WO2019239727A1 - Substrate processing method and substrate processing device - Google Patents

Substrate processing method and substrate processing device Download PDF

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Publication number
WO2019239727A1
WO2019239727A1 PCT/JP2019/017178 JP2019017178W WO2019239727A1 WO 2019239727 A1 WO2019239727 A1 WO 2019239727A1 JP 2019017178 W JP2019017178 W JP 2019017178W WO 2019239727 A1 WO2019239727 A1 WO 2019239727A1
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Prior art keywords
substrate
main surface
solution
nozzle
oxidizing solution
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PCT/JP2019/017178
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French (fr)
Japanese (ja)
Inventor
和宏 藤田
淳靖 三浦
基村　雅洋
徹 江戸
信行 宮路
知浩 植村
Original Assignee
株式会社Ｓｃｒｅｅｎホールディングス
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Publication of WO2019239727A1 publication Critical patent/WO2019239727A1/en

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    • 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

Definitions

  • the present invention relates to a substrate processing method and a substrate processing apparatus.
  • substrate In the manufacturing process of a semiconductor substrate (hereinafter simply referred to as “substrate”), various processes are performed on the surface of the substrate.
  • a chemical solution for etching is supplied to the vicinity of the peripheral portion of the upper surface of the rotating substrate, and an etching inhibitory solution is supplied to the vicinity of the peripheral portion of the lower surface of the substrate.
  • Water is supplied. Part of the pure water goes over the edge of the substrate to the upper surface of the substrate due to surface tension and collides with the chemical solution. Thereby, the chemical solution is diluted at the site where the pure water and the chemical solution collide, and the etching rate can be reduced at the site.
  • the present invention is directed to a substrate processing method, and an object thereof is to appropriately etch a processing region while protecting a peripheral portion.
  • the substrate processing method a) by rotating the disk-shaped substrate in a horizontal state and discharging an oxidizing solution for oxidizing one main surface of the substrate from the nozzle toward the substrate, Supplying the oxidizing solution to the peripheral portion of the one main surface; and b) discharging an etching solution for etching the one main surface from the nozzle toward the substrate while rotating the substrate in a horizontal state. And the step of supplying the etching solution to a processing region located inside the peripheral edge on the one main surface.
  • the processing region can be appropriately etched on one main surface of the substrate while protecting the peripheral portion with the oxidizing solution.
  • the oxidizing solution in the step a), is discharged from the nozzle located on the other main surface side of the substrate toward the other main surface, and the outer periphery of the substrate rotates.
  • the oxidizing solution is supplied to the peripheral portion of the one main surface via the end surface.
  • the oxidizing solution is discharged from the nozzle located on the other main surface side toward the center of the other main surface.
  • the steps a) and b) are performed at the same time.
  • the etching solution is discharged from the nozzle located on the one main surface side of the substrate toward the processing region. Good.
  • both the etching solution discharged to the one main surface and the oxidizing solution discharged to the other main surface are heated.
  • the radius of the substrate is 150 mm
  • the rotation speed of the substrate in the steps a) and b) is 50 to 300 rpm.
  • a laminated film including a plurality of first material films formed of a first material and a plurality of second material films formed of a second material different from the first material.
  • a hole extending in the thickness direction is formed in the laminated film, and in the step b)
  • the plurality of second material films included in the stacked film are selectively etched through the holes.
  • the etching solution has alkalinity.
  • a substrate processing apparatus includes a substrate holding unit that holds a disk-shaped substrate in a horizontal state, a substrate rotation mechanism that rotates the substrate holding unit about a central axis that faces in the up-down direction, and one of the substrates.
  • An oxidizing solution supply section for supplying the oxidizing solution to a peripheral portion of the one main surface by discharging an oxidizing solution for oxidizing the main surface of the main surface toward the rotating substrate from the nozzle; and the one main surface
  • An etching solution supply unit for supplying the etching solution to a processing region located inside the peripheral portion on the one main surface by discharging an etching solution for etching the substrate toward the rotating substrate from the nozzle.
  • FIG. 1 is a diagram showing a configuration of a substrate processing apparatus 1 according to an embodiment of the present invention.
  • the substrate processing apparatus 1 is a single wafer processing apparatus that processes the disk-shaped substrates 9 one by one.
  • the substrate processing apparatus 1 includes a substrate holding unit 21, a substrate rotating mechanism 22, a cup 23, an etching solution supply unit 3, and an oxidizing solution supply unit 4.
  • the substrate holding part 21 has a disk-like base part 211 centering on a central axis J1 facing in the up-down direction.
  • a plurality of chuck pins 212 are provided on the upper surface of the base portion 211.
  • the plurality of chuck pins 212 are arranged at equal intervals in the circumferential direction on a circumference centered on the central axis J1.
  • the substrate holding unit 21 holds the substrate 9
  • the plurality of chuck pins 212 are pressed against the outer peripheral edge of the substrate 9.
  • the center of the substrate 9 held by the substrate holding part 21 is located on the central axis J1.
  • the upper surface of the base portion 211 is parallel to a main surface 92 (hereinafter referred to as “lower surface 92”) facing downward of the substrate 9, and both face each other with a gap.
  • the substrate rotation mechanism 22 having a motor rotates the other end of the shaft portion 221, the substrate holding portion 21 rotates together with the substrate 9 about the central axis J1.
  • the cup 23 has a substantially cylindrical shape surrounding the base portion 211.
  • various processing liquids scattered from the outer peripheral edge of the rotating substrate 9 are received by the inner peripheral surface of the cup 23 and collected.
  • the upper part of the cup 23 can be moved up and down by a cup lifting mechanism (not shown).
  • the upper part of the cup 23 is lowered, and the cup 23 is prevented from interfering with an external transport mechanism.
  • the oxidizing solution supply unit 4 includes a lower nozzle 41 and an oxidizing solution supply source 42.
  • the lower nozzle 41 extends in the vertical direction.
  • a hollow portion extending in the vertical direction is provided on the central axis J1
  • the lower nozzle 41 is disposed in the hollow portion.
  • the upper end surface of the lower nozzle 41 is disposed in the vicinity of the upper surface of the base portion 211.
  • the lower nozzle 41 is located on the lower surface 92 side of the substrate 9 held by the substrate holding unit 21.
  • the upper end surface of the lower nozzle 41 directly faces the lower surface 92 of the substrate 9.
  • An oxidizing solution supply source 42 is connected to the lower end of the lower nozzle 41 via a valve, and the oxidizing solution is supplied from the oxidizing solution supply source 42 to the lower nozzle 41.
  • the oxidizing solution is discharged upward from a discharge port provided at the center of the upper end surface of the lower nozzle 41. That is, the oxidizing solution is discharged from the lower nozzle 41 toward the center of the lower surface 92 of the substrate 9. Details of the oxidizing solution will be described later.
  • a chemical liquid supply source 43 and a rinse liquid supply source 44 are further connected to the lower nozzle 41 via valves.
  • the chemical solution from the chemical solution supply source 43 By supplying the chemical solution from the chemical solution supply source 43 to the lower nozzle 41, the chemical solution is discharged from the lower nozzle 41 toward the center of the lower surface 92 of the substrate 9.
  • the rinse liquid from the rinse liquid supply source 44 By supplying the rinse liquid from the rinse liquid supply source 44 to the lower nozzle 41, the rinse liquid is discharged from the lower nozzle 41 toward the center of the lower surface 92.
  • the lower nozzle 41 and the chemical liquid supply source 43 constitute a lower surface chemical liquid supply unit
  • the lower nozzle 41 and the rinse liquid supply source 44 constitute a lower surface rinse liquid supply unit.
  • the lower nozzle 41 is shared by the oxidizing solution supply unit 4, the lower chemical solution supply unit, and the lower rinse solution supply unit.
  • One or both of the lower surface chemical liquid supply unit and the lower surface rinse liquid supply unit may have a nozzle separate from the lower nozzle 41.
  • the etchant supply unit 3 includes an upper nozzle 31 and an etchant supply source 32.
  • the upper nozzle 31 extends in the vertical direction.
  • the upper nozzle 31 is located on the main surface 91 (hereinafter referred to as “upper surface 91”) side facing the upper side of the substrate 9. Specifically, the upper nozzle 31 is disposed above the central portion of the upper surface 91. The lower end surface of the upper nozzle 31 directly faces the upper surface 91.
  • An etching solution supply source 32 is connected to the upper end of the upper nozzle 31 via a valve, and the etching solution is supplied from the etching solution supply source 32 to the upper nozzle 31.
  • the etching solution is discharged downward from a discharge port provided at the center of the lower end surface of the upper nozzle 31. That is, the etching solution is discharged from the upper nozzle 31 toward the center of the upper surface 91 of the substrate 9. Details of the etching solution will be described later.
  • a chemical solution supply source 33 and a rinse solution supply source 34 are further connected to the upper nozzle 31 via valves.
  • the chemical solution is discharged from the upper nozzle 31 toward the center of the upper surface 91 of the substrate 9.
  • the rinse liquid is discharged from the upper nozzle 31 toward the center of the upper surface 91.
  • the upper nozzle 31 and the chemical liquid supply source 33 constitute an upper surface chemical liquid supply unit
  • the upper nozzle 31 and the rinse liquid supply source 34 constitute an upper surface rinse liquid supply unit.
  • the upper nozzle 31 is shared by the etching solution supply unit 3, the upper surface chemical solution supply unit, and the upper surface rinse solution supply unit.
  • One or both of the upper surface chemical liquid supply unit and the upper surface rinse liquid supply unit may have a nozzle separate from the upper nozzle 31.
  • the chemical liquid supply source 33 may also serve as the chemical liquid supply source 43
  • the rinse liquid supply source 34 may also serve as the rinse liquid supply source 44.
  • the substrate processing apparatus 1 further includes an organic solvent supply unit 5.
  • the organic solvent supply unit 5 includes an auxiliary nozzle 51 and an organic solvent supply source 52.
  • the auxiliary nozzle 51 is disposed above the substrate 9.
  • An organic solvent supply source 52 is connected to the auxiliary nozzle 51 via a valve. By supplying the organic solvent from the organic solvent supply source 52 to the auxiliary nozzle 51, the organic solvent is discharged from the auxiliary nozzle 51 toward the center of the upper surface 91 of the substrate 9.
  • a nozzle moving mechanism that moves each of the upper nozzle 31 and the auxiliary nozzle 51 may be provided.
  • the nozzle moving mechanism selectively arranges the upper nozzle 31 and the auxiliary nozzle 51 at a facing position facing the upper surface 91 of the substrate 9 and a standby position away from the substrate 9 in the horizontal direction.
  • the nozzle moving mechanism may move the upper nozzle 31 and the auxiliary nozzle 51 individually.
  • FIG. 2 is a view showing the vicinity of the peripheral edge portion 93 of the substrate 9, and shows a cross section of the substrate 9 in a plane including the central axis J1.
  • the substrate 9 includes a substrate body 90 and a thin film 911.
  • the thin film 911 is formed on the upper surface of the substrate body 90 with a predetermined material (for example, amorphous silicon) and covers the entire upper surface.
  • the upper surface 91 of the substrate 9 is the surface of the thin film 911.
  • the lower surface 92 of the substrate 9 is the lower surface of the substrate body 90.
  • a thin film may be formed on the lower surface 92.
  • the thin film 911 is also provided on a part of the outer peripheral end surface 94 (so-called bevel surface) of the substrate 9.
  • the peripheral edge portion 93 described above is an annular portion including the outer peripheral end surface 94 and the vicinity thereof on the substrate 9.
  • the substrate 9 is held in a state in which the peripheral portion 93 of the substrate 9 is in contact with the holding portion of the container and the portion inside the peripheral portion 93 is not in contact with any member. .
  • the etching solution used in the substrate processing apparatus 1 is capable of etching the thin film 911, such as TMY (trimethyl-2hydroxyethylammonium hydroxide), TMAH (tetramethylammonium hydroxide), ammonia.
  • TMY trimethyl-2hydroxyethylammonium hydroxide
  • TMAH tetramethylammonium hydroxide
  • ammonia an etching solution having alkalinity such as water (NH 4 OH) is exemplified.
  • an aqueous solution of TMY is used as an etching solution.
  • An acidic etchant may be used.
  • the oxidizing solution used in the substrate processing apparatus 1 is capable of oxidizing the thin film 911 (that is, forming an oxide film), hydrogen peroxide water (H 2 O 2 ), ammonia water, Examples thereof include a mixed solution of hydrogen peroxide water and ozone water.
  • hydrogen peroxide is used as the oxidizing solution.
  • FIG. 3 is a diagram showing a flow in which the substrate processing apparatus 1 processes the substrate 9.
  • the substrate 9 to be processed is loaded in advance by an external transfer mechanism and held by the substrate holding unit 21.
  • the substrate rotation mechanism 22 starts to rotate the substrate 9 (step S11).
  • the substrate 9 rotates together with the substrate holding unit 21 in a horizontal state.
  • a chemical solution is supplied to the central portion of the upper surface 91 of the substrate 9 by the upper surface chemical solution supply unit via the upper nozzle 31 disposed at the opposite position, and the central portion of the lower surface 92 is supplied by the lower surface chemical solution supply unit via the lower nozzle 41.
  • the chemical solution is supplied to (step S12).
  • the chemical solution spreads toward the outer peripheral edge of the substrate 9 by the rotation of the substrate 9, and the chemical solution is supplied to the entire upper surface 91 and the lower surface 92.
