WO2016152371A1 - Procédé de traitement de substrat et dispositif de traitement de substrat - Google Patents

Procédé de traitement de substrat et dispositif de traitement de substrat Download PDF

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Publication number
WO2016152371A1
WO2016152371A1 PCT/JP2016/055646 JP2016055646W WO2016152371A1 WO 2016152371 A1 WO2016152371 A1 WO 2016152371A1 JP 2016055646 W JP2016055646 W JP 2016055646W WO 2016152371 A1 WO2016152371 A1 WO 2016152371A1
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WIPO (PCT)
Prior art keywords
substrate
spm
mixed
hydrogen peroxide
hydrofluoric acid
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PCT/JP2016/055646
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English (en)
Japanese (ja)
Inventor
佑介 秋月
Original Assignee
株式会社Ｓｃｒｅｅｎホールディングス
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
Priority claimed from JP2015246629A external-priority patent/JP6493839B2/ja
Application filed by 株式会社Ｓｃｒｅｅｎホールディングス filed Critical 株式会社Ｓｃｒｅｅｎホールディングス
Priority to CN201680017231.0A priority Critical patent/CN107430987B/zh
Priority to US15/559,076 priority patent/US10668497B2/en
Priority to KR1020177026290A priority patent/KR101988848B1/ko
Publication of WO2016152371A1 publication Critical patent/WO2016152371A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C11/00—Component parts, details or accessories not specifically provided for in groups B05C1/00 - B05C9/00
    • B05C11/10—Storage, supply or control of liquid or other fluent material; Recovery of excess liquid or other fluent material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • 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
    • H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05C11/00—Component parts, details or accessories not specifically provided for in groups B05C1/00 - B05C9/00
    • B05C11/02—Apparatus for spreading or distributing liquids or other fluent materials already applied to a surface ; Controlling means therefor; Control of the thickness of a coating by spreading or distributing liquids or other fluent materials already applied to the coated surface
    • B05C11/08—Spreading liquid or other fluent material by manipulating the work, e.g. tilting

Definitions

  • the present invention relates to a substrate processing apparatus and a substrate processing method for removing a resist from the surface of a substrate.
  • substrates to be processed include semiconductor wafers, liquid crystal display substrates, plasma display substrates, optical disk substrates, magnetic disk substrates, magneto-optical disk substrates, photomask substrates, ceramic substrates, and solar cells. For example.
  • the surface layer of the resist is hardened due to carbonization and alteration of the resist, so that a hardened layer may be formed on the surface of the resist.
  • Patent Document 1 proposes a method of removing a resist from the surface of a substrate without ashing even a resist having a hardened layer on the surface. This document discloses a method of supplying high-temperature SPM to a substrate in order to remove the resist whose surface layer is cured by ion implantation from the substrate.
  • an object of the present invention is to provide a substrate processing method and a substrate processing apparatus that can satisfactorily remove the resist from the surface of the substrate.
  • One embodiment of the present invention is a substrate processing method for removing a resist from a surface of a substrate, wherein a mixing step of mixing a hydrogen peroxide solution and hydrofluoric acid to generate a mixed solution of the hydrogen peroxide solution and hydrofluoric acid. And, after the mixing step, a mixture step of mixing the hydrogen peroxide solution and hydrofluoric acid with sulfuric acid to generate an HF mixed SPM that is a mixture solution of sulfuric acid, hydrogen peroxide solution, and hydrofluoric acid. And a supply step of supplying the HF mixed SPM to the surface of the substrate.
  • the hydrogen peroxide solution and hydrofluoric acid mixed in the mixing step may both be at room temperature.
  • the generating step may be a step of mixing the hydrogen peroxide solution and hydrofluoric acid mixed solution with sulfuric acid at a position away from the substrate.
  • the generating step may be a step of mixing the hydrogen peroxide solution and hydrofluoric acid mixed solution and sulfuric acid on the surface of the substrate.
  • Another embodiment of the present invention includes a substrate holding unit for holding a substrate whose surface is covered with a resist, and sulfuric acid, hydrogen peroxide solution, and hydrofluoric acid on the surface of the substrate held by the substrate holding unit.
  • the SPM supply unit supplies an HF mixed SPM that is a mixed solution of the above, and the SPM supply unit mixes hydrogen peroxide solution and hydrofluoric acid to generate a mixture solution of hydrogen peroxide solution and hydrofluoric acid.
  • the mixing unit mixes the hydrogen peroxide solution and hydrofluoric acid, the hydrogen peroxide solution and hydrofluoric acid mixed solution and sulfuric acid are mixed to generate an HF mixed SPM, and A substrate processing apparatus is provided. According to this configuration, it is possible to satisfactorily remove the resist while suppressing damage to devices on the wafer.
  • the mixing unit may include a mixing tank in which hydrogen peroxide solution and hydrofluoric acid are separately supplied, and the mixture solution of the hydrogen peroxide solution and hydrofluoric acid supplied to the HF mixed SPM generating unit is stored. . According to this configuration, the hydrogen peroxide solution and the hydrofluoric acid can be reliably mixed before the mixed solution of the hydrogen peroxide solution and the hydrofluoric acid is mixed with the sulfuric acid.
  • the mixing unit may further include a stirring unit for stirring the mixed solution in the mixing tank.
  • a stirring unit for stirring the mixed solution in the mixing tank.
  • the stirring unit may be a rotor that rotates in the liquid mixture stored in the mixing tank, or may be a bubbling unit that generates bubbles in the liquid mixture stored in the mixing tank.
  • the stirring unit may include a bubbling unit that generates bubbles in the mixed solution by discharging gas from a gas discharge port disposed in the mixed solution stored in the mixing tank. According to this configuration, the hydrogen peroxide solution and hydrofluoric acid are uniformly mixed by the generation of bubbles.
  • the mixing unit may mix a hydrogen peroxide solution and a smaller amount of hydrofluoric acid than the hydrogen peroxide solution.
  • the HF mixed SPM generating unit may mix sulfuric acid and the mixed liquid in a smaller amount than the sulfuric acid. According to this configuration, it is possible to generate an HF mixed SPM capable of peeling the resist while suppressing damage to the substrate, that is, an HF mixed SPM having a low HF concentration.
  • FIG. 1 is a schematic plan view showing a substrate processing apparatus according to an embodiment of the present invention. It is the schematic diagram which looked at the inside of the chamber with which the substrate processing apparatus shown in FIG. 1 was equipped horizontally. It is a block diagram which shows the control apparatus with which the substrate processing apparatus was equipped. It is a flowchart which shows an example of the resist removal process performed by the processing unit shown in FIG. It is a figure which shows the conditions and result of a resist removal test. It is a figure which shows a part of substrate processing apparatus which concerns on other embodiment of this invention. It is a figure which shows a part of substrate processing apparatus which concerns on other embodiment of this invention.
  • FIG. 1 is a schematic plan view showing a substrate processing apparatus 1 according to an embodiment of the present invention.
  • FIG. 2 is a schematic view of the inside of the chamber 4 provided in the substrate processing apparatus 1 as viewed horizontally.
  • the substrate processing apparatus 1 is a single-wafer type apparatus that processes a disk-shaped substrate W such as a semiconductor wafer one by one.
  • the substrate processing apparatus 1 includes a plurality of load ports LP that hold a plurality of carriers C that accommodate a substrate W, and a plurality of processing units 2 that process the substrate W transferred from the plurality of load ports LP with a processing liquid or a processing gas.
  • substrate transfer robots IR and CR that transfer the substrate W between the plurality of load ports LP and the plurality of processing units 2, and the control device 3 that controls the substrate processing apparatus 1.
  • each processing unit 2 is a single-wafer type unit.
  • Each processing unit 2 holds a box-shaped chamber 4 having an internal space and a single substrate W in the chamber 4 in a horizontal posture, and the substrate W around a vertical rotation axis A1 passing through the center of the substrate W.
  • SPM, H 2 O 2 and HF mixed SPM (hereinafter collectively referred to as SPM, etc.) are supplied to a spin chuck (substrate holding unit) 5 that rotates the substrate and a substrate W held on the spin chuck 5
  • HF mixed SPM means SPM to which HF is added.
  • the spin chuck 5 includes a disc-shaped spin base 10 held in a horizontal posture, a plurality of chuck pins 11 that hold the substrate W in a horizontal posture above the spin base 10, and a central portion of the spin base 10.
  • a rotation shaft 12 extending downward, and a spin motor 13 that rotates the rotation shaft 12 to rotate the substrate W and the spin base 10 around the rotation axis A1.
  • the spin chuck 5 is not limited to a clamping chuck in which a plurality of chuck pins 11 are brought into contact with the peripheral end surface of the substrate W, and the back surface (lower surface) of the substrate W, which is a non-device forming surface, is adsorbed to the upper surface of the spin base 10.
  • a vacuum chuck that holds the substrate W horizontally may be used.
  • the cup 9 is disposed outward (in a direction away from the rotation axis A1) from the substrate W held by the spin chuck 5.
  • the cup 9 surrounds the periphery of the spin base 10.
  • the processing liquid supplied to the substrate W is shaken off around the substrate W.
  • the upper end portion 9 a of the cup 9 that opens upward is disposed above the spin base 10. Therefore, the processing liquid such as SPM and rinse liquid discharged around the substrate W is received by the cup 9. Then, the processing liquid received by the cup 9 is sent to a collecting device or a draining device (not shown).
  • the rinsing liquid supply unit 8 includes a rinsing liquid nozzle 35 that discharges the rinsing liquid toward the substrate W held by the spin chuck 5, a rinsing liquid pipe 36 that supplies the rinsing liquid to the rinsing liquid nozzle 35, and a rinsing liquid pipe. And a rinsing liquid valve 37 for switching supply and stop of the rinsing liquid from 36 to the rinsing liquid nozzle 35.
  • the rinse liquid nozzle 35 is a fixed nozzle that discharges the rinse liquid in a state where the discharge port of the rinse liquid nozzle 35 is stationary.
  • the rinsing liquid supply unit 8 may include a rinsing liquid nozzle moving unit that moves the rinsing liquid landing position relative to the upper surface of the substrate W by moving the rinsing liquid nozzle 35.
  • the rinse liquid is, for example, pure water (deionized water) at room temperature (about 23 ° C.).
  • the temperature of pure water is not limited to room temperature, and may be higher than room temperature (for example, 70 to 90 ° C.). That is, the rinse liquid may be warm water (pure water having a temperature higher than normal temperature).
  • the rinse liquid is not limited to pure water, but may be any of carbonated water, electrolytic ion water, hydrogen water, ozone water, and hydrochloric acid water having a diluted concentration (for example, about 10 to 100 ppm).
  • the SPM supply unit 6 includes an SPM nozzle 14 that selectively discharges SPM and the like toward the upper surface of the substrate W, a first nozzle arm 15 having the SPM nozzle 14 attached to the tip, and a first nozzle arm 15. And a first nozzle moving unit 16 that moves the SPM nozzle 14.
  • the SPM nozzle 14 is, for example, a straight nozzle that selectively discharges SPM or the like in a continuous flow state.
  • the SPM nozzle 14 is applied to the first nozzle arm 15 in a vertical posture that discharges the processing liquid in a direction perpendicular to the upper surface of the substrate W. It is attached.
  • the first nozzle arm 15 extends in the horizontal direction and is provided to be rotatable around a first swing axis (not shown) extending in the vertical direction around the spin chuck 5.
  • the SPM nozzle 14 is an inward direction in which SPM or the like is discharged in a discharge direction inclined with respect to the upper surface of the substrate W so that the SPM or the like is deposited inward (rotation axis A1 side) from the discharge port. It may be held by the first nozzle arm 15 in a posture, or with respect to the upper surface of the substrate W so that SPM or the like is deposited outside the discharge port (on the opposite side to the rotation axis A1). You may hold
  • the first nozzle moving unit 16 rotates the first nozzle arm 15 around the first swing axis, thereby causing the SPM nozzle 14 to move horizontally along a trajectory passing through the center of the upper surface of the substrate W in plan view. Move.
  • the first nozzle moving unit 16 includes a processing position where the SPM discharged from the SPM nozzle 14 is deposited on the upper surface of the substrate W and a home position where the SPM nozzle 14 is positioned around the spin chuck 5 in plan view. In the meantime, the SPM nozzle 14 is moved horizontally.
  • the processing position includes a central position where the SPM discharged from the SPM nozzle 14 lands on the center of the upper surface of the substrate W, and a peripheral position where the SPM discharged from the SPM nozzle 14 lands on the periphery of the upper surface of the substrate W. Including.
  • the SPM supply unit 6 is connected to the SPM nozzle 14 and is connected to the sulfuric acid pipe 17 to which H 2 SO 4 is supplied from the sulfuric acid supply source.
  • the SPM supply unit 6 is connected to the SPM nozzle 14 and is mixed with hydrogen peroxide and hydrofluoric acid.
  • a mixed liquid pipe 27 to which hydrogen oxide water is supplied.
  • the upstream end of the mixed liquid pipe 27 is connected to the mixing unit 30, and the downstream end of the mixed liquid pipe 27 is connected to the SPM nozzle 14.
  • the mixing unit 30 is an example of a mixing unit that mixes H 2 O 2 and HF before being mixed with H 2 SO 4 .
  • the mixing unit 30 is connected to a hydrogen peroxide water pipe 18 to which H 2 O 2 is supplied from a hydrogen peroxide supply source, and a hydrofluoric acid pipe 28 to which HF is supplied from a hydrofluoric acid supply source.
  • H 2 SO 4 supplied from the sulfuric acid supply source, H 2 O 2 supplied from the hydrogen peroxide supply source, and HF supplied from the hydrofluoric acid supply source are all aqueous solutions.
  • the concentration of H 2 SO 4 is, for example, 90 to 98%
  • the concentration of H 2 O 2 is, for example, 30 to 50%
  • the concentration of HF is, for example, 47 to 51%.
  • the sulfuric pipe 17, a sulfate valve 19 for opening and closing the sulfuric pipe 17, the sulfuric acid flow rate adjusting valve 20 to change the flow rate of H 2 SO 4, a heater 21 for heating the H 2 SO 4 is from SPM nozzle 14 side They are inserted in this order.
  • the sulfuric acid flow rate adjusting valve 20 includes a valve body in which a valve seat is provided, a valve body that opens and closes the valve seat, and an actuator that moves the valve body between an open position and a closed position. Including. The same applies to the other valves. The actuator of each valve is controlled by the control device 3.
  • the heater 21 maintains H 2 SO 4 at a temperature higher than room temperature (a constant temperature within a range of 70 to 100 ° C., for example, 90 ° C.).
  • Heater 21 for heating the H 2 SO 4 may be a heater of one-pass system as shown in FIG. 2, for heating the H 2 SO 4 by circulating H 2 SO 4 in a circulating path including a heater A circulating heater may be used.
  • the one-pass method is a method in which the heated liquid passes through the heater only once
  • the circulation method is a method in which the heated liquid passes through the heater a plurality of times.
  • the hydrogen peroxide solution pipe 18 includes a hydrogen peroxide solution valve 22 that opens and closes the hydrogen peroxide solution pipe 18 and a hydrogen peroxide solution flow rate adjustment valve 23 that changes the flow rate of H 2 O 2.
  • the mixing unit 30 is supplied with normal temperature (about 23 ° C.) H 2 O 2 whose temperature is not adjusted through the hydrogen peroxide pipe 18.
  • a micropump 31 for supplying HF to the mixing unit 30 is interposed.
  • the micropump 31 has a function of sending the liquid downstream and a function of blocking the flow of the liquid.
  • HF at room temperature (about 23 ° C.) whose temperature is not adjusted is supplied to the mixing unit 30 through the hydrofluoric acid pipe 28.
  • the flow rate of HF sent from the micropump 31 to the mixing unit 30 is controlled by the control device 3.
  • the micropump 31 is an example of a hydrofluoric acid switching unit that switches between a supply state in which HF is supplied to the mixing unit 30 and a supply stop state in which the supply of HF to the mixing unit 30 is stopped.
  • the hydrofluoric acid switching unit may be a hydrofluoric acid valve 32 (see FIG. 6) that opens and closes the hydrofluoric acid pipe 28.
  • the mixing unit 30 is a substantially cylindrical member, and H 2 O 2 and HF are stirred and mixed inside the mixing unit 30.
  • the mixing unit 30 may be a mixing valve having the functions of the hydrogen peroxide solution valve 22 and the hydrofluoric acid switching unit. In this case, the hydrogen peroxide valve 22 and the hydrofluoric acid switching unit may be omitted.
  • the flow rates of H 2 O 2 and HF flowing into the mixing unit 30 are adjusted by the hydrogen peroxide flow rate adjusting valve 23 and the micropump 31.
  • the flow rate of H 2 O 2 is 300 ml / min.
  • the flow rate of HF is, for example, 90 ⁇ l / min. It is. Even when the flow rates are different from each other as in this example, H 2 O 2 and HF are uniformly mixed by being stirred in the mixing unit 30.
  • the SPM nozzle 14 has, for example, a substantially cylindrical casing.
  • a mixing chