, reduce the environmental load.
　また、基板処理装置１は、回転部６０により第１電極４１および基板Ｗのうち少なくとも一方を回転させることで、基板Ｗの表面に供給した処理液Ｌを表面全体に容易に広げることができる。また、第１電極４１は、金、パラジウム、カーボン、ボロンドープダイアモンド（ＢＤＤ）のうち少なくとも１つの層を電極面４１１ａに有することで、酸素過電圧を大きくして、ＯＨラジカルを処理液Ｌ内に容易に生成することができる。特に、第１電極４１が陽極の場合には、ＢＤＤを適用することで、第１電極４１によるＯＨラジカルの生成を一層効率化することが可能となる。また、第１電極４１の対向部４１１、４１１Ａは、上方のノズル３１から吐出される処理液Ｌを通過させる孔（貫通孔４１３、メッシュ）を有することで、基板Ｗの表面に安定的に処理液Ｌを供給し続けることができる。 Further, the substrate processing apparatus 1 can easily spread the processing liquid L supplied to the surface of the substrate W over the entire surface by rotating at least one of the first electrode 41 and the substrate W using the rotating section 60. Further, the first electrode 41 has at least one layer of gold, palladium, carbon, and boron-doped diamond (BDD) on the electrode surface 411a to increase oxygen overvoltage and direct OH radicals into the processing liquid L. can be easily generated. In particular, when the first electrode 41 is an anode, by applying BDD, it is possible to further improve the efficiency of generating OH radicals by the first electrode 41. In addition, the opposing parts 411 and 411A of the first electrode 41 have holes (through holes 413, mesh) through which the processing liquid L discharged from the upper nozzle 31 passes, so that the surface of the substrate W can be stably processed. Liquid L can be continuously supplied.
　さらに、基板処理装置１および基板処理方法は、処理液Ｌとして電解質を含む水溶液を用いることで、処理液Ｌの電解を促進することが可能となる。特に、水溶液として、ＨＦ、ＨＣｌ、ＮＨ４ＯＨ、ＴＭＡＨ、Ｈ２Ｏ２、Ｈ２ＳＯ４、Ｈ３ＰＯ４、ＨＮＯ３のうち少なくとも１つを含むことで、ＯＨラジカルを充分に生成することができる。 Further, in the substrate processing apparatus 1 and the substrate processing method, by using an aqueous solution containing an electrolyte as the processing liquid L, it becomes possible to promote electrolysis of the processing liquid L. In particular, the aqueous solution contains at least one of HF, HCl, NH 4 OH, TMAH, H 2 O 2 , H 2 SO 4 , H 3 PO 4 , and HNO 3 to sufficiently generate OH radicals. Can be done.
　またさらに、基板処理装置１および基板処理方法は、検出ユニット８０により処理容器１０とは別に処理液Ｌに生じるＯＨラジカルを検出することで、給電部４０により印加する電圧を精度よく調整することができる。特に、基板処理装置１は、リアクタ８４においてＯＨラジカルと反応して生成された蛍光性を持つ物質を、光学的に検出する検出機構８６により検出することで、ＯＨラジカルの量を容易に検出することが可能となる。基板処理装置１は、反応液としてテレフタル酸を適用することで、ＯＨラジカルと反応して蛍光性を持つようになり、ＯＨラジカルの量を安定的に検出することができる。 Furthermore, in the substrate processing apparatus 1 and the substrate processing method, by detecting OH radicals generated in the processing liquid L separately from the processing container 10 using the detection unit 80, it is possible to accurately adjust the voltage applied by the power supply unit 40. can. In particular, the substrate processing apparatus 1 easily detects the amount of OH radicals by optically detecting a fluorescent substance generated by reacting with OH radicals in the reactor 84. becomes possible. By applying terephthalic acid as a reaction liquid, the substrate processing apparatus 1 reacts with OH radicals, becomes fluorescent, and can stably detect the amount of OH radicals.
　なお、本開示の基板処理装置１および基板処理方法は、上記の実施形態に限定されず、種々の変形例をとり得る。例えば上記の説明では、基板処理装置１は、レジスト膜を除去対象Ａとしたが、基板Ｗの表面にある金属膜、窒化金属膜、ポリマ残渣についても、同様の基板処理を行うことができる。例えば、金属膜は、Ｗ、ＴｉＮ、Ｃｏ、Ｎｉ、Ｒｕ、Ｍｏ、Ａｌのうち少なくとも１つであることで、処理液Ｌで生成されたＯＨラジカルによって良好に除去される。 Note that the substrate processing apparatus 1 and substrate processing method of the present disclosure are not limited to the above embodiments, and may take various modifications. For example, in the above description, the substrate processing apparatus 1 uses the resist film as the removal target A, but the same substrate processing can also be performed on the metal film, metal nitride film, and polymer residue on the surface of the substrate W. For example, if the metal film is at least one of W, TiN, Co, Ni, Ru, Mo, and Al, the metal film can be effectively removed by the OH radicals generated in the treatment liquid L.
　以下、他の変形例に係る基板処理装置１および基板処理方法について、図５～図１１を参照しながら説明していく。 Hereinafter, a substrate processing apparatus 1 and a substrate processing method according to other modified examples will be described with reference to FIGS. 5 to 11.
　図５（Ａ）に示す第２変形例のように、第１電極４１は、基板Ｗの表面を部分的に覆う対向部４１１Ｂを有し、電極回転部４４（図１参照）により対向部４１１Ｂを回転させる構成を採ってもよい。対向部４１１Ｂは、例えば、基板Ｗの直径以上に延在する細長い長方形状の平板に形成され、回転に伴って基板Ｗの表面全体に対向することができる。また、ノズル３１から吐出される処理液Ｌは、対向部４１１Ｂが吐出口３１ａに非対向の際に、基板Ｗの表面に供給される。この場合でも、給電部４０は、給電により対向部４１１Ｂ付近にＯＨラジカルを生成することで、基板Ｗの除去対象Ａを良好に除去することができる。 As in the second modification shown in FIG. 5A, the first electrode 41 has a facing portion 411B that partially covers the surface of the substrate W, and the facing portion 411B is rotated by the electrode rotating portion 44 (see FIG. 1). A configuration may also be adopted in which the rotation is performed. The opposing portion 411B is formed, for example, into an elongated rectangular flat plate extending beyond the diameter of the substrate W, and can face the entire surface of the substrate W as it rotates. Furthermore, the processing liquid L discharged from the nozzle 31 is supplied to the surface of the substrate W when the opposing portion 411B is not opposed to the discharge port 31a. Even in this case, the power supply section 40 can satisfactorily remove the removal target A of the substrate W by generating OH radicals near the opposing section 411B by power supply.
　図５（Ｂ）に示す第３変形例のように、第１電極４１、中心部が幅狭で外周縁が幅広な扇状の対向部４１１Ｃを有し、電極回転部４４により対向部４１１Ｃを回転させる構成を採ってもよい。このように対向部４１１Ｃを適用することで、基板Ｗの外周縁付近の表面に対して対向部４１１Ｃがより長く対向するようになり、基板Ｗの外周縁付近の除去対象Ａをより安定的に除去することができる。 As in the third modification shown in FIG. 5(B), the first electrode 41 has a fan-shaped facing part 411C with a narrow center and a wide outer peripheral edge, and the facing part 411C is rotated by the electrode rotating part 44. A configuration may also be adopted in which the By applying the facing part 411C in this way, the facing part 411C can face the surface near the outer periphery of the substrate W for a longer time, and the removal target A near the outer periphery of the substrate W can be more stably removed. Can be removed.
　図６に示す第４変形例のように、回転部６０は、電極回転部４４（図１参照）を備えずに、第１電極４１を固定する固定構造４８を備えた構成でもよい。この場合、回転部６０は、基板回転部６１により基板Ｗを回転させ、基板Ｗの表面に供給された処理液Ｌを基板Ｗの表面全体に広げる。また、給電部４０は、固定構造４８を介して第１電極４１に電圧を印加することで、処理液Ｌ内にＯＨラジカルを生成することができる。要するに、基板処理装置１は、基板Ｗの表面全体にＯＨラジカルを生成できれば、基板Ｗの表面全体に処理液Ｌを供給する手段について特に限定されない。例えば、回転部６０は、電極回転部４４を備える一方で、基板回転部６１を備えない（基板Ｗを回転させない）構成であっても、第１電極４１の回転に伴って基板Ｗの表面上に処理液Ｌを広げることができる。 As in the fourth modification shown in FIG. 6, the rotating section 60 may be configured to include a fixing structure 48 for fixing the first electrode 41 without including the electrode rotating section 44 (see FIG. 1). In this case, the rotating unit 60 causes the substrate rotating unit 61 to rotate the substrate W, and spreads the processing liquid L supplied to the surface of the substrate W over the entire surface of the substrate W. Furthermore, 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, the means for supplying the processing liquid L to the entire surface of the substrate W in the substrate processing apparatus 1 is not particularly limited as long as it can generate OH radicals over the entire surface of the substrate W. For example, even if the rotating unit 60 includes the electrode rotating unit 44 but does not include the substrate rotating unit 61 (does not rotate the substrate W), as the first electrode 41 rotates, the surface of the substrate W may be rotated. The processing liquid L can be spread over the entire area.
　図７（Ａ）に示すように、第５変形例に係る第１電極４１Ａは、上記の実施形態のように基板Ｗの表面全体の除去対象Ａを除去する構成とせずに、基板Ｗの外周縁付近の除去対象Ａを除去する構成となっている。具体的には、第１電極４１Ａは、固定構造４８に固定される連結部４１５と、連結部４１５に支持されて基板Ｗの表面の上方に短く突出する突部４１６とを有する。突部４１６は、基板Ｗの外周縁のみに対向可能な長さに設定され、かつ基板Ｗの外周縁の周方向の一部分に近接している。基板処理装置１は、回転部６０（基板回転部６１）により基板Ｗを回転させつつ、ノズル３１から基板Ｗの表面に処理液Ｌを供給し、また給電部４０により第１電極４１Ａおよび第２電極４２に電圧を印加する。これにより、第１電極４１Ａの突部４１６は、基板Ｗの外周縁付近の処理液Ｌ内にＯＨラジカルを生成し、このＯＨラジカルにより外周縁付近の除去対象を良好に除去することができる。 As shown in FIG. 7(A), the first electrode 41A according to the fifth modification does not have a configuration in which the removal target A is removed from the entire surface of the substrate W as in the above-described embodiment. The configuration is such that the removal target A near the periphery is removed. Specifically, the first electrode 41A includes a connecting portion 415 fixed to the fixing structure 48, and a protruding portion 416 that is supported by the connecting portion 415 and protrudes briefly above the surface of the substrate W. The protrusion 416 is set to a length such that it can face only the outer peripheral edge of the substrate W, and is close to a portion of the outer peripheral edge of the substrate W in the circumferential direction. The substrate processing apparatus 1 supplies the processing liquid L to the surface of the substrate W from the nozzle 31 while rotating the substrate W using the rotating section 60 (substrate rotating section 61), and supplies the processing liquid L to the surface of the substrate W from the nozzle 31, and also supplies the first electrode 41A and the second electrode using the power supply section 40. A voltage is applied to the electrode 42. Thereby, the protrusion 416 of the first electrode 41A generates OH radicals in the processing liquid L near the outer periphery of the substrate W, and the object to be removed near the outer periphery can be favorably removed by the OH radicals.
　図７（Ｂ）に示すように、第６変形例に係る第１電極４１Ｂは、基板Ｗの外周縁付近の除去対象Ａを除去するため、突部４１６に代えて基板の外周縁付近を周回するリング部４１７を有する。この場合でも、基板処理装置１は、基板Ｗの外周縁付近の除去対象を良好に除去することができる。 As shown in FIG. 7B, the first electrode 41B according to the sixth modification rotates around the outer periphery of the substrate instead of the protrusion 416 in order to remove the removal target A near the outer periphery of the substrate W. It has a ring part 417. Even in this case, the substrate processing apparatus 1 can effectively remove the object to be removed near the outer peripheral edge of the substrate W.
　図８に示すように、第７変形例に係る基板処理装置１は、第１電極４１Ｃの電極軸部４１２の内部に流路４１２ａを形成し、この流路４１２ａにノズル３１の突出端部を挿入している。流路４１２ａは、第１電極４１の対向部４１１、４１１Ａ～４１１Ｃの中心に形成された開口に連通している。液供給部３０および給電部４０は、ノズル３１の吐出口３１ａから吐出した処理液Ｌを、開口から処理空間ＰＳに流入させる。またこの場合、電極移動部４５は、ノズル３１および第１電極４１を一体に移動させるように構成される。 As shown in FIG. 8, the substrate processing apparatus 1 according to the seventh modification has a flow path 412a formed inside the electrode shaft portion 412 of the first electrode 41C, and the protruding end of the nozzle 31 inserted into the flow path 412a. It is inserted. The flow path 412a communicates with an opening formed at 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 cause the processing liquid L discharged from the discharge port 31a of the nozzle 31 to flow into the processing space PS from the opening. Further, in this case, the electrode moving unit 45 is configured to move the nozzle 31 and the first electrode 41 together.
　このように電極軸部４１２の内部を通して処理液Ｌを供給する構成でも、基板処理装置１は、電極面４１１ａと基板Ｗの表面の間の処理空間ＰＳに処理液Ｌを安定的に供給して、処理液Ｌの電解を行うことができる。したがって、第１電極４１付近で生成されたＯＨラジカルが基板Ｗの除去対象Ａを良好に除去できる。特に、この構成では、対向部４１１に貫通孔４１３を備える必要がなくなるため、対向部４１１の上面に処理液Ｌが当たることによる飛び散りを確実に回避することができる。 Even with this configuration 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. , the treatment liquid L can be electrolyzed. Therefore, the OH radicals generated near the first electrode 41 can effectively remove the removal target A of the substrate W. In particular, with this configuration, since it is not necessary to provide the through hole 413 in the facing part 411, it is possible to reliably avoid scattering caused by the processing liquid L hitting the upper surface of the facing part 411.
　図９に示すように、第８変形例に係る基板処理装置１Ａは、処理液Ｌに基板Ｗを浸漬した状態で、第１電極４１および第２電極４２に電圧を印加する構成となっている。具体的には、保持部２０は、基板Ｗを真空吸着するチャック機構２２を有すると共に、基板Ｗの径方向外側に基板Ｗよりも上方に突出し、また周方向に環状に周回する枠部２３を有する。これにより、基板Ｗを載置する載置面および枠部２３の内側は、処理液Ｌを貯留可能な貯留空間２４となる。 As shown in FIG. 9, the substrate processing apparatus 1A according to the eighth modification is configured to apply a voltage to the first electrode 41 and the second electrode 42 while the substrate W is immersed in the processing liquid L. . Specifically, the holding part 20 has a chuck mechanism 22 that vacuum-chucks the substrate W, and also has a frame part 23 that protrudes outward in the radial direction of the substrate W and above the substrate W, and that circulates annularly in the circumferential direction. have Thereby, the mounting surface on which the substrate W is mounted and the inside of the frame portion 23 become a storage space 24 in which the processing liquid L can be stored.
　液供給部３０は、貯留空間２４の上方で、処理液Ｌを供給するノズル３１を有する。ノズル３１は、処理液Ｌを供給した後にカップ５０から退避する。なお、ノズル３１は、エッチング処理時に貯留空間２４の上方に待機し、貯留空間２４の処理液Ｌが減った場合に処理液Ｌを補充する構成でもよい。 The liquid supply unit 30 has a nozzle 31 that supplies the processing liquid L above the storage space 24. The nozzle 31 retreats from the cup 50 after supplying the processing liquid L. Note that the nozzle 31 may be configured to stand by 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 decreases.
　給電部４０は、基板Ｗに対向する対向部４１１を有する第１電極４１と、第１電極４１の水平方向外側において貯留空間２４に挿入される第２電極４２と、を有する。第１電極４１は、電極移動部４５に接続されている。なお、本変形例では回転部６０（基板回転部６１および電極回転部４４）を備えない構成であるが、基板処理装置１Ａは、基板Ｗや第１電極４１を回転させる回転部６０を備えた構成でもよい。 The power feeding 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 on the horizontal outer side of the first electrode 41. The first electrode 41 is connected to an electrode moving section 45 . Note that although this modification does not include the rotating section 60 (the substrate rotating section 61 and the electrode rotating section 44), the substrate processing apparatus 1A is equipped with the rotating section 60 that rotates the substrate W and the first electrode 41. It can also be a configuration.
　このように構成された基板処理装置１Ａは、貯留空間２４に処理液Ｌを貯留した状態で、電源４３により第１電極４１および第２電極４２に電圧を印加すると、第１電極４１の電極面４１１ａ付近にＯＨラジカルが生成される。したがって、この基板処理装置１Ａでも、生成したＯＨラジカルにより基板Ｗの表面の除去対象Ａを除去することができる。特に、基板処理装置１Ａは、電解時に処理液Ｌの乱流が抑制されることで、除去対象Ａをより均一的に除去することが可能となる。 In the substrate processing apparatus 1A configured as described above, when a voltage is applied to the first electrode 41 and the second electrode 42 by the power source 43 with the processing liquid L stored in the storage space 24, the electrode surface of the first electrode 41 OH radicals are generated near 411a. Therefore, this substrate processing apparatus 1A can also remove the removal target A on the surface of the substrate W using the generated OH radicals. In particular, the substrate processing apparatus 1A can more uniformly remove the removal target A by suppressing the turbulent flow of the processing liquid L during electrolysis.
　図１０（Ａ）～図１０（Ｃ）に示す第９変形例に係る基板処理装置１Ｂは、基板Ｗのリンス洗浄工程時に、エッチング処理を行った第１電極４１を合わせて洗浄する構成としている。詳細には、基板処理装置１Ｂは、電極移動部４５として第１電極４１を支持する支持アーム４５ａと、支持アーム４５ａを回転させるアーム回転部４５ｂと、を有する。図１０（Ａ）に示すように、基板処理装置１Ｂは、エッチング処理時に、基板Ｗの鉛直方向上側かつ基板Ｗの近傍位置に第１電極４１を配置して、処理液Ｌ内にＯＨラジカルを生成することより、基板Ｗの除去対象Ａを除去する。 The substrate processing apparatus 1B according to the ninth modification shown in FIGS. 10(A) to 10(C) is configured to simultaneously clean the first electrode 41 that has been subjected to the etching process during the rinsing process of the substrate W. . Specifically, the substrate processing apparatus 1B includes a support arm 45a that supports the first electrode 41 as an electrode moving section 45, and an arm rotation section 45b that rotates the support arm 45a. As shown in FIG. 10A, the substrate processing apparatus 1B disposes the first electrode 41 above the substrate W in the vertical direction and in the vicinity of the substrate W, and generates OH radicals in the processing liquid L during the etching process. By generating, the removal target A of the substrate W is removed.
　そして、エッチング処理後に、基板処理装置１Ｂは、アーム回転部４５ｂにより支持アーム４５ａを回転させて、第１電極４１を電極退避位置に移動させる。これにより、基板Ｗの表面が露出されると共に、第１電極４１は電極退避位置において別の処理を行うことが可能となる。 After the etching process, the substrate processing apparatus 1B rotates the support arm 45a using the arm rotating section 45b to move the first electrode 41 to the electrode retracted position. As a result, the surface of the substrate W is exposed, and the first electrode 41 can perform another process at the electrode retracted position.
　基板処理装置１Ｂは、露出された基板Ｗに対しては上記したリンス洗浄工程およびスピン乾燥工程を行う（図４も参照）。例えば、基板処理装置１Ｂは、リンス洗浄工程において、リンス液（ＤＩＷ）を吐出する洗浄用ノズル３３を基板Ｗの上方に移動させて、リンス液を供給しつつ基板Ｗを回転させる。 The substrate processing apparatus 1B performs the above-mentioned rinsing process and spin drying process on the exposed substrate W (see also FIG. 4). For example, in the rinsing process, the substrate processing apparatus 1B moves the cleaning nozzle 33 that discharges a rinsing liquid (DIW) above the substrate W, and rotates the substrate W while supplying the rinsing liquid.
　一方、電極退避位置に配置された第１電極４１に対しては、電極リンス工程およびエアブロー乾燥工程を順に行う。例えば、基板処理装置１Ｂは、電極リンス工程において、リンス液（ＤＩＷ）を吐出するバーノズル３４を第１電極４１の上方（または下方）に移動させて、リンス液を供給しつつ当該バーノズル３４をスライドさせる。これにより、電解に使用した第１電極４１を洗浄することができる。その後のエアブロー乾燥工程でも、基板処理装置１Ｂは、図示しないブロアを第１電極４１の上方（または下方）に移動させて、第１電極４１に付着したリンス液を除去する。このように、基板処理装置１Ｂは、第１電極４１を洗浄することで、第１電極４１の耐久性を高めて、第１電極４１を長期にわたって使用することができる。 On the other hand, the first electrode 41 placed in the electrode retracted position is subjected to an electrode rinsing process and an air blow drying process in this order. For example, in the electrode rinsing step, the substrate processing apparatus 1B moves the bar nozzle 34 that discharges the rinsing liquid (DIW) above (or below) the first electrode 41, and slides the bar nozzle 34 while supplying the rinsing liquid. let Thereby, the first electrode 41 used for electrolysis can be cleaned. In the subsequent air blow drying step as well, the substrate processing apparatus 1B moves a blower (not shown) above (or below) the first electrode 41 to remove the rinse liquid adhering to the first electrode 41. In this way, by cleaning the first electrode 41, the substrate processing apparatus 1B can increase the durability of the first electrode 41 and use the first electrode 41 for a long period of time.
　また、図１１に示す第１０変形例のように、基板処理装置１Ｃは、基板Ｗを複数枚ずつ同時に処理するバッチ式の装置に構成されてもよい。バッチ式の基板処理装置１Ｃは、処理液Ｌを貯留すると共に、複数の基板Ｗを収容可能な処理槽１５（処理容器）を有し、処理槽１５に貯留した処理液Ｌに複数の基板Ｗが一括で浸漬される。例えば、各基板Ｗは、図示しない保持部により鉛直方向に沿って延在するように保持される。さらに、基板処理装置１Ｃは、処理槽１５内に処理液Ｌを供給する図示しない液供給部を有する。 Further, as in the tenth modification shown in FIG. 11, the substrate processing apparatus 1C may be configured as a batch-type apparatus that simultaneously processes a plurality of substrates W. The batch-type substrate processing apparatus 1C has a processing tank 15 (processing container) that stores processing liquid L and can accommodate a plurality of substrates W. are immersed in one batch. For example, each substrate W is held by a holding section (not shown) so as to extend along the vertical direction. Furthermore, the substrate processing apparatus 1C has a liquid supply section (not shown) that supplies the processing liquid L into the processing tank 15.
　そして、基板処理装置１Ｃは、保持状態の各基板Ｗの近傍位置に、第１電極４１をそれぞれ配置する。また、第２電極４２は、処理槽１５内の適宜の位置に配置される。これにより、基板処理装置１Ｃは、電源４３から第１電極４１および第２電極４２に適宜の電圧を印加することで、複数の第１電極４１毎にＯＨラジカルを生成することができる。各第１電極４１に隣接して配置された基板Ｗは、ＯＨラジカルにより除去対象Ａが良好に除去されることになる。 Then, the substrate processing apparatus 1C arranges the first electrodes 41 at positions near each substrate W in the held state. Further, the second electrode 42 is arranged at an appropriate position within the processing tank 15. Thereby, 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 source 43 to the first electrode 41 and the second electrode 42. In the substrate W disposed adjacent to each first electrode 41, the removal target A is successfully removed by the OH radicals.
　今回開示された実施形態に係る基板処理装置１および基板処理方法は、すべての点において例示であって制限的なものではない。実施形態は、添付の請求の範囲およびその主旨を逸脱することなく、様々な形態で変形および改良が可能である。上記複数の実施形態に記載された事項は、矛盾しない範囲で他の構成も取り得ることができ、また、矛盾しない範囲で組み合わせることができる。 The substrate processing apparatus 1 and substrate processing method according to the embodiment disclosed herein are illustrative in all respects and are not restrictive. The embodiments can be modified and improved in various ways without departing from the scope and spirit of the appended claims. The matters described in the plurality of embodiments described above may be configured in other ways without being inconsistent, and may be combined without being inconsistent.
　本願は、日本特許庁に２０２２年６月１４日に出願された基礎出願２０２２‐０９５８７４号の優先権を主張するものであり、その全内容を参照によりここに援用する。 This application claims priority to Basic Application No. 2022-095874 filed with the Japan Patent Office on June 14, 2022, and its entire contents are incorporated herein by reference.
１　　　　　基板処理装置
２０　　　　保持部
３０　　　　液供給部
４１　　　　第１電極
４２　　　　第２電極
４３　　　　電源
９０　　　　制御部
Ａ　　　　　除去対象
Ｌ　　　　　処理液
Ｗ　　　　　基板 1 Substrate processing apparatus 20 Holding section 30 Liquid supply section 41 First electrode 42 Second electrode 43 Power supply 90 Control section A Removal target L Processing liquid W Substrate

Claims (20)

  1. 　基板の除去対象を処理液で除去する基板処理装置であって、
    　前記基板を保持する保持部と、
    　前記保持部に保持された前記基板に前記処理液を供給する液供給部と、
    　前記保持部に保持された前記基板に対して間隔をおいて配置され、かつ前記液供給部から供給される前記処理液に接触する電極と、
    　前記電極に電圧を印加する電源と、
    　前記液供給部および前記電源を制御する制御部と、を備え、
    　前記制御部は、前記液供給部から供給した前記処理液に前記電極および前記基板を接触させた状態として前記電極に電圧を印加することで、前記処理液にＯＨラジカルを生成して、前記ＯＨラジカルを前記除去対象に付与する、
    　基板処理装置。     A substrate processing apparatus that removes a substrate to be removed using a processing liquid,
    a holding part that holds the substrate;
    a liquid supply unit that supplies the processing liquid to the substrate held by the holding unit;
    an electrode disposed at a distance from the substrate held by the holding unit and in contact with the processing liquid supplied from the liquid supply unit;
    a power source that applies voltage to the electrode;
    A control unit that controls the liquid supply unit and the power supply,
    The control unit generates OH radicals in the processing liquid by applying a voltage to the electrodes with the electrodes and the substrate in contact with the processing liquid supplied from the liquid supply unit. applying radicals to the removal target;
    Substrate processing equipment.
  2. 　前記電極および前記保持部に保持された前記基板のうち少なくとも一方を、他方に対して相対的に回転させる回転部を有し、
    　前記制御部は、基板処理において設定した目標回転速度で前記回転部を回転させる、
    　請求項１に記載の基板処理装置。     a rotating part that rotates at least one of the electrode and the substrate held by the holding part relative to the other;
    The control unit rotates the rotating unit at a target rotation speed set in substrate processing.
    The substrate processing apparatus according to claim 1.
  3. 　前記電極は、第１電極および第２電極を含み、
    　前記第１電極は、当該第１電極と前記基板の間に流入した前記処理液に接触し、
    　前記第２電極は、前記第１電極よりも前記基板から離れた位置で、前記液供給部により供給され続ける前記処理液を通して前記第１電極と導通する、
    　請求項１に記載の基板処理装置。     The electrode includes a first electrode and a second electrode,
    the first electrode contacts the processing liquid that has flowed between the first electrode and the substrate;
    The second electrode is electrically connected to the first electrode through the processing liquid that is continuously supplied by the liquid supply unit at a position farther from the substrate than the first electrode.
    The substrate processing apparatus according to claim 1.
  4. 　前記第１電極は、金、パラジウム、カーボン、ボロンドープダイアモンドのうち少なくとも１つの層を電極面に有する、
    　請求項３に記載の基板処理装置。     The first electrode has at least one layer of gold, palladium, carbon, and boron-doped diamond on the electrode surface.
    The substrate processing apparatus according to claim 3.
  5. 　前記第１電極は、陽極であり、
    　前記陽極は、ボロンドープダイアモンドを前記電極面に有する、
    　請求項４に記載の基板処理装置。     The first electrode is an anode,
    The anode has boron-doped diamond on the electrode surface.
    The substrate processing apparatus according to claim 4.
  6. 　前記第１電極と、前記保持部に保持された前記基板との間隔は、０．５ｍｍ～５ｍｍの範囲に設定される、
    　請求項３に記載の基板処理装置。     The distance between the first electrode and the substrate held by the holding part is set in a range of 0.5 mm to 5 mm.
    The substrate processing apparatus according to claim 3.
  7. 　前記第１電極は、前記保持部に保持された前記基板の表面全体に対向する対向部を有し、
    　前記対向部は、前記液供給部から吐出された前記処理液を通過させる複数の孔を有する、
    　請求項３に記載の基板処理装置。     The first electrode has a facing portion facing the entire surface of the substrate held by the holding portion,
    The opposing part has a plurality of holes through which the processing liquid discharged from the liquid supply part passes.
    The substrate processing apparatus according to claim 3.
  8. 　前記第１電極を回転させる回転部を有し、
    　前記第１電極は、前記保持部に保持された前記基板の中心から外周まで延在する長方形状の対向部を有する、
    　請求項３に記載の基板処理装置。     comprising a rotating part that rotates 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.
    The substrate processing apparatus according to claim 3.
  9. 　前記第１電極を回転させる回転部を有し、
    　前記第１電極は、前記基板の中心から外周に向かって周方向の幅が広がる扇状の対向部を有する、
    　請求項３に記載の基板処理装置。     comprising a rotating part that rotates the first electrode,
    The first electrode has a fan-shaped opposing portion whose circumferential width increases from the center of the substrate toward the outer periphery.
    The substrate processing apparatus according to claim 3.
  10. 　前記基板を回転させる回転部を有し、
    　前記第１電極は、前記保持部に保持された前記基板の外周縁の周方向の一部分のみと対向する突部を有する、
    　請求項３に記載の基板処理装置。     comprising a rotating part that rotates the substrate,
    The first electrode has a protrusion that faces only a portion in the circumferential direction of the outer periphery of the substrate held by the holding part.
    The substrate processing apparatus according to claim 3.
  11. 　前記第１電極は、前記保持部に保持された前記基板の外周縁を周方向に延在するリング部を有する、
    　請求項３に記載の基板処理装置。     The first electrode has a ring portion that extends in a circumferential direction around the outer periphery of the substrate held by the holding portion.
    The substrate processing apparatus according to claim 3.
  12. 　前記第１電極は、前記保持部に保持された前記基板の表面に対向する対向部と、前記対向部を支持する電極軸部と、を有し、
    　前記液供給部は、前記電極軸部の内部の流路を介して前記対向部と前記基板の表面の間に前記処理液を供給する、
    　請求項３に記載の基板処理装置。     The first electrode has a facing part facing the surface of the substrate held by the holding part, and an electrode shaft part supporting the facing part,
    The liquid supply section supplies the processing liquid between the opposing section and the surface of the substrate via a flow path inside the electrode shaft section.
    The substrate processing apparatus according to claim 3.
  13. 　前記処理液は、電解質を含む水溶液である、
    　請求項１に記載の基板処理装置。     The treatment liquid is an aqueous solution containing an electrolyte,
    The substrate processing apparatus according to claim 1.
  14. 　前記水溶液は、ＨＦ、ＨＣｌ、ＮＨ４ＯＨ、ＴＭＡＨ、Ｈ２Ｏ２、Ｈ２ＳＯ４、Ｈ３ＰＯ４、ＨＮＯ３のうち少なくとも１つを含む、
    　請求項１３に記載の基板処理装置。     The aqueous solution contains at least one of HF , HCl, NH4OH , TMAH, H2O2 , H2SO4 , H3PO4 , and HNO3 .
    The substrate processing apparatus according to claim 13.
  15. 　前記除去対象は、前記基板の表面に形成されたレジスト膜、金属膜または窒化金属膜、もしくは前記基板の表面に残存するポリマ残渣である、
    　請求項１に記載の基板処理装置。     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.
    The substrate processing apparatus according to claim 1.
  16. 　前記除去対象は、前記金属膜である場合にＷ、Ｃｏ、Ｎｉ、Ｒｕ、Ｍｏ、Ａｌのうち少なくとも１つを含み、前記窒化金属膜である場合にＴｉＮを含む、
    　請求項１５に記載の基板処理装置。     The object to be removed contains at least one of W, Co, Ni, Ru, Mo, and Al when the object is the metal film, and contains TiN when the object is the nitride metal film.
    The substrate processing apparatus according to claim 15.
  17. 　前記基板を処理する処理容器と、
    　前記処理容器とは別に設けられ、前記処理容器に供給する前記処理液が別に流入される検出ユニットを備え、
    　前記検出ユニットは、流入した前記処理液に対して前記処理容器の前記電極と同じ電圧を印加することで、前記処理液に生じる前記ＯＨラジカルを検出する、
    　請求項１乃至１６のいずれか１項に記載の基板処理装置。     a processing container for processing the substrate;
    a detection unit provided separately from the processing container, into which the processing liquid supplied to the processing container is separately introduced;
    The detection unit detects the OH radicals generated in the processing liquid by applying the same voltage as the electrode of the processing container to the processing liquid that has flowed in.
    A substrate processing apparatus according to any one of claims 1 to 16.
  18. 　前記検出ユニットは、生成された前記ＯＨラジカルと反応して蛍光性を持つ物質に生成される反応液と、前記処理液とを混合した混合液に電圧を印加するリアクタと、前記リアクタにおいて生成された蛍光性を持つ物質を光学的に検出する検出機構と、を有する、
    　請求項１７に記載の基板処理装置。     The detection unit includes a reactor that applies a voltage to a mixture of the treatment liquid and a reaction liquid that reacts with the generated OH radicals to produce a fluorescent substance, and a a detection mechanism for optically detecting a fluorescent substance;
    The substrate processing apparatus according to claim 17.
  19. 　前記反応液は、テレフタル酸である、
    　請求項１８に記載の基板処理装置。     the reaction solution is terephthalic acid,
    The substrate processing apparatus according to claim 18.
  20. 　基板の除去対象を処理液で除去する基板処理方法であって、
    　保持部により前記基板を保持する工程と、
    　前記保持部に保持された前記基板に前記処理液を供給する工程と、
    　前記保持部に保持された前記基板に対して間隔をおいて配置される電極に、電源から電圧を印加する工程と、を有し、
    　前記処理液を供給する工程では、前記処理液に前記電極および前記基板を接触させた状態とし、
    　前記電圧を印加する工程では、当該電圧の印加に伴い前記電極に接触した前記処理液にＯＨラジカルを生成して、前記ＯＨラジカルを前記除去対象に付与する、
    　基板処理方法。     A substrate processing method for removing a target to be removed on a substrate with a processing liquid, the method comprising:
    holding the substrate by a holding part;
    supplying the processing liquid to the substrate held by the holding section;
    applying a voltage from a power source to electrodes arranged at intervals with respect to the substrate held by the holding part,
    In the step of supplying the processing liquid, the electrode and the substrate are brought into contact with the processing liquid,
    In the step of applying the voltage, OH radicals are generated in the treatment liquid in contact with the electrode as the voltage is applied, and the OH radicals are applied to the removal target.
    Substrate processing method.
PCT/JP2023/020290 2022-06-14 2023-05-31 Substrate treatment device and substrate treatment method WO2023243409A1 (en)

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