  • the chemical liquid scattered from the outer peripheral edge of the substrate 9 is received and collected by the inner peripheral surface of the cup 23 (the same applies when supplying a rinse liquid, an oxidizing liquid and an etching liquid described later).
  • the chemical solution is, for example, DHF (dilute hydrofluoric acid), and the natural oxide films on the upper surface 91 and the lower surface 92 are removed by supplying the chemical solution.
  • DHF dilute hydrofluoric acid
  • other types of chemical solutions may be used.
  • the discharge of the chemical liquid is stopped.
  • the rinsing liquid is supplied to the central portion of the upper surface 91 by the upper surface rinsing liquid supply unit via the upper nozzle 31 and the rinsing liquid is supplied to the central portion of the lower surface 92 by the lower surface rinsing liquid supply unit via the lower nozzle 41.
  • the rinse liquid spreads toward the outer peripheral edge of the substrate 9 by the rotation of the substrate 9, and the rinse liquid is supplied to the entire upper surface 91 and the lower surface 92.
  • the rinse liquid is, for example, pure water, and the chemical liquid attached to the upper surface 91 and the lower surface 92 is removed by supplying the rinse liquid.
  • a rinse liquid other than pure water may be used. The discharge of the rinse liquid is continued for a predetermined time and then stopped.
  • the oxidizing solution supply source 42 supplies the oxidizing solution to the lower nozzle 41, whereby the oxidizing solution is continuously discharged from the lower nozzle 41 toward the center of the lower surface 92 (step S14).
  • the etching solution supply source 32 supplies the etching solution to the upper nozzle 31 so that the etching solution is continuously discharged from the upper nozzle 31 toward the center of the upper surface 91 (step S15).
  • the discharge of the oxidizing solution from the lower nozzle 41 and the discharge of the etching solution from the upper nozzle 31 are started almost simultaneously.
  • the oxidizing solution spreads toward the outer peripheral edge of the substrate 9 by the rotation of the substrate 9, and the oxidizing solution is supplied to the entire lower surface 92.
  • the substrate main body 90 is formed of a non-oxide (for example, silicon), and a uniform oxide film is formed on the entire lower surface 92 by an oxidation reaction with an oxidizing solution. A part of the oxidizing solution is scattered at the outer peripheral edge. Another part of the oxidizing solution adheres to the outer peripheral end surface 94 due to surface tension and reaches the peripheral edge portion 93 of the upper surface 91. In other words, the oxidizing solution discharged from the lower nozzle 41 toward the lower surface 92 is supplied to the peripheral portion 93 of the upper surface 91 via the outer peripheral end surface 94.
  • the etching solution spreads toward the outer peripheral edge of the substrate 9 by the rotation of the substrate 9.
  • the oxidizing solution is present at the peripheral edge portion 93 of the upper surface 91. Therefore, as shown in FIG. 4, the etching solution 81 and the oxidizing solution 82 are mixed at the peripheral edge portion 93 of the upper surface 91.
  • the etching solution 81 and the oxidizing solution 82 in the vicinity of the peripheral portion 93 are schematically shown, and a portion where the etching solution 81 and the oxidizing solution 82 are mixed is denoted by reference numeral 83.
  • the etching solution 81 is mixed with the oxidizing solution 82, thereby suppressing the etching of the substrate 9 (here, the etching of the thin film 911).
  • the upper surface 91 is microscopically oxidized by the oxidizing solution 82 (microscopically forming an oxide film). This is considered to be because it is protected from the etching solution 81.
  • the concentration of hydrogen peroxide in the oxidizing solution 82 is, for example, 8% by weight or more, preferably 15% in order to more reliably suppress the etching at the peripheral portion 93. % Or more.
  • the thin film 911 is etched by the etching solution 81 in a region 95 (hereinafter referred to as “processing region 95”) inside the peripheral portion 93 on the upper surface 91.
  • FIG. 5 shows the substrate 9 in which the thin film 911 is etched in the processing region 95, and illustration of the etching solution 81 and the oxidizing solution 82 is omitted.
  • an oxidizing solution 82 discharged from the lower nozzle 41 toward the lower surface 92 while appropriately etching the processing region 95 with an etching solution discharged from the upper nozzle 31 toward the processing region 95 on the upper surface 91.
  • the peripheral edge portion 93 of the upper surface 91 can be protected (the etching rate can be made sufficiently low or etching can be prevented).
  • the outer peripheral end surface 94 (bevel surface) of the substrate 9 is also protected by the oxidizing solution 82.
  • the etching solution supply source 32 has a heater, and the etching solution 81 heated to a predetermined temperature (for example, 85 ° C.) is discharged onto the upper surface 91. Thereby, in the processing region 95, the thin film 911 is etched at a relatively high etching rate.
  • the oxidizing solution supply source 42 includes a heater, and the oxidizing solution 82 heated to a predetermined temperature (for example, 70 ° C.) is discharged to the lower surface 92.
  • the high temperature oxidizing solution 82 is generated, for example, by mixing high temperature pure water and normal temperature hydrogen peroxide.
  • the high temperature etching solution 81 may be generated by mixing high temperature pure water with room temperature TMY or the like.
  • the conditions for causing the oxidizing solution 82 discharged from the lower nozzle 41 toward the lower surface 92 to reach the peripheral edge 93 of the upper surface 91 are appropriately determined according to the radius of the substrate 9 and the type of the oxidizing solution 82.
  • the rotation speed of the substrate 9 is set to 50 to 300 rpm, for example. The As a result, the oxidizing solution 82 can appropriately reach the peripheral edge 93 of the upper surface 91.
  • the rotation speed of the substrate 9 is preferably set to 100 to 200 rpm. More preferably, the rotation speed of the substrate 9 is 150 to 200 rpm.
  • the discharge of the oxidizing solution 82 and the etching solution 81 is continued for a predetermined time, the discharge of both is stopped. Subsequently, the rinsing liquid is supplied to the central portion of the upper surface 91 by the upper surface rinsing liquid supply unit via the upper nozzle 31, and the rinsing liquid is supplied to the central portion of the lower surface 92 by the lower surface rinsing liquid supply unit via the lower nozzle 41. Is supplied (step S16). On the upper surface 91 and the lower surface 92, the rinse liquid spreads toward the outer peripheral edge of the substrate 9 by the rotation of the substrate 9, and the rinse liquid is supplied to the entire upper surface 91 and the lower surface 92. By supplying the rinse liquid, the etching liquid 81 adhering to the upper surface 91 and the oxidizing liquid 82 adhering to the lower surface 92 are removed. The discharge of the rinse liquid is continued for a predetermined time and then stopped.
  • the organic solvent is supplied to the central portion of the upper surface 91 by the organic solvent supply unit 5 through the auxiliary nozzle 51 arranged at the facing position (step S17).
  • the organic solvent spreads toward the outer peripheral edge of the substrate 9 by the rotation of the substrate 9, and the organic solvent is supplied to the entire upper surface 91.
  • the organic solvent is, for example, IPA (isopropyl alcohol), and the rinse liquid on the upper surface 91 is replaced with the organic solvent.
  • an organic solvent other than IPA may be used. The discharge of the organic solvent is continued for a predetermined time and then stopped.
  • the substrate rotation mechanism 22 makes the rotation speed of the substrate 9 higher than that at the time of supplying the processing liquid (that is, the chemical liquid, the rinsing liquid, the oxidizing liquid, the etching liquid, and the organic solvent).
  • 9 is started (spin dry) (step S18).
  • the rotation of the substrate 9 is stopped (step S19).
  • the substrate 9 is unloaded from the substrate processing apparatus 1 by an external transport mechanism. Thus, the processing of the substrate 9 in the substrate processing apparatus 1 is completed.
  • the thin film 911 is removed in the processing region 95 on the upper surface 91 of the substrate 9 and the thin film 911 is left in the peripheral portion 93 is described for the sake of simplicity. May be used in various processes.
  • FIG. 6 shows another example of the substrate.
  • a laminated film 912 is formed inside the peripheral edge 93 on the upper surface of the substrate body 90. That is, the stacked film 912 is provided in the processing region 95 on the upper surface 91.
  • the stacked film 912 includes a plurality of first material films 913 formed of a first material and a plurality of second material films 914 formed of a second material different from the first material.
  • the first material film 913 and the second material film 914 are alternately provided in the thickness direction (stacking direction).
  • the first material film 913 is an insulating film such as a silicon oxide film.
  • the first material film 913 may be a film made of a material having a sufficiently low etching rate with an etchant (a material that is hardly etched), and may be a silicon nitride film, TEOS (tetraethoxysilane), or the like.
  • the second material film 914 is a polysilicon film.
  • the second material film 914 may be a film of another material having a relatively high etching rate with the etching solution.
  • the laminated film 912 is not formed on the surface of the peripheral edge portion 93 on the upper surface of the substrate body 90.
  • the surface of the peripheral edge portion 93 of the upper surface 91 of the substrate 9a is the surface of the substrate body 90.
  • the substrate body 90 is made of a non-oxide (for example, silicon), and the etching rate of the substrate body 90 with the etching solution is relatively high. Further, the surface of the substrate body 90 can be oxidized by an oxidizing solution.
  • the peripheral edge portion 93 of the upper surface 91 may be a film surface of a material that can be etched with an etching solution and oxidized with an oxidizing solution, such as the second material film 914.
  • the lower surface 92 of the substrate 9 a is the lower surface of the substrate body 90.
  • the lower surface 92 of the substrate 9a may be the surface of a thin film formed on the lower surface of the substrate body 90.
  • a plurality of holes 915 extending in the thickness direction with respect to the stacked film 912 are formed in advance by an external apparatus.
  • Each hole 915 penetrates the plurality of first material films 913 and the plurality of second material films 914. Formation of the hole 915 is performed by reactive ion etching, for example.
  • the supply of the chemical liquid to the upper surface 91 and the lower surface 92 and the supply of the rinse liquid to the upper surface 91 and the lower surface 92 are sequentially performed while rotating the substrate 9a in the same manner as described above.
  • FIG. 3 steps S11 to S13.
  • the discharge of the oxidizing solution from the lower nozzle 41 to the central portion of the lower surface 92 and the discharge of the etching solution from the upper nozzle 31 to the central portion of the upper surface 91 are started almost simultaneously (steps S14 and S15).
  • the oxidizing solution spreads toward the outer peripheral edge of the substrate 9a by the rotation of the substrate 9a, and an oxide film is formed.
  • a part of the oxidizing solution is supplied to the peripheral edge portion 93 of the upper surface 91 via the outer peripheral end surface 94 (see FIG. 4).
  • the etching solution spreads toward the outer peripheral edge of the substrate 9a by the rotation of the substrate 9a. In the peripheral portion 93 of the upper surface 91, the etching is suppressed by mixing the etching solution and the oxidizing solution.
  • the second material film 914 is selectively etched by the etchant that has entered the hole 915.
  • the first material film 913 is hardly etched by the etchant.
  • the second material film 914 recedes from the inner peripheral surface of the hole 915. In other words, a structure in which the first material film 913 protrudes inward from the inner peripheral surface of the expanded hole 915 is obtained.
  • the treatment region 95 is also a treatment liquid that can be oxidized.
  • the discharge of the oxidizing solution and the etching solution is continued for a predetermined time and then stopped. Subsequently, the supply of the rinse liquid to the upper surface 91 and the lower surface 92 and the supply of the organic solvent to the upper surface 91 are sequentially performed (steps S16 and S17). After the substrate 9a is dried at high speed, the rotation of the substrate 9a is stopped (steps S18 and S19), and the processing of the substrate 9a in the substrate processing apparatus 1 is completed.
  • the etching amount at the peripheral edge portion 93 of the upper surface 91 is increased (for example, the etching amount is several tens of ⁇ m with respect to the original thickness of 775 ⁇ m). In this case, a problem occurs in the transfer of the substrate 9a in the subsequent process.
  • the peripheral portion 93 of the upper surface 91 is protected by the oxidizing solution, thereby suppressing the peripheral portion 93 from being etched in the selective etching of the second material film 914 that requires a long time. can do.
  • the thickness of the oxide film formed on the lower surface 92 of the substrate 9a and the peripheral portion 93 of the upper surface 91 is several nanometers, there is no problem in transporting the substrate 9a and it is necessary to remove it. Absent.
  • the outer peripheral end surface 94 (bevel surface) of the substrate 9a is also protected by the oxidizing solution, it is possible to prevent the diameter of the substrate 9a from being reduced.
  • FIG. 9 is a diagram showing another example of the substrate processing apparatus.
  • the structure of the oxidizing solution supply part 4a is different from the substrate processing apparatus 1 of FIG.
  • Other configurations are the same as those of the substrate processing apparatus 1 of FIG. 1, and the same components are denoted by the same reference numerals.
  • the oxidizing solution supply unit 4 a includes an oxidizing solution nozzle 41 a located on the upper surface 91 side of the substrate 9.
  • the oxidizing solution nozzle 41a extends in the vertical direction, and is supported by being inclined with respect to the vertical direction so that the lower end surface on which the discharge port is formed is located on the outer side in the radial direction with respect to the upper end surface. .
  • the discharge port of the oxidizing solution nozzle 41 a faces the vicinity of the peripheral edge portion 93 of the upper surface 91.
  • the oxidizing solution is discharged from the oxidizing solution nozzle 41a toward the peripheral portion 93 of the upper surface 91.
  • the discharge direction of the oxidizing solution in the oxidizing solution nozzle 41a is directed downward and radially outward.
  • the discharge of the oxidizing solution from the oxidizing solution nozzle 41a to the peripheral portion 93 of the upper surface 91 and the discharge of the etching solution from the upper nozzle 31 to the central portion of the upper surface 91 are started almost simultaneously.
  • the thin film 911 (see FIG. 2) is etched by the etchant.
  • the etching is suppressed by mixing the etching solution and the oxidizing solution.
  • the substrate 9a of FIG. 6 may be processed in the substrate processing apparatus 1a of FIG.
  • the step of supplying the oxidizing solution to the peripheral portion 93 of the upper surface 91 and the etching into the processing region 95 located inside the peripheral portion 93 are performed. And a step of supplying a liquid.
  • the processing region 95 of the upper surface 91 is caused by the splashing of the oxidizing solution discharged from the oxidizing solution nozzle 41a toward the peripheral portion 93 of the upper surface 91.
  • the oxidizing solution adheres to the surface.
  • the surface of a part of the thin film 911 or the second material film 914 is oxidized, the surface (oxide film surface) is hardly etched by the etchant.
  • the step of supplying the oxidizing solution to the peripheral portion 93 of the upper surface 91 and the step of supplying the etching solution to the processing region 95 located inside the peripheral portion 93 can be performed separately.
  • the oxidizing solution is discharged from the lower nozzle 41 toward the lower surface 92 while rotating the substrates 9 and 9 a.
  • pure water is discharged from the upper nozzle 31 toward the center of the upper surface 91.
  • the processing of the substrates 9 and 9a is performed. It is possible to efficiently perform (that is, shorten the time required for processing). Also in this case, the entry of the oxidizing solution into the processing region 95 can be suppressed by the etching solution, and the processing region 95 can be appropriately etched.
  • the substrate processing and the substrate processing apparatus 1, 1a can be variously modified.
  • the peripheral portion 93 of the lower surface 92 is protected by the oxidizing solution that flows from the upper surface 91 to the lower surface 92 by discharging the oxidizing solution from the upper nozzle 31 and discharging the etching solution from the lower nozzle 41.
  • the processing region (the processing region of the lower surface 92) located inside the peripheral edge portion 93 may be etched.
  • the etching solution may be discharged from the lower nozzle 41 while discharging the oxidizing solution from the oxidizing solution nozzle facing the peripheral edge portion 93 of the lower surface 92.
  • the oxidizing liquid that oxidizes one main surface of the substrates 9 and 9a is discharged from the nozzle toward the substrates 9 and 9a, whereby the peripheral edge of the one main surface is obtained.
  • the step of supplying the oxidizing solution to the portion 93 and the etching solution for etching the one main surface are ejected from the nozzle toward the substrates 9 and 9a, so that the one main surface is positioned inside the peripheral portion 93.
  • region can be etched appropriately, protecting the peripheral part 93 with an oxidizing solution.
  • the lower nozzle 41 may be disposed at a position facing the peripheral edge portion 93 of the lower surface 92 of the substrates 9 and 9a. Also in this case, the oxidizing solution can be supplied to the peripheral edge portion 93 of the upper surface 91 via the outer peripheral end surface 94 of the rotating substrates 9 and 9a.
  • the lower nozzle 41 is directed toward the center of the lower surface 92. It is preferable that the oxidizing solution is discharged. When an oxide film is formed on the entire lower surface 92, the lower surface 92 can be protected by the oxide film in subsequent steps.
  • the etching solution does not necessarily have to be discharged toward the central portion of the upper surface 91, and the etching solution from the upper nozzle 31 toward the inner side of the peripheral portion 93 and the outer side of the central portion on the upper surface 91. May be discharged.
  • the processing region where etching is performed does not necessarily include the central portion.
  • a substrate holding portion that holds the central portion of the lower surface 92 by suction may be provided.
  • the substrate to be processed in the substrate processing apparatus 1 or 1a is not limited to a semiconductor substrate, and may be another substrate.

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Abstract

In this substrate processing device, there are performed: a step in which an oxidizing liquid (82) that causes an upper surface (91) of a substrate (9) to oxidize is discharged from a nozzle toward the substrate (9), which rotates, whereby the oxidizing liquid (82) is supplied to the peripheral edge part (93) of the upper surface (91); and a step in which an etching liquid (81) that etches the upper surface (91) is discharged from the nozzle toward the rotating substrate (9), whereby the etching liquid (81) is supplied to a treatment region (95) positioned on the inner side of the peripheral edge part (93), on the upper surface (91). This makes it possible to suitably etch the processing region (95) in the upper surface (91) while protecting the peripheral edge part (93) using the oxidizing liquid (82).

Description

基板処理方法および基板処理装置Substrate processing method and substrate processing apparatus
　本発明は、基板処理方法および基板処理装置に関する。 The present invention relates to a substrate processing method and a substrate processing apparatus.
　従来、半導体基板（以下、単に「基板」という。）の製造工程では、基板の表面に対して各種処理が行われる。例えば、特開２０１６－１３９７４３号公報（文献１）では、回転している基板の上面の周縁部近傍にエッチング用の薬液を供給しつつ、基板の下面の周縁部近傍にエッチング阻害液である純水が供給される。純水の一部は、表面張力により基板の端縁を超えて基板の上面まで回り込み、薬液と衝突する。これにより、純水と薬液とが衝突する部位において薬液が希釈され、当該部位においてエッチングレートを低下させることが可能となる。 Conventionally, in the manufacturing process of a semiconductor substrate (hereinafter simply referred to as “substrate”), various processes are performed on the surface of the substrate. For example, in Japanese Patent Laid-Open No. 2016-139743 (Reference 1), a chemical solution for etching is supplied to the vicinity of the peripheral portion of the upper surface of the rotating substrate, and an etching inhibitory solution is supplied to the vicinity of the peripheral portion of the lower surface of the substrate. Water is supplied. Part of the pure water goes over the edge of the substrate to the upper surface of the substrate due to surface tension and collides with the chemical solution. Thereby, the chemical solution is diluted at the site where the pure water and the chemical solution collide, and the etching rate can be reduced at the site.
　ところで、文献１の手法では、上面の周縁部において、純水による薬液の希釈によりエッチングレートを低下させているのみであるため、周縁部が想定以上にエッチングされてしまう可能性がある。周縁部がエッチングされると、後続の工程における基板の搬送等において不具合が生じる可能性がある。したがって、周縁部を保護しつつ、周縁部の内側に位置する処理領域を適切にエッチングすることが可能な新規な手法が求められている。 By the way, in the method of Document 1, only the etching rate is reduced by the dilution of the chemical solution with pure water at the peripheral portion of the upper surface, so that the peripheral portion may be etched more than expected. When the peripheral portion is etched, there is a possibility that a problem may occur in transporting the substrate in the subsequent process. Therefore, there is a need for a new technique that can appropriately etch the processing region located inside the peripheral portion while protecting the peripheral portion.
　本発明は、基板処理方法に向けられており、周縁部を保護しつつ、処理領域を適切にエッチングすることを目的としている。 The present invention is directed to a substrate processing method, and an object thereof is to appropriately etch a processing region while protecting a peripheral portion.
　本発明に係る基板処理方法は、ａ）円板状の基板を水平状態で回転しつつ、前記基板の一の主面を酸化させる酸化液を、前記基板に向けてノズルから吐出することにより、前記一の主面の周縁部に前記酸化液を供給する工程と、ｂ）前記基板を水平状態で回転しつつ、前記一の主面をエッチングするエッチング液を、前記基板に向けてノズルから吐出することにより、前記一の主面において前記周縁部の内側に位置する処理領域に前記エッチング液を供給する工程とを備える。 In the substrate processing method according to the present invention, a) by rotating the disk-shaped substrate in a horizontal state and discharging an oxidizing solution for oxidizing one main surface of the substrate from the nozzle toward the substrate, Supplying the oxidizing solution to the peripheral portion of the one main surface; and b) discharging an etching solution for etching the one main surface from the nozzle toward the substrate while rotating the substrate in a horizontal state. And the step of supplying the etching solution to a processing region located inside the peripheral edge on the one main surface.
　本発明によれば、基板の一の主面において、酸化液により周縁部を保護しつつ、処理領域を適切にエッチングすることができる。 According to the present invention, the processing region can be appropriately etched on one main surface of the substrate while protecting the peripheral portion with the oxidizing solution.
　本発明の一の好ましい形態では、前記ａ）工程において、前記基板の他の主面側に位置する前記ノズルから前記他の主面に向けて前記酸化液が吐出され、回転する前記基板の外周端面を経由して、前記酸化液が前記一の主面の前記周縁部に供給される。 In one preferable mode of the present invention, in the step a), the oxidizing solution is discharged from the nozzle located on the other main surface side of the substrate toward the other main surface, and the outer periphery of the substrate rotates. The oxidizing solution is supplied to the peripheral portion of the one main surface via the end surface.
　この場合に、前記ａ）工程において、前記他の主面側に位置する前記ノズルから前記他の主面の中央部に向けて前記酸化液が吐出されることが好ましい。 In this case, in the step a), it is preferable that the oxidizing solution is discharged from the nozzle located on the other main surface side toward the center of the other main surface.
　また、前記ａ）およびｂ）工程が同時に行われ、前記ｂ）工程において、前記基板の前記一の主面側に位置する前記ノズルから、前記処理領域に向けて前記エッチング液が吐出されてもよい。 In addition, the steps a) and b) are performed at the same time. In the step b), the etching solution is discharged from the nozzle located on the one main surface side of the substrate toward the processing region. Good.
　この場合に、前記一の主面に吐出される前記エッチング液、および、前記他の主面に吐出される前記酸化液の双方が加熱されていることが好ましい。 In this case, it is preferable that both the etching solution discharged to the one main surface and the oxidizing solution discharged to the other main surface are heated.
　例えば、前記基板の半径が１５０ｍｍであり、前記ａ）およびｂ）工程における前記基板の回転数が、５０～３００ｒｐｍである。 For example, the radius of the substrate is 150 mm, and the rotation speed of the substrate in the steps a) and b) is 50 to 300 rpm.
　本発明の他の好ましい形態では、第１材料により形成された複数の第１材料膜と、前記第１材料とは異なる第２材料により形成された複数の第２材料膜とを含む積層膜が、前記基板の前記一の主面において前記処理領域に設けられており、前記ｂ）工程の前に、厚さ方向に延びる孔部が前記積層膜に形成されており、前記ｂ）工程において、前記積層膜に含まれる前記複数の第２材料膜が、前記孔部を介して選択的にエッチングされる。 In another preferred embodiment of the present invention, a laminated film including a plurality of first material films formed of a first material and a plurality of second material films formed of a second material different from the first material. , Provided in the processing region on the one main surface of the substrate, and before the step b), a hole extending in the thickness direction is formed in the laminated film, and in the step b) The plurality of second material films included in the stacked film are selectively etched through the holes.
　本発明の他の好ましい形態では、前記エッチング液がアルカリ性を有する。 In another preferred embodiment of the present invention, the etching solution has alkalinity.
　本発明は、基板処理装置にも向けられている。本発明に係る基板処理装置は、円板状の基板を水平状態で保持する基板保持部と、上下方向を向く中心軸を中心として前記基板保持部を回転する基板回転機構と、前記基板の一の主面を酸化させる酸化液を、回転する前記基板に向けてノズルから吐出することにより、前記一の主面の周縁部に前記酸化液を供給する酸化液供給部と、前記一の主面をエッチングするエッチング液を、回転する前記基板に向けてノズルから吐出することにより、前記一の主面において前記周縁部の内側に位置する処理領域に前記エッチング液を供給するエッチング液供給部とを備える。 The present invention is also directed to a substrate processing apparatus. A substrate processing apparatus according to the present invention includes a substrate holding unit that holds a disk-shaped substrate in a horizontal state, a substrate rotation mechanism that rotates the substrate holding unit about a central axis that faces in the up-down direction, and one of the substrates. An oxidizing solution supply section for supplying the oxidizing solution to a peripheral portion of the one main surface by discharging an oxidizing solution for oxidizing the main surface of the main surface toward the rotating substrate from the nozzle; and the one main surface An etching solution supply unit for supplying the etching solution to a processing region located inside the peripheral portion on the one main surface by discharging an etching solution for etching the substrate toward the rotating substrate from the nozzle. Prepare.
　上述の目的および他の目的、特徴、態様および利点は、添付した図面を参照して以下に行うこの発明の詳細な説明により明らかにされる。 The above object and other objects, features, aspects, and advantages will become apparent from the following detailed description of the present invention with reference to the accompanying drawings.
基板処理装置の構成を示す図である。It is a figure which shows the structure of a substrate processing apparatus. 基板の周縁部近傍を示す図である。It is a figure which shows the peripheral part vicinity of a board | substrate. 基板を処理する流れを示す図である。It is a figure which shows the flow which processes a board | substrate. 基板の処理を説明するための図である。It is a figure for demonstrating the process of a board | substrate. 基板の処理を説明するための図である。It is a figure for demonstrating the process of a board | substrate. 基板の他の例を示す図である。It is a figure which shows the other example of a board | substrate. 基板の処理を説明するための図である。It is a figure for demonstrating the process of a board | substrate. 基板の処理を説明するための図である。It is a figure for demonstrating the process of a board | substrate. 基板処理装置の他の例を示す図である。It is a figure which shows the other example of a substrate processing apparatus.
　図１は、本発明の一の実施の形態に係る基板処理装置１の構成を示す図である。基板処理装置１は、円板状の基板９を１枚ずつ処理する枚葉式の装置である。基板処理装置１は、基板保持部２１と、基板回転機構２２と、カップ２３と、エッチング液供給部３と、酸化液供給部４とを備える。 FIG. 1 is a diagram showing a configuration of a substrate processing apparatus 1 according to an embodiment of the present invention. The substrate processing apparatus 1 is a single wafer processing apparatus that processes the disk-shaped substrates 9 one by one. The substrate processing apparatus 1 includes a substrate holding unit 21, a substrate rotating mechanism 22, a cup 23, an etching solution supply unit 3, and an oxidizing solution supply unit 4.
　基板保持部２１は、上下方向を向く中心軸Ｊ１を中心とする円板状のベース部２１１を有する。ベース部２１１の上面には、複数のチャックピン２１２が設けられる。複数のチャックピン２１２は、中心軸Ｊ１を中心とする円周上において、周方向に等間隔に配置される。基板保持部２１が基板９を保持する際には、複数のチャックピン２１２が、基板９の外周縁に押し付けられる。これにより、基板９がベース部２１１の上方において水平状態で保持される。基板保持部２１により保持された基板９の中心は、中心軸Ｊ１上に位置する。ベース部２１１の上面は、基板９の下方を向く主面９２（以下、「下面９２」という。）と平行であり、両者は隙間を空けて互いに対向する。 The substrate holding part 21 has a disk-like base part 211 centering on a central axis J1 facing in the up-down direction. A plurality of chuck pins 212 are provided on the upper surface of the base portion 211. The plurality of chuck pins 212 are arranged at equal intervals in the circumferential direction on a circumference centered on the central axis J1. When the substrate holding unit 21 holds the substrate 9, the plurality of chuck pins 212 are pressed against the outer peripheral edge of the substrate 9. As a result, the substrate 9 is held in a horizontal state above the base portion 211. The center of the substrate 9 held by the substrate holding part 21 is located on the central axis J1. The upper surface of the base portion 211 is parallel to a main surface 92 (hereinafter referred to as “lower surface 92”) facing downward of the substrate 9, and both face each other with a gap.
　ベース部２１１の下面の中央には、中心軸Ｊ１を中心とするシャフト部２２１の一端が固定される。モータを有する基板回転機構２２が、シャフト部２２１の他端部を回転することにより、基板保持部２１が基板９と共に中心軸Ｊ１を中心として回転する。カップ２３は、ベース部２１１の周囲を囲む略筒状である。後述する基板９の処理では、回転する基板９の外周縁から飛散する各種処理液が、カップ２３の内周面により受けられ、回収される。基板処理装置１では、図示省略のカップ昇降機構により、カップ２３の上部が上下方向に昇降可能である。基板処理装置１への基板９の搬入搬出時には、カップ２３の上部が下降して、カップ２３が外部の搬送機構と干渉することが防止される。 At the center of the lower surface of the base portion 211, one end of the shaft portion 221 centered on the central axis J1 is fixed. When the substrate rotation mechanism 22 having a motor rotates the other end of the shaft portion 221, the substrate holding portion 21 rotates together with the substrate 9 about the central axis J1. The cup 23 has a substantially cylindrical shape surrounding the base portion 211. In the processing of the substrate 9 described later, various processing liquids scattered from the outer peripheral edge of the rotating substrate 9 are received by the inner peripheral surface of the cup 23 and collected. In the substrate processing apparatus 1, the upper part of the cup 23 can be moved up and down by a cup lifting mechanism (not shown). When the substrate 9 is carried into and out of the substrate processing apparatus 1, the upper part of the cup 23 is lowered, and the cup 23 is prevented from interfering with an external transport mechanism.
　酸化液供給部４は、下部ノズル４１と、酸化液供給源４２とを備える。下部ノズル４１は、上下方向に延びる。ベース部２１１およびシャフト部２２１には、上下方向に延びる中空部が中心軸Ｊ１上に設けられており、当該中空部内に下部ノズル４１が配置される。下部ノズル４１の上端面は、ベース部２１１の上面近傍に配置される。下部ノズル４１は、基板保持部２１に保持された基板９の下面９２側に位置する。下部ノズル４１の上端面は、基板９の下面９２に直接的に対向する。下部ノズル４１の下端には、酸化液供給源４２が弁を介して接続され、酸化液供給源４２から下部ノズル４１に酸化液が供給される。酸化液は、下部ノズル４１の上端面の中央に設けられた吐出口から上方に吐出される。すなわち、下部ノズル４１から、基板９の下面９２の中央部に向けて酸化液が吐出される。酸化液の詳細については後述する。 The oxidizing solution supply unit 4 includes a lower nozzle 41 and an oxidizing solution supply source 42. The lower nozzle 41 extends in the vertical direction. In the base portion 211 and the shaft portion 221, a hollow portion extending in the vertical direction is provided on the central axis J1, and the lower nozzle 41 is disposed in the hollow portion. The upper end surface of the lower nozzle 41 is disposed in the vicinity of the upper surface of the base portion 211. The lower nozzle 41 is located on the lower surface 92 side of the substrate 9 held by the substrate holding unit 21. The upper end surface of the lower nozzle 41 directly faces the lower surface 92 of the substrate 9. An oxidizing solution supply source 42 is connected to the lower end of the lower nozzle 41 via a valve, and the oxidizing solution is supplied from the oxidizing solution supply source 42 to the lower nozzle 41. The oxidizing solution is discharged upward from a discharge port provided at the center of the upper end surface of the lower nozzle 41. That is, the oxidizing solution is discharged from the lower nozzle 41 toward the center of the lower surface 92 of the substrate 9. Details of the oxidizing solution will be described later.
　下部ノズル４１には、薬液供給源４３およびリンス液供給源４４が弁を介してさらに接続される。薬液供給源４３から下部ノズル４１に薬液が供給されることにより、下部ノズル４１から、基板９の下面９２の中央部に向けて薬液が吐出される。リンス液供給源４４から下部ノズル４１にリンス液が供給されることにより、下部ノズル４１から、下面９２の中央部に向けてリンス液が吐出される。基板処理装置１では、下部ノズル４１および薬液供給源４３により下面薬液供給部が構成され、下部ノズル４１およびリンス液供給源４４により下面リンス液供給部が構成される。酸化液供給部４、下面薬液供給部および下面リンス液供給部では、下部ノズル４１が共有されている。下面薬液供給部および下面リンス液供給部の一方または双方が、下部ノズル４１とは個別のノズルを有してもよい。 A chemical liquid supply source 43 and a rinse liquid supply source 44 are further connected to the lower nozzle 41 via valves. By supplying the chemical solution from the chemical solution supply source 43 to the lower nozzle 41, the chemical solution is discharged from the lower nozzle 41 toward the center of the lower surface 92 of the substrate 9. By supplying the rinse liquid from the rinse liquid supply source 44 to the lower nozzle 41, the rinse liquid is discharged from the lower nozzle 41 toward the center of the lower surface 92. In the substrate processing apparatus 1, the lower nozzle 41 and the chemical liquid supply source 43 constitute a lower surface chemical liquid supply unit, and the lower nozzle 41 and the rinse liquid supply source 44 constitute a lower surface rinse liquid supply unit. The lower nozzle 41 is shared by the oxidizing solution supply unit 4, the lower chemical solution supply unit, and the lower rinse solution supply unit. One or both of the lower surface chemical liquid supply unit and the lower surface rinse liquid supply unit may have a nozzle separate from the lower nozzle 41.
　エッチング液供給部３は、上部ノズル３１と、エッチング液供給源３２とを備える。上部ノズル３１は、上下方向に延びる。上部ノズル３１は、基板９の上方を向く主面９１（以下、「上面９１」という。）側に位置する。詳細には、上部ノズル３１は、上面９１の中央部の上方に配置される。上部ノズル３１の下端面は、上面９１に直接的に対向する。上部ノズル３１の上端には、エッチング液供給源３２が弁を介して接続され、エッチング液供給源３２から上部ノズル３１にエッチング液が供給される。エッチング液は、上部ノズル３１の下端面の中央に設けられた吐出口から下方に吐出される。すなわち、上部ノズル３１から、基板９の上面９１の中央部に向けてエッチング液が吐出される。エッチング液の詳細については後述する。 The etchant supply unit 3 includes an upper nozzle 31 and an etchant supply source 32. The upper nozzle 31 extends in the vertical direction. The upper nozzle 31 is located on the main surface 91 (hereinafter referred to as “upper surface 91”) side facing the upper side of the substrate 9. Specifically, the upper nozzle 31 is disposed above the central portion of the upper surface 91. The lower end surface of the upper nozzle 31 directly faces the upper surface 91. An etching solution supply source 32 is connected to the upper end of the upper nozzle 31 via a valve, and the etching solution is supplied from the etching solution supply source 32 to the upper nozzle 31. The etching solution is discharged downward from a discharge port provided at the center of the lower end surface of the upper nozzle 31. That is, the etching solution is discharged from the upper nozzle 31 toward the center of the upper surface 91 of the substrate 9. Details of the etching solution will be described later.
　上部ノズル３１には、薬液供給源３３およびリンス液供給源３４が弁を介してさらに接続される。薬液供給源３３から上部ノズル３１に薬液が供給されることにより、上部ノズル３１から、基板９の上面９１の中央部に向けて薬液が吐出される。リンス液供給源３４から上部ノズル３１にリンス液が供給されることにより、上部ノズル３１から、上面９１の中央部に向けてリンス液が吐出される。基板処理装置１では、上部ノズル３１および薬液供給源３３により上面薬液供給部が構成され、上部ノズル３１およびリンス液供給源３４により上面リンス液供給部が構成される。エッチング液供給部３、上面薬液供給部および上面リンス液供給部では、上部ノズル３１が共有されている。上面薬液供給部および上面リンス液供給部の一方または双方が、上部ノズル３１とは個別のノズルを有してもよい。また、薬液供給源３３が薬液供給源４３を兼ねてもよく、リンス液供給源３４がリンス液供給源４４を兼ねてもよい。 A chemical solution supply source 33 and a rinse solution supply source 34 are further connected to the upper nozzle 31 via valves. By supplying the chemical solution from the chemical solution supply source 33 to the upper nozzle 31, the chemical solution is discharged from the upper nozzle 31 toward the center of the upper surface 91 of the substrate 9. By supplying the rinse liquid from the rinse liquid supply source 34 to the upper nozzle 31, the rinse liquid is discharged from the upper nozzle 31 toward the center of the upper surface 91. In the substrate processing apparatus 1, the upper nozzle 31 and the chemical liquid supply source 33 constitute an upper surface chemical liquid supply unit, and the upper nozzle 31 and the rinse liquid supply source 34 constitute an upper surface rinse liquid supply unit. The upper nozzle 31 is shared by the etching solution supply unit 3, the upper surface chemical solution supply unit, and the upper surface rinse solution supply unit. One or both of the upper surface chemical liquid supply unit and the upper surface rinse liquid supply unit may have a nozzle separate from the upper nozzle 31. Further, the chemical liquid supply source 33 may also serve as the chemical liquid supply source 43, and the rinse liquid supply source 34 may also serve as the rinse liquid supply source 44.
　基板処理装置１は、有機溶剤供給部５をさらに備える。有機溶剤供給部５は、補助ノズル５１と、有機溶剤供給源５２とを備える。補助ノズル５１は、基板９の上方に配置される。補助ノズル５１には、有機溶剤供給源５２が弁を介して接続される。有機溶剤供給源５２から補助ノズル５１に有機溶剤が供給されることにより、補助ノズル５１から、基板９の上面９１の中央部に向けて有機溶剤が吐出される。基板処理装置１では、上部ノズル３１および補助ノズル５１のそれぞれを移動するノズル移動機構が設けられてもよい。ノズル移動機構は、上部ノズル３１および補助ノズル５１を、基板９の上面９１に対向する対向位置と、基板９から水平方向に離れた待機位置とに選択的に配置する。ノズル移動機構は、上部ノズル３１および補助ノズル５１を個別に移動してもよい。 The substrate processing apparatus 1 further includes an organic solvent supply unit 5. The organic solvent supply unit 5 includes an auxiliary nozzle 51 and an organic solvent supply source 52. The auxiliary nozzle 51 is disposed above the substrate 9. An organic solvent supply source 52 is connected to the auxiliary nozzle 51 via a valve. By supplying the organic solvent from the organic solvent supply source 52 to the auxiliary nozzle 51, the organic solvent is discharged from the auxiliary nozzle 51 toward the center of the upper surface 91 of the substrate 9. In the substrate processing apparatus 1, a nozzle moving mechanism that moves each of the upper nozzle 31 and the auxiliary nozzle 51 may be provided. The nozzle moving mechanism selectively arranges the upper nozzle 31 and the auxiliary nozzle 51 at a facing position facing the upper surface 91 of the substrate 9 and a standby position away from the substrate 9 in the horizontal direction. The nozzle moving mechanism may move the upper nozzle 31 and the auxiliary nozzle 51 individually.
　図２は、基板９の周縁部９３近傍を示す図であり、中心軸Ｊ１を含む面における基板９の断面を示している。基板９は、基板本体９０と、薄膜９１１とを備える。薄膜９１１は、基板本体９０の上面に所定の材料（例えば、アモルファスシリコン）により形成され、当該上面の全体を覆う。基板９の上面９１は、薄膜９１１の表面である。基板９の下面９２は、基板本体９０の下面である。下面９２に、薄膜が形成されてもよい。薄膜９１１は、基板９の外周端面９４（いわゆる、ベベル面）の一部にも設けられる。既述の周縁部９３は、基板９における、外周端面９４およびその近傍を含む環状の部位である。基板９を収納する容器では、基板９の周縁部９３が当該容器の保持部と接触し、かつ、周縁部９３よりも内側の部位はいずれの部材とも接触しない状態で、基板９が保持される。 FIG. 2 is a view showing the vicinity of the peripheral edge portion 93 of the substrate 9, and shows a cross section of the substrate 9 in a plane including the central axis J1. The substrate 9 includes a substrate body 90 and a thin film 911. The thin film 911 is formed on the upper surface of the substrate body 90 with a predetermined material (for example, amorphous silicon) and covers the entire upper surface. The upper surface 91 of the substrate 9 is the surface of the thin film 911. The lower surface 92 of the substrate 9 is the lower surface of the substrate body 90. A thin film may be formed on the lower surface 92. The thin film 911 is also provided on a part of the outer peripheral end surface 94 (so-called bevel surface) of the substrate 9. The peripheral edge portion 93 described above is an annular portion including the outer peripheral end surface 94 and the vicinity thereof on the substrate 9. In the container that stores the substrate 9, the substrate 9 is held in a state in which the peripheral portion 93 of the substrate 9 is in contact with the holding portion of the container and the portion inside the peripheral portion 93 is not in contact with any member. .
　ここで、基板処理装置１において用いられるエッチング液は、上記薄膜９１１をエッチングすることが可能なものであり、ＴＭＹ（トリメチル－２ヒドロキシエチルアンモニウムハイドロオキサイド）、ＴＭＡＨ（テトラメチルアンモニウムハイドロオキサイド）、アンモニア水（ＮＨ４ＯＨ）等のアルカリ性を有するエッチング液が例示される。本実施の形態では、エッチング液としてＴＭＹの水溶液が用いられる。酸性のエッチング液が用いられてもよい。また、基板処理装置１において用いられる酸化液は、上記薄膜９１１を酸化させる（すなわち、酸化膜を形成する）ことが可能なものであり、過酸化水素水（Ｈ２Ｏ２）、アンモニア水と過酸化水素水の混合液、オゾン水等が例示される。本実施の形態では、酸化液として過酸化水素水が用いられる。 Here, the etching solution used in the substrate processing apparatus 1 is capable of etching the thin film 911, such as TMY (trimethyl-2hydroxyethylammonium hydroxide), TMAH (tetramethylammonium hydroxide), ammonia. An etching solution having alkalinity such as water (NH 4 OH) is exemplified. In this embodiment, an aqueous solution of TMY is used as an etching solution. An acidic etchant may be used. Further, the oxidizing solution used in the substrate processing apparatus 1 is capable of oxidizing the thin film 911 (that is, forming an oxide film), hydrogen peroxide water (H 2 O 2 ), ammonia water, Examples thereof include a mixed solution of hydrogen peroxide water and ozone water. In the present embodiment, hydrogen peroxide is used as the oxidizing solution.
　図３は、基板処理装置１が基板９を処理する流れを示す図である。図１の基板処理装置１では、事前に、外部の搬送機構により処理対象の基板９が搬入され、基板保持部２１により保持されている。基板９の処理では、まず、基板回転機構２２により基板９の回転が開始される（ステップＳ１１）。基板９は、水平状態で基板保持部２１と共に回転する。また、対向位置に配置された上部ノズル３１を介して、上面薬液供給部により基板９の上面９１の中央部に薬液が供給され、下面薬液供給部により下部ノズル４１を介して下面９２の中央部に薬液が供給される（ステップＳ１２）。 FIG. 3 is a diagram showing a flow in which the substrate processing apparatus 1 processes the substrate 9. In the substrate processing apparatus 1 of FIG. 1, the substrate 9 to be processed is loaded in advance by an external transfer mechanism and held by the substrate holding unit 21. In the processing of the substrate 9, first, the substrate rotation mechanism 22 starts to rotate the substrate 9 (step S11). The substrate 9 rotates together with the substrate holding unit 21 in a horizontal state. Further, a chemical solution is supplied to the central portion of the upper surface 91 of the substrate 9 by the upper surface chemical solution supply unit via the upper nozzle 31 disposed at the opposite position, and the central portion of the lower surface 92 is supplied by the lower surface chemical solution supply unit via the lower nozzle 41. The chemical solution is supplied to (step S12).
　上面９１および下面９２では、基板９の回転により薬液が基板９の外周縁に向かって広がり、上面９１および下面９２の全体に薬液が供給される。基板９の外周縁から飛散する薬液は、カップ２３の内周面により受けられて回収される（後述のリンス液、酸化液およびエッチング液の供給時において同様）。薬液は、例えばＤＨＦ（希フッ酸）であり、薬液の供給により、上面９１および下面９２の自然酸化膜が除去される。基板処理装置１では、他の種類の薬液が用いられてもよい。 On the upper surface 91 and the lower surface 92, the chemical solution spreads toward the outer peripheral edge of the substrate 9 by the rotation of the substrate 9, and the chemical solution is supplied to the entire upper surface 91 and the lower surface 92. The chemical liquid scattered from the outer peripheral edge of the substrate 9 is received and collected by the inner peripheral surface of the cup 23 (the same applies when supplying a rinse liquid, an oxidizing liquid and an etching liquid described later). The chemical solution is, for example, DHF (dilute hydrofluoric acid), and the natural oxide films on the upper surface 91 and the lower surface 92 are removed by supplying the chemical solution. In the substrate processing apparatus 1, other types of chemical solutions may be used.
　薬液の吐出が所定時間継続されると、薬液の吐出が停止される。続いて、上面リンス液供給部により上部ノズル３１を介して上面９１の中央部にリンス液が供給されるとともに、下面リンス液供給部により下部ノズル４１を介して下面９２の中央部にリンス液が供給される（ステップＳ１３）。上面９１および下面９２では、基板９の回転によりリンス液が基板９の外周縁に向かって広がり、上面９１および下面９２の全体にリンス液が供給される。リンス液は、例えば純水であり、リンス液の供給により、上面９１および下面９２に付着する薬液が除去される。基板処理装置１では、純水以外のリンス液が用いられてもよい。リンス液の吐出は所定時間継続され、その後、停止される。 When the discharge of the chemical liquid is continued for a predetermined time, the discharge of the chemical liquid is stopped. Subsequently, the rinsing liquid is supplied to the central portion of the upper surface 91 by the upper surface rinsing liquid supply unit via the upper nozzle 31 and the rinsing liquid is supplied to the central portion of the lower surface 92 by the lower surface rinsing liquid supply unit via the lower nozzle 41. Is supplied (step S13). On the upper surface 91 and the lower surface 92, the rinse liquid spreads toward the outer peripheral edge of the substrate 9 by the rotation of the substrate 9, and the rinse liquid is supplied to the entire upper surface 91 and the lower surface 92. The rinse liquid is, for example, pure water, and the chemical liquid attached to the upper surface 91 and the lower surface 92 is removed by supplying the rinse liquid. In the substrate processing apparatus 1, a rinse liquid other than pure water may be used. The discharge of the rinse liquid is continued for a predetermined time and then stopped.
　続いて、酸化液供給源４２が下部ノズル４１に酸化液を供給することにより、下部ノズル４１から、下面９２の中央部に向けて酸化液が連続的に吐出される（ステップＳ１４）。また、エッチング液供給源３２が上部ノズル３１にエッチング液を供給することにより、上部ノズル３１から、上面９１の中央部に向けてエッチング液が連続的に吐出される（ステップＳ１５）。本処理例では、下部ノズル４１からの酸化液の吐出と、上部ノズル３１からのエッチング液の吐出とがほぼ同時に開始される。 Subsequently, the oxidizing solution supply source 42 supplies the oxidizing solution to the lower nozzle 41, whereby the oxidizing solution is continuously discharged from the lower nozzle 41 toward the center of the lower surface 92 (step S14). In addition, the etching solution supply source 32 supplies the etching solution to the upper nozzle 31 so that the etching solution is continuously discharged from the upper nozzle 31 toward the center of the upper surface 91 (step S15). In the present processing example, the discharge of the oxidizing solution from the lower nozzle 41 and the discharge of the etching solution from the upper nozzle 31 are started almost simultaneously.
　このとき、下面９２では、基板９の回転により酸化液が基板９の外周縁に向かって広がり、下面９２の全体に酸化液が供給される。基板本体９０は非酸化物（例えばシリコン）により形成されており、酸化液による酸化反応により、下面９２の全体に均一な酸化膜が形成される。外周縁では、酸化液の一部が飛散する。酸化液の他の一部は、表面張力により外周端面９４に付着し、上面９１の周縁部９３に到達する。換言すると、下部ノズル４１から下面９２に向けて吐出された酸化液は、外周端面９４を経由して上面９１の周縁部９３に供給される。 At this time, on the lower surface 92, the oxidizing solution spreads toward the outer peripheral edge of the substrate 9 by the rotation of the substrate 9, and the oxidizing solution is supplied to the entire lower surface 92. The substrate main body 90 is formed of a non-oxide (for example, silicon), and a uniform oxide film is formed on the entire lower surface 92 by an oxidation reaction with an oxidizing solution. A part of the oxidizing solution is scattered at the outer peripheral edge. Another part of the oxidizing solution adheres to the outer peripheral end surface 94 due to surface tension and reaches the peripheral edge portion 93 of the upper surface 91. In other words, the oxidizing solution discharged from the lower nozzle 41 toward the lower surface 92 is supplied to the peripheral portion 93 of the upper surface 91 via the outer peripheral end surface 94.
　上面９１では、基板９の回転によりエッチング液が基板９の外周縁に向かって広がる。既述のように、上面９１の周縁部９３には、酸化液が存在する。したがって、図４に示すように、上面９１の周縁部９３においてエッチング液８１および酸化液８２が混合される。図４では、周縁部９３近傍におけるエッチング液８１および酸化液８２を模式的に示しており、エッチング液８１と酸化液８２とが混合した部分に符号８３を付している。上面９１の周縁部９３では、エッチング液８１に酸化液８２が混合されることにより、基板９のエッチング（ここでは、薄膜９１１のエッチング）が抑制される。エッチング液８１と酸化液８２との混合により、基板９のエッチングが抑制される理由は明確ではないが、上面９１が、酸化液８２により微視的に酸化され（微視的に酸化膜が形成され）、エッチング液８１から保護されるためであると考えられる。酸化液８２として過酸化水素水を用いる場合に、周縁部９３におけるエッチングをより確実に抑制するには、酸化液８２における過酸化水素の濃度は、例えば８重量％以上であり、好ましくは１５重量％以上である。 On the upper surface 91, the etching solution spreads toward the outer peripheral edge of the substrate 9 by the rotation of the substrate 9. As described above, the oxidizing solution is present at the peripheral edge portion 93 of the upper surface 91. Therefore, as shown in FIG. 4, the etching solution 81 and the oxidizing solution 82 are mixed at the peripheral edge portion 93 of the upper surface 91. In FIG. 4, the etching solution 81 and the oxidizing solution 82 in the vicinity of the peripheral portion 93 are schematically shown, and a portion where the etching solution 81 and the oxidizing solution 82 are mixed is denoted by reference numeral 83. In the peripheral portion 93 of the upper surface 91, the etching solution 81 is mixed with the oxidizing solution 82, thereby suppressing the etching of the substrate 9 (here, the etching of the thin film 911). Although the reason why the etching of the substrate 9 is suppressed by mixing the etching solution 81 and the oxidizing solution 82 is not clear, the upper surface 91 is microscopically oxidized by the oxidizing solution 82 (microscopically forming an oxide film). This is considered to be because it is protected from the etching solution 81. In the case where hydrogen peroxide water is used as the oxidizing solution 82, the concentration of hydrogen peroxide in the oxidizing solution 82 is, for example, 8% by weight or more, preferably 15% in order to more reliably suppress the etching at the peripheral portion 93. % Or more.
　一方、上面９１において周縁部９３よりも内側の領域９５（以下、「処理領域９５」という。）では、エッチング液８１により薄膜９１１がエッチングされる。図５では、処理領域９５において薄膜９１１がエッチングされた基板９を示しており、エッチング液８１および酸化液８２の図示を省略している。基板処理装置１では、上部ノズル３１から上面９１の処理領域９５に向けて吐出されるエッチング液により処理領域９５を適切にエッチングしつつ、下部ノズル４１から下面９２に向けて吐出される酸化液８２により上面９１の周縁部９３を保護する（エッチングレートを十分に低くする、または、エッチングを防止する）ことが可能となる。実際には、基板９の外周端面９４（ベベル面）も酸化液８２により保護される。 On the other hand, the thin film 911 is etched by the etching solution 81 in a region 95 (hereinafter referred to as “processing region 95”) inside the peripheral portion 93 on the upper surface 91. FIG. 5 shows the substrate 9 in which the thin film 911 is etched in the processing region 95, and illustration of the etching solution 81 and the oxidizing solution 82 is omitted. In the substrate processing apparatus 1, an oxidizing solution 82 discharged from the lower nozzle 41 toward the lower surface 92 while appropriately etching the processing region 95 with an etching solution discharged from the upper nozzle 31 toward the processing region 95 on the upper surface 91. As a result, the peripheral edge portion 93 of the upper surface 91 can be protected (the etching rate can be made sufficiently low or etching can be prevented). Actually, the outer peripheral end surface 94 (bevel surface) of the substrate 9 is also protected by the oxidizing solution 82.
　好ましい基板処理装置１では、エッチング液供給源３２がヒータを有し、所定の温度（例えば８５℃）に加熱されたエッチング液８１が上面９１に吐出される。これにより、処理領域９５では、比較的高いエッチングレートで薄膜９１１がエッチングされる。より好ましくは、酸化液供給源４２がヒータを有し、所定の温度（例えば７０℃）に加熱された酸化液８２が下面９２に吐出される。これにより、エッチング液８１の高温状態が維持されやすくなり、処理領域９５のエッチングレートをより高くすることが可能となる。高温の酸化液８２は、例えば、高温の純水と常温の過酸化水素とを混合することにより生成される。高温のエッチング液８１が、同様に、高温の純水と常温のＴＭＹ等とを混合することにより生成されてもよい。 In the preferred substrate processing apparatus 1, the etching solution supply source 32 has a heater, and the etching solution 81 heated to a predetermined temperature (for example, 85 ° C.) is discharged onto the upper surface 91. Thereby, in the processing region 95, the thin film 911 is etched at a relatively high etching rate. More preferably, the oxidizing solution supply source 42 includes a heater, and the oxidizing solution 82 heated to a predetermined temperature (for example, 70 ° C.) is discharged to the lower surface 92. As a result, the high temperature state of the etching solution 81 is easily maintained, and the etching rate of the processing region 95 can be further increased. The high temperature oxidizing solution 82 is generated, for example, by mixing high temperature pure water and normal temperature hydrogen peroxide. Similarly, the high temperature etching solution 81 may be generated by mixing high temperature pure water with room temperature TMY or the like.
　下部ノズル４１から下面９２に向けて吐出された酸化液８２を、上面９１の周縁部９３に到達させる条件は、基板９の半径、および、酸化液８２の種類等に応じて適宜決定される。一例では、基板９の半径が１５０ｍｍであり、かつ、下部ノズル４１から酸化液８２が毎分１～２Ｌの流量で吐出される場合に、基板９の回転数が、例えば５０～３００ｒｐｍに設定される。これにより、酸化液８２を上面９１の周縁部９３に適切に到達させることが可能となる。基板処理装置１では、基板９の回転数が低いほど、酸化液８２が外周端面９４から到達する上面９１の領域の幅（外周端面９４から内側に向かう径方向の幅であり、以下、「混合領域における幅」という。）の平均値が大きくなり、周方向における当該幅のばらつきも大きくなる。したがって、混合領域におけるある程度の幅（例えば、１～３ｍｍ）を確保しつつ、当該幅のばらつきを低減するという観点では、基板９の回転数は、１００～２００ｒｐｍに設定されることが好ましい。より好ましくは、基板９の回転数は、１５０～２００ｒｐｍである。 The conditions for causing the oxidizing solution 82 discharged from the lower nozzle 41 toward the lower surface 92 to reach the peripheral edge 93 of the upper surface 91 are appropriately determined according to the radius of the substrate 9 and the type of the oxidizing solution 82. In one example, when the radius of the substrate 9 is 150 mm and the oxidizing solution 82 is discharged from the lower nozzle 41 at a flow rate of 1 to 2 L / min, the rotation speed of the substrate 9 is set to 50 to 300 rpm, for example. The As a result, the oxidizing solution 82 can appropriately reach the peripheral edge 93 of the upper surface 91. In the substrate processing apparatus 1, the lower the rotation speed of the substrate 9, the width of the region of the upper surface 91 where the oxidizing solution 82 reaches from the outer peripheral end surface 94 (the width in the radial direction from the outer peripheral end surface 94 to the inner side. The average value of “width in the region”) increases, and the variation in the width in the circumferential direction also increases. Therefore, from the viewpoint of reducing a variation in the width while securing a certain width (for example, 1 to 3 mm) in the mixed region, the rotation speed of the substrate 9 is preferably set to 100 to 200 rpm. More preferably, the rotation speed of the substrate 9 is 150 to 200 rpm.
　酸化液８２およびエッチング液８１の吐出が所定時間継続されると、両者の吐出が停止される。続いて、上面リンス液供給部により上部ノズル３１を介して上面９１の中央部にリンス液が供給されるとともに、下面リンス液供給部により下部ノズル４１を介して下面９２の中央部にリンス液が供給される（ステップＳ１６）。上面９１および下面９２では、基板９の回転によりリンス液が基板９の外周縁に向かって広がり、上面９１および下面９２の全体にリンス液が供給される。リンス液の供給により、上面９１に付着するエッチング液８１、および、下面９２に付着する酸化液８２が除去される。リンス液の吐出は所定時間継続され、その後、停止される。 When the discharge of the oxidizing solution 82 and the etching solution 81 is continued for a predetermined time, the discharge of both is stopped. Subsequently, the rinsing liquid is supplied to the central portion of the upper surface 91 by the upper surface rinsing liquid supply unit via the upper nozzle 31, and the rinsing liquid is supplied to the central portion of the lower surface 92 by the lower surface rinsing liquid supply unit via the lower nozzle 41. Is supplied (step S16). On the upper surface 91 and the lower surface 92, the rinse liquid spreads toward the outer peripheral edge of the substrate 9 by the rotation of the substrate 9, and the rinse liquid is supplied to the entire upper surface 91 and the lower surface 92. By supplying the rinse liquid, the etching liquid 81 adhering to the upper surface 91 and the oxidizing liquid 82 adhering to the lower surface 92 are removed. The discharge of the rinse liquid is continued for a predetermined time and then stopped.
　続いて、対向位置に配置された補助ノズル５１を介して、有機溶剤供給部５により上面９１の中央部に有機溶剤が供給される（ステップＳ１７）。上面９１では、基板９の回転により有機溶剤が基板９の外周縁に向かって広がり、上面９１の全体に有機溶剤が供給される。有機溶剤は、例えばＩＰＡ（イソプロピルアルコール）であり、上面９１上のリンス液が有機溶剤に置換される。基板処理装置１では、ＩＰＡ以外の有機溶剤が用いられてもよい。有機溶剤の吐出は所定時間継続され、その後、停止される。 Subsequently, the organic solvent is supplied to the central portion of the upper surface 91 by the organic solvent supply unit 5 through the auxiliary nozzle 51 arranged at the facing position (step S17). On the upper surface 91, the organic solvent spreads toward the outer peripheral edge of the substrate 9 by the rotation of the substrate 9, and the organic solvent is supplied to the entire upper surface 91. The organic solvent is, for example, IPA (isopropyl alcohol), and the rinse liquid on the upper surface 91 is replaced with the organic solvent. In the substrate processing apparatus 1, an organic solvent other than IPA may be used. The discharge of the organic solvent is continued for a predetermined time and then stopped.
　有機溶剤の供給が完了すると、基板回転機構２２が基板９の回転速度を上記処理液（すなわち、薬液、リンス液、酸化液、エッチング液および有機溶剤）の供給時よりも高くすることにより、基板９の乾燥処理（スピンドライ）が開始される（ステップＳ１８）。乾燥処理が完了すると、基板９の回転が停止される（ステップＳ１９）。基板９は、外部の搬送機構により基板処理装置１から搬出される。以上により、基板処理装置１における基板９の処理が完了する。 When the supply of the organic solvent is completed, the substrate rotation mechanism 22 makes the rotation speed of the substrate 9 higher than that at the time of supplying the processing liquid (that is, the chemical liquid, the rinsing liquid, the oxidizing liquid, the etching liquid, and the organic solvent). 9 is started (spin dry) (step S18). When the drying process is completed, the rotation of the substrate 9 is stopped (step S19). The substrate 9 is unloaded from the substrate processing apparatus 1 by an external transport mechanism. Thus, the processing of the substrate 9 in the substrate processing apparatus 1 is completed.
　上記処理例では、説明を簡単にするため、基板９の上面９１における処理領域９５において薄膜９１１を除去し、周縁部９３において薄膜９１１を残す場合について説明したが、基板処理装置１は、基板９に対する様々な処理において用いられてもよい。 In the above processing example, the case where the thin film 911 is removed in the processing region 95 on the upper surface 91 of the substrate 9 and the thin film 911 is left in the peripheral portion 93 is described for the sake of simplicity. May be used in various processes.
　図６は、基板の他の例を示す図である。図６の基板９ａでは、基板本体９０の上面において周縁部９３の内側に積層膜９１２が形成される。すなわち、上面９１の処理領域９５に、積層膜９１２が設けられる。積層膜９１２は、第１材料により形成された複数の第１材料膜９１３と、第１材料とは異なる第２材料により形成された複数の第２材料膜９１４とを含む。第１材料膜９１３と第２材料膜９１４とは、厚さ方向（積層方向）に交互に設けられる。例えば、第１材料膜９１３は、シリコン酸化膜等の絶縁膜である。第１材料膜９１３は、エッチング液によるエッチングレートが十分に低い材料（ほとんどエッチングされない材料）の膜であればよく、シリコン窒化膜や、ＴＥＯＳ（テトラエトキシシラン）等であってもよい。第２材料膜９１４はポリシリコン膜である。第２材料膜９１４は、エッチング液によるエッチングレートが比較的高い他の材料の膜であってもよい。 FIG. 6 shows another example of the substrate. In the substrate 9 a of FIG. 6, a laminated film 912 is formed inside the peripheral edge 93 on the upper surface of the substrate body 90. That is, the stacked film 912 is provided in the processing region 95 on the upper surface 91. The stacked film 912 includes a plurality of first material films 913 formed of a first material and a plurality of second material films 914 formed of a second material different from the first material. The first material film 913 and the second material film 914 are alternately provided in the thickness direction (stacking direction). For example, the first material film 913 is an insulating film such as a silicon oxide film. The first material film 913 may be a film made of a material having a sufficiently low etching rate with an etchant (a material that is hardly etched), and may be a silicon nitride film, TEOS (tetraethoxysilane), or the like. The second material film 914 is a polysilicon film. The second material film 914 may be a film of another material having a relatively high etching rate with the etching solution.
　一方、基板本体９０の上面における周縁部９３の表面には、積層膜９１２は形成されない。基板９ａの上面９１の周縁部９３の表面とは、基板本体９０の表面である。基板本体９０は、非酸化物（例えばシリコン）により形成されており、基板本体９０に対するエッチング液によるエッチングレートは比較的高い。また、基板本体９０の表面は、酸化液により酸化し得る。上面９１の周縁部９３が、第２材料膜９１４等、エッチング液によりエッチングされ、かつ、酸化液により酸化し得る材料の膜表面であってもよい。基板９ａの下面９２は、基板本体９０の下面である。基板９ａの下面９２が、基板本体９０の下面に形成された薄膜の表面であってもよい。 On the other hand, the laminated film 912 is not formed on the surface of the peripheral edge portion 93 on the upper surface of the substrate body 90. The surface of the peripheral edge portion 93 of the upper surface 91 of the substrate 9a is the surface of the substrate body 90. The substrate body 90 is made of a non-oxide (for example, silicon), and the etching rate of the substrate body 90 with the etching solution is relatively high. Further, the surface of the substrate body 90 can be oxidized by an oxidizing solution. The peripheral edge portion 93 of the upper surface 91 may be a film surface of a material that can be etched with an etching solution and oxidized with an oxidizing solution, such as the second material film 914. The lower surface 92 of the substrate 9 a is the lower surface of the substrate body 90. The lower surface 92 of the substrate 9a may be the surface of a thin film formed on the lower surface of the substrate body 90.
　基板処理装置１が基板９ａを処理する際には、図７に示すように、積層膜９１２に対して厚さ方向に延びる複数の孔部９１５が、外部の装置により予め形成されている。各孔部９１５は、複数の第１材料膜９１３および複数の第２材料膜９１４を貫通する。孔部９１５の形成は、例えば、反応性イオンエッチングによって行われる。 When the substrate processing apparatus 1 processes the substrate 9a, as shown in FIG. 7, a plurality of holes 915 extending in the thickness direction with respect to the stacked film 912 are formed in advance by an external apparatus. Each hole 915 penetrates the plurality of first material films 913 and the plurality of second material films 914. Formation of the hole 915 is performed by reactive ion etching, for example.
　基板処理装置１における基板９ａの処理では、上記と同様に、基板９ａを回転しつつ、上面９１および下面９２への薬液の供給、および、上面９１および下面９２へのリンス液の供給が順に行われる（図３：ステップＳ１１～Ｓ１３）。続いて、下部ノズル４１から下面９２の中央部への酸化液の吐出と、上部ノズル３１から上面９１の中央部へのエッチング液の吐出とが、ほぼ同時に開始される（ステップＳ１４，Ｓ１５）。 In the processing of the substrate 9a in the substrate processing apparatus 1, the supply of the chemical liquid to the upper surface 91 and the lower surface 92 and the supply of the rinse liquid to the upper surface 91 and the lower surface 92 are sequentially performed while rotating the substrate 9a in the same manner as described above. (FIG. 3: steps S11 to S13). Subsequently, the discharge of the oxidizing solution from the lower nozzle 41 to the central portion of the lower surface 92 and the discharge of the etching solution from the upper nozzle 31 to the central portion of the upper surface 91 are started almost simultaneously (steps S14 and S15).
　下面９２では、基板９ａの回転により酸化液が基板９ａの外周縁に向かって広がり、酸化膜が形成される。また、酸化液の一部が、外周端面９４を経由して上面９１の周縁部９３に供給される（図４参照）。上面９１では、基板９ａの回転によりエッチング液が基板９ａの外周縁に向かって広がる。上面９１の周縁部９３では、エッチング液および酸化液が混合されることにより、エッチングが抑制される。 On the lower surface 92, the oxidizing solution spreads toward the outer peripheral edge of the substrate 9a by the rotation of the substrate 9a, and an oxide film is formed. A part of the oxidizing solution is supplied to the peripheral edge portion 93 of the upper surface 91 via the outer peripheral end surface 94 (see FIG. 4). On the upper surface 91, the etching solution spreads toward the outer peripheral edge of the substrate 9a by the rotation of the substrate 9a. In the peripheral portion 93 of the upper surface 91, the etching is suppressed by mixing the etching solution and the oxidizing solution.
　上面９１の処理領域９５では、孔部９１５に入り込んだエッチング液により、第２材料膜９１４が選択的にエッチングされる。第１材料膜９１３は、エッチング液により、ほとんどエッチングされない。その結果、図８に示すように、第２材料膜９１４が孔部９１５の内周面から後退する。換言すると、広がった孔部９１５の内周面から、第１材料膜９１３が内側に突出した構造が得られる。なお、仮に、孔部９１５における第２材料膜９１４の表面に酸化液が付着した場合、第２材料膜９１４の当該表面は酸化するため、酸化液は、上面９１の周縁部９３のみならず、処理領域９５も酸化させることが可能な処理液であるといえる。 In the processing region 95 on the upper surface 91, the second material film 914 is selectively etched by the etchant that has entered the hole 915. The first material film 913 is hardly etched by the etchant. As a result, as shown in FIG. 8, the second material film 914 recedes from the inner peripheral surface of the hole 915. In other words, a structure in which the first material film 913 protrudes inward from the inner peripheral surface of the expanded hole 915 is obtained. Note that, if an oxidizing solution adheres to the surface of the second material film 914 in the hole 915, the surface of the second material film 914 is oxidized, so that the oxidizing solution is not only the peripheral portion 93 of the upper surface 91, It can be said that the treatment region 95 is also a treatment liquid that can be oxidized.
　酸化液およびエッチング液の吐出は所定時間継続され、その後、停止される。続いて、上面９１および下面９２へのリンス液の供給、および、上面９１への有機溶剤の供給が順に行われる（ステップＳ１６，Ｓ１７）。高速回転での基板９ａの乾燥後、基板９ａの回転が停止され（ステップＳ１８，Ｓ１９）、基板処理装置１における基板９ａの処理が完了する。 The discharge of the oxidizing solution and the etching solution is continued for a predetermined time and then stopped. Subsequently, the supply of the rinse liquid to the upper surface 91 and the lower surface 92 and the supply of the organic solvent to the upper surface 91 are sequentially performed (steps S16 and S17). After the substrate 9a is dried at high speed, the rotation of the substrate 9a is stopped (steps S18 and S19), and the processing of the substrate 9a in the substrate processing apparatus 1 is completed.
　積層膜９１２が設けられる基板９ａの処理では、孔部９１５を介した第２材料膜９１４の選択的エッチングに長時間を要する。したがって、仮に、酸化液を供給することなく処理を行うと、上面９１の周縁部９３におけるエッチング量が大きくなり（例えば、元の厚さ７７５μｍに対して、エッチング量が数十μｍとなる。）、後続の工程における基板９ａの搬送等において不具合が生じてしまう。 In the processing of the substrate 9a provided with the laminated film 912, it takes a long time to selectively etch the second material film 914 through the hole 915. Therefore, if the treatment is performed without supplying the oxidizing solution, the etching amount at the peripheral edge portion 93 of the upper surface 91 is increased (for example, the etching amount is several tens of μm with respect to the original thickness of 775 μm). In this case, a problem occurs in the transfer of the substrate 9a in the subsequent process.
　これに対し、基板処理装置１では、上面９１の周縁部９３を酸化液により保護することにより、長時間を要する第２材料膜９１４の選択的エッチングにおいて、周縁部９３がエッチングされることを抑制することができる。その結果、上記不具合の発生を防止することができる。なお、基板９ａの下面９２、および、上面９１の周縁部９３に形成される酸化膜の厚さは、数ｎｍであるため、基板９ａの搬送等において問題となることはなく、除去する必要もない。上記処理では、基板９ａの外周端面９４（ベベル面）も酸化液により保護されるため、基板９ａの直径が小さくなることも防止される。 On the other hand, in the substrate processing apparatus 1, the peripheral portion 93 of the upper surface 91 is protected by the oxidizing solution, thereby suppressing the peripheral portion 93 from being etched in the selective etching of the second material film 914 that requires a long time. can do. As a result, it is possible to prevent the occurrence of the above problems. Since the thickness of the oxide film formed on the lower surface 92 of the substrate 9a and the peripheral portion 93 of the upper surface 91 is several nanometers, there is no problem in transporting the substrate 9a and it is necessary to remove it. Absent. In the above process, since the outer peripheral end surface 94 (bevel surface) of the substrate 9a is also protected by the oxidizing solution, it is possible to prevent the diameter of the substrate 9a from being reduced.
　図９は、基板処理装置の他の例を示す図である。図９の基板処理装置１ａでは、酸化液供給部４ａの構成が、図１の基板処理装置１と相違する。他の構成は、図１の基板処理装置１と同様であり、同じ構成に同じ符号を付す。 FIG. 9 is a diagram showing another example of the substrate processing apparatus. In the substrate processing apparatus 1a of FIG. 9, the structure of the oxidizing solution supply part 4a is different from the substrate processing apparatus 1 of FIG. Other configurations are the same as those of the substrate processing apparatus 1 of FIG. 1, and the same components are denoted by the same reference numerals.
　酸化液供給部４ａは、基板９の上面９１側に位置する酸化液ノズル４１ａを備える。酸化液ノズル４１ａは、上下方向に沿って延びており、吐出口が形成された下端面が、上端面よりも径方向の外側に位置するように、上下方向に対して傾斜して支持される。また、酸化液ノズル４１ａの吐出口は、上面９１の周縁部９３の近傍に対向する。酸化液は、酸化液ノズル４１ａから上面９１の周縁部９３に向かって吐出される。酸化液ノズル４１ａにおける酸化液の吐出方向は、下方かつ径方向外側を向く。 The oxidizing solution supply unit 4 a includes an oxidizing solution nozzle 41 a located on the upper surface 91 side of the substrate 9. The oxidizing solution nozzle 41a extends in the vertical direction, and is supported by being inclined with respect to the vertical direction so that the lower end surface on which the discharge port is formed is located on the outer side in the radial direction with respect to the upper end surface. . Further, the discharge port of the oxidizing solution nozzle 41 a faces the vicinity of the peripheral edge portion 93 of the upper surface 91. The oxidizing solution is discharged from the oxidizing solution nozzle 41a toward the peripheral portion 93 of the upper surface 91. The discharge direction of the oxidizing solution in the oxidizing solution nozzle 41a is directed downward and radially outward.
　基板処理装置１ａでは、酸化液ノズル４１ａから上面９１の周縁部９３への酸化液の吐出と、上部ノズル３１から上面９１の中央部へのエッチング液の吐出とが、ほぼ同時に開始される。上面９１の処理領域９５では、エッチング液により薄膜９１１（図２参照）がエッチングされる。上面９１の周縁部９３では、エッチング液および酸化液が混合されることにより、エッチングが抑制される。このように、基板処理装置１ａにおいても、酸化液により上面９１の周縁部９３を保護しつつ、処理領域９５を適切にエッチングすることが可能となる。もちろん、図９の基板処理装置１ａにおいて、図６の基板９ａが処理されてもよい。 In the substrate processing apparatus 1a, the discharge of the oxidizing solution from the oxidizing solution nozzle 41a to the peripheral portion 93 of the upper surface 91 and the discharge of the etching solution from the upper nozzle 31 to the central portion of the upper surface 91 are started almost simultaneously. In the processing region 95 on the upper surface 91, the thin film 911 (see FIG. 2) is etched by the etchant. In the peripheral portion 93 of the upper surface 91, the etching is suppressed by mixing the etching solution and the oxidizing solution. Thus, also in the substrate processing apparatus 1a, it is possible to appropriately etch the processing region 95 while protecting the peripheral edge portion 93 of the upper surface 91 with the oxidizing solution. Of course, the substrate 9a of FIG. 6 may be processed in the substrate processing apparatus 1a of FIG.
　以上に説明したように、基板処理装置１，１ａにおける基板９，９ａの処理では、上面９１の周縁部９３に酸化液を供給する工程と、周縁部９３の内側に位置する処理領域９５にエッチング液を供給する工程とが行われる。これにより、基板９，９ａの上面９１において、酸化液により周縁部９３を保護しつつ、処理領域９５を適切にエッチングすることが実現される。 As described above, in the processing of the substrates 9 and 9a in the substrate processing apparatuses 1 and 1a, the step of supplying the oxidizing solution to the peripheral portion 93 of the upper surface 91 and the etching into the processing region 95 located inside the peripheral portion 93 are performed. And a step of supplying a liquid. Thereby, on the upper surface 91 of the substrates 9 and 9a, it is possible to appropriately etch the processing region 95 while protecting the peripheral portion 93 with the oxidizing solution.
　ところで、図９の基板処理装置１ａでは、基板９，９ａの処理において、酸化液ノズル４１ａから上面９１の周縁部９３に向けて吐出された酸化液の液跳ね等により、上面９１の処理領域９５に酸化液が付着する可能性がある。この場合に、薄膜９１１または第２材料膜９１４の一部の表面が酸化すると、当該表面（酸化膜表面）がエッチング液によりほとんどエッチングされなくなる。これに対し、図１の基板処理装置１では、基板９，９ａの下面９２側に位置する下部ノズル４１から下面９２に向けて酸化液が吐出されるため、基板９，９ａに向けて吐出された酸化液の液跳ね等により、上面９１の処理領域９５に酸化液が付着することを防止することができる。 By the way, in the substrate processing apparatus 1a of FIG. 9, in the processing of the substrates 9 and 9a, the processing region 95 of the upper surface 91 is caused by the splashing of the oxidizing solution discharged from the oxidizing solution nozzle 41a toward the peripheral portion 93 of the upper surface 91. There is a possibility that the oxidizing solution adheres to the surface. In this case, when the surface of a part of the thin film 911 or the second material film 914 is oxidized, the surface (oxide film surface) is hardly etched by the etchant. On the other hand, in the substrate processing apparatus 1 of FIG. 1, since the oxidizing solution is discharged toward the lower surface 92 from the lower nozzle 41 located on the lower surface 92 side of the substrates 9, 9a, it is discharged toward the substrates 9, 9a. It is possible to prevent the oxidizing solution from adhering to the processing region 95 on the upper surface 91 due to the splashing of the oxidizing solution.
　基板処理装置１，１ａでは、上面９１の周縁部９３に酸化液を供給する工程と、周縁部９３の内側に位置する処理領域９５にエッチング液を供給する工程とを個別に行うことも可能である。例えば、図１の基板処理装置１において、基板９，９ａを回転しつつ、下部ノズル４１から下面９２に向けて酸化液が吐出される。また、酸化液の吐出に並行して、上部ノズル３１から上面９１の中央部に向けて純水が吐出される。これにより、外周端面９４を介して到達した酸化液により上面９１の周縁部９３に酸化膜が形成されるとともに、純水により処理領域９５への酸化液の浸入が抑制される。その後、上部ノズル３１から上面９１の中央部に向けてエッチング液が吐出される。これにより、基板９，９ａの上面９１において、酸化液により形成される酸化膜を用いて周縁部９３を保護しつつ、処理領域９５を適切にエッチングすることが可能となる。図９の基板処理装置１ａにおいても同様である。なお、エッチング液を処理領域９５に供給する前に、上面９１の周縁部９３に酸化膜を形成する場合も、実質的には、周縁部９３が酸化液により保護されていると捉えることができる。 In the substrate processing apparatuses 1 and 1a, the step of supplying the oxidizing solution to the peripheral portion 93 of the upper surface 91 and the step of supplying the etching solution to the processing region 95 located inside the peripheral portion 93 can be performed separately. is there. For example, in the substrate processing apparatus 1 of FIG. 1, the oxidizing solution is discharged from the lower nozzle 41 toward the lower surface 92 while rotating the substrates 9 and 9 a. In parallel with the discharge of the oxidizing solution, pure water is discharged from the upper nozzle 31 toward the center of the upper surface 91. As a result, an oxide film is formed on the peripheral edge portion 93 of the upper surface 91 by the oxidizing solution that has reached through the outer peripheral end surface 94, and the penetration of the oxidizing solution into the processing region 95 is suppressed by pure water. Thereafter, an etching solution is discharged from the upper nozzle 31 toward the center of the upper surface 91. As a result, the processing region 95 can be appropriately etched on the upper surface 91 of the substrates 9 and 9a while protecting the peripheral portion 93 using the oxide film formed by the oxidizing solution. The same applies to the substrate processing apparatus 1a of FIG. Note that even when an oxide film is formed on the peripheral edge portion 93 of the upper surface 91 before supplying the etching solution to the processing region 95, it can be considered that the peripheral edge portion 93 is substantially protected by the oxidizing solution. .
　一方、上面９１の周縁部９３に酸化液を供給する工程と、周縁部９３の内側に位置する処理領域９５にエッチング液を供給する工程とを同時に行う場合には、基板９，９ａの処理を効率よく行う（すなわち、処理に要する時間を短くする）ことが可能となる。また、この場合も、処理領域９５への酸化液の浸入をエッチング液により抑制することができ、処理領域９５を適切にエッチングすることができる。 On the other hand, when the step of supplying the oxidizing solution to the peripheral portion 93 of the upper surface 91 and the step of supplying the etching solution to the processing region 95 located inside the peripheral portion 93 are performed simultaneously, the processing of the substrates 9 and 9a is performed. It is possible to efficiently perform (that is, shorten the time required for processing). Also in this case, the entry of the oxidizing solution into the processing region 95 can be suppressed by the etching solution, and the processing region 95 can be appropriately etched.
　上記基板処理および基板処理装置１，１ａでは様々な変形が可能である。 The substrate processing and the substrate processing apparatus 1, 1a can be variously modified.
　図１の基板処理装置１では、上部ノズル３１から酸化液を吐出し、下部ノズル４１からエッチング液を吐出することにより、上面９１から下面９２に回り込む酸化液により下面９２の周縁部９３を保護しつつ、周縁部９３の内側に位置する処理領域（下面９２の処理領域）がエッチングされてもよい。図９の基板処理装置１ａにおいても同様に、下面９２の周縁部９３に対向する酸化液ノズルから酸化液を吐出しつつ、下部ノズル４１からエッチング液が吐出されてもよい。 In the substrate processing apparatus 1 of FIG. 1, the peripheral portion 93 of the lower surface 92 is protected by the oxidizing solution that flows from the upper surface 91 to the lower surface 92 by discharging the oxidizing solution from the upper nozzle 31 and discharging the etching solution from the lower nozzle 41. However, the processing region (the processing region of the lower surface 92) located inside the peripheral edge portion 93 may be etched. Similarly, in the substrate processing apparatus 1 a of FIG. 9, the etching solution may be discharged from the lower nozzle 41 while discharging the oxidizing solution from the oxidizing solution nozzle facing the peripheral edge portion 93 of the lower surface 92.
　以上のように、基板処理装置１，１ａでは、基板９，９ａの一の主面を酸化させる酸化液を、基板９，９ａに向けてノズルから吐出することにより、当該一の主面の周縁部９３に酸化液を供給する工程と、当該一の主面をエッチングするエッチング液を、基板９，９ａに向けてノズルから吐出することにより、当該一の主面において周縁部９３の内側に位置する処理領域にエッチング液を供給する工程とが行われる。これにより、基板９，９ａの当該一の主面において、酸化液により周縁部９３を保護しつつ、処理領域を適切にエッチングすることができる。 As described above, in the substrate processing apparatuses 1 and 1a, the oxidizing liquid that oxidizes one main surface of the substrates 9 and 9a is discharged from the nozzle toward the substrates 9 and 9a, whereby the peripheral edge of the one main surface is obtained. The step of supplying the oxidizing solution to the portion 93 and the etching solution for etching the one main surface are ejected from the nozzle toward the substrates 9 and 9a, so that the one main surface is positioned inside the peripheral portion 93. And a step of supplying an etching solution to the processing region to be performed. Thereby, in the said one main surface of the board | substrates 9 and 9a, a process area | region can be etched appropriately, protecting the peripheral part 93 with an oxidizing solution.
　図１の基板処理装置１において、基板９，９ａの下面９２の周縁部９３に対向する位置に、下部ノズル４１が配置されてもよい。この場合も、回転する基板９，９ａの外周端面９４を経由して、酸化液を上面９１の周縁部９３に供給することが可能である。酸化液により基板９，９ａの下面９２が酸化する場合に、下面９２の全体を均一な状態とする（均一な酸化膜を形成する）という観点では、下部ノズル４１から下面９２の中央部に向けて酸化液が吐出されることが好ましい。下面９２の全体に酸化膜を形成する場合、後続の工程において、当該酸化膜により、下面９２を保護することが可能となる。 In the substrate processing apparatus 1 of FIG. 1, the lower nozzle 41 may be disposed at a position facing the peripheral edge portion 93 of the lower surface 92 of the substrates 9 and 9a. Also in this case, the oxidizing solution can be supplied to the peripheral edge portion 93 of the upper surface 91 via the outer peripheral end surface 94 of the rotating substrates 9 and 9a. When the lower surface 92 of the substrates 9 and 9a is oxidized by the oxidizing solution, from the viewpoint of making the entire lower surface 92 uniform (forming a uniform oxide film), the lower nozzle 41 is directed toward the center of the lower surface 92. It is preferable that the oxidizing solution is discharged. When an oxide film is formed on the entire lower surface 92, the lower surface 92 can be protected by the oxide film in subsequent steps.
　エッチング液は、必ずしも上面９１の中央部に向けて吐出される必要はなく、上面９１において、周縁部９３よりも内側、かつ、中央部よりも外側の位置に向けて、上部ノズル３１からエッチング液が吐出されてもよい。すなわち、エッチングが行われる処理領域は、必ずしも中央部を含む必要はない。 The etching solution does not necessarily have to be discharged toward the central portion of the upper surface 91, and the etching solution from the upper nozzle 31 toward the inner side of the peripheral portion 93 and the outer side of the central portion on the upper surface 91. May be discharged. In other words, the processing region where etching is performed does not necessarily include the central portion.
　基板９，９ａの下面９２の中央部に向けて、いずれの処理液も吐出しない場合には、下面９２の中央部を吸着保持する基板保持部が設けられてもよい。 When neither processing solution is discharged toward the central portion of the lower surface 92 of the substrates 9 and 9a, a substrate holding portion that holds the central portion of the lower surface 92 by suction may be provided.
　基板処理装置１，１ａにおいて処理が行われる基板は半導体基板には限定されず、他の基板であってもよい。 The substrate to be processed in the substrate processing apparatus 1 or 1a is not limited to a semiconductor substrate, and may be another substrate.
　上記実施の形態および各変形例における構成は、相互に矛盾しない限り適宜組み合わされてよい。 The configurations in the above embodiment and each modification may be combined as appropriate as long as they do not contradict each other.
　発明を詳細に描写して説明したが、既述の説明は例示的であって限定的なものではない。したがって、本発明の範囲を逸脱しない限り、多数の変形や態様が可能であるといえる。 Although the invention has been described in detail, the above description is illustrative and not restrictive. Therefore, it can be said that many modifications and embodiments are possible without departing from the scope of the present invention.
　１，１ａ　　基板処理装置
　３　　エッチング液供給部
　４，４ａ　　酸化液供給部
　９，９ａ　　基板
　２１　　基板保持部
　２２　　基板回転機構
　３１　　上部ノズル
　４１　　下部ノズル
　４１ａ　　酸化液ノズル
　８１　　エッチング液
　８２　　酸化液
　９１　　（基板の）上面
　９２　　（基板の）下面
　９３　　（基板の）周縁部
　９４　　（基板の）外周端面
　９５　　（基板上の）処理領域
　９１２　　積層膜
　９１３　　第１材料膜
　９１４　　第２材料膜
　９１５　　孔部
　Ｊ１　　中心軸
　Ｓ１１～Ｓ１９　　ステップ DESCRIPTION OF SYMBOLS 1,1a Substrate processing apparatus 3 Etching solution supply unit 4, 4a Oxidizing solution supply unit 9, 9a Substrate 21 Substrate holding unit 22 Substrate rotating mechanism 31 Upper nozzle 41 Lower nozzle 41a Oxidizing solution nozzle 81 Etching solution 82 Oxidizing solution 91 (Substrate of substrate ) Upper surface 92 (Substrate) lower surface 93 (Substrate) peripheral edge 94 (Substrate) outer peripheral end surface 95 (On substrate) processing region 912 Laminated film 913 First material film 914 Second material film 915 Hole J1 Central axis S11 ~ S19 Step

Claims (9)

  1. 　基板処理方法であって、
    　ａ）円板状の基板を水平状態で回転しつつ、前記基板の一の主面を酸化させる酸化液を、前記基板に向けてノズルから吐出することにより、前記一の主面の周縁部に前記酸化液を供給する工程と、
    　ｂ）前記基板を水平状態で回転しつつ、前記一の主面をエッチングするエッチング液を、前記基板に向けてノズルから吐出することにより、前記一の主面において前記周縁部の内側に位置する処理領域に前記エッチング液を供給する工程と、
    を備える。     A substrate processing method comprising:
    a) While rotating the disk-shaped substrate in a horizontal state, an oxidizing solution that oxidizes one main surface of the substrate is discharged from the nozzle toward the substrate, thereby forming a peripheral portion of the one main surface. Supplying the oxidizing solution;
    b) An etching solution for etching the one main surface is discharged from the nozzle toward the substrate while rotating the substrate in a horizontal state, so that the one main surface is positioned inside the peripheral portion. Supplying the etching solution to the processing region;
    Is provided.
  2. 　請求項１に記載の基板処理方法であって、
    　前記ａ）工程において、前記基板の他の主面側に位置する前記ノズルから前記他の主面に向けて前記酸化液が吐出され、回転する前記基板の外周端面を経由して、前記酸化液が前記一の主面の前記周縁部に供給される。     The substrate processing method according to claim 1,
    In the step a), the oxidizing solution is discharged from the nozzle located on the other main surface side of the substrate toward the other main surface, and passes through the outer peripheral end surface of the rotating substrate, thereby the oxidizing solution. Is supplied to the peripheral portion of the one main surface.
  3. 　請求項２に記載の基板処理方法であって、
    　前記ａ）工程において、前記他の主面側に位置する前記ノズルから前記他の主面の中央部に向けて前記酸化液が吐出される。     The substrate processing method according to claim 2,
    In the step a), the oxidizing solution is discharged from the nozzle located on the other main surface side toward the center of the other main surface.
  4. 　請求項２または３に記載の基板処理方法であって、
    　前記ａ）およびｂ）工程が同時に行われ、
    　前記ｂ）工程において、前記基板の前記一の主面側に位置する前記ノズルから、前記処理領域に向けて前記エッチング液が吐出される。     The substrate processing method according to claim 2 or 3,
    The steps a) and b) are performed simultaneously;
    In the step b), the etching solution is discharged from the nozzle located on the one main surface side of the substrate toward the processing region.
  5. 　請求項４に記載の基板処理方法であって、
    　前記一の主面に吐出される前記エッチング液、および、前記他の主面に吐出される前記酸化液の双方が加熱されている。     The substrate processing method according to claim 4,
    Both the etching solution discharged to the one main surface and the oxidizing solution discharged to the other main surface are heated.
  6. 　請求項４または５に記載の基板処理方法であって、
    　前記基板の半径が１５０ｍｍであり、
    　前記ａ）およびｂ）工程における前記基板の回転数が、５０～３００ｒｐｍである。     A substrate processing method according to claim 4 or 5, wherein
    The radius of the substrate is 150 mm;
    The number of rotations of the substrate in the steps a) and b) is 50 to 300 rpm.
  7. 　請求項１ないし６のいずれか１つに記載の基板処理方法であって、
    　第１材料により形成された複数の第１材料膜と、前記第１材料とは異なる第２材料により形成された複数の第２材料膜とを含む積層膜が、前記基板の前記一の主面において前記処理領域に設けられており、
    　前記ｂ）工程の前に、厚さ方向に延びる孔部が前記積層膜に形成されており、
    　前記ｂ）工程において、前記積層膜に含まれる前記複数の第２材料膜が、前記孔部を介して選択的にエッチングされる。     A substrate processing method according to any one of claims 1 to 6, comprising:
    A laminated film including a plurality of first material films formed of a first material and a plurality of second material films formed of a second material different from the first material is the one main surface of the substrate. In the processing area,
    Before the step b), a hole extending in the thickness direction is formed in the laminated film,
    In the step b), the plurality of second material films included in the stacked film are selectively etched through the holes.
  8. 　請求項１ないし７のいずれか１つに記載の基板処理方法であって、
    　前記エッチング液がアルカリ性を有する。     A substrate processing method according to any one of claims 1 to 7,
    The etching solution has alkalinity.
  9. 　基板処理装置であって、
    　円板状の基板を水平状態で保持する基板保持部と、
    　上下方向を向く中心軸を中心として前記基板保持部を回転する基板回転機構と、
    　前記基板の一の主面を酸化させる酸化液を、回転する前記基板に向けてノズルから吐出することにより、前記一の主面の周縁部に前記酸化液を供給する酸化液供給部と、
    　前記一の主面をエッチングするエッチング液を、回転する前記基板に向けてノズルから吐出することにより、前記一の主面において前記周縁部の内側に位置する処理領域に前記エッチング液を供給するエッチング液供給部と、
    を備える。     A substrate processing apparatus,
    A substrate holding unit for holding a disk-shaped substrate in a horizontal state;
    A substrate rotation mechanism that rotates the substrate holding portion about a central axis that faces the vertical direction;
    An oxidizing solution supply unit for supplying the oxidizing solution to the peripheral portion of the one main surface by discharging an oxidizing solution for oxidizing one main surface of the substrate from the nozzle toward the rotating substrate;
    Etching that etches the one main surface from the nozzle toward the rotating substrate, thereby supplying the etching solution to a processing region located inside the peripheral portion on the one main surface. A liquid supply unit;
    Is provided.
PCT/JP2019/017178 2018-06-15 2019-04-23 Substrate processing method and substrate processing device WO2019239727A1 (en)

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JP2009238860A (en) * 2008-03-26 2009-10-15 Dainippon Screen Mfg Co Ltd Substrate processing apparatus and substrate processing method
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JP2003124180A (en) * 2001-10-16 2003-04-25 Ebara Corp Substrate processor
JP2009238860A (en) * 2008-03-26 2009-10-15 Dainippon Screen Mfg Co Ltd Substrate processing apparatus and substrate processing method
JP2011211094A (en) * 2010-03-30 2011-10-20 Dainippon Screen Mfg Co Ltd Substrate treatment apparatus, and substrate treatment method
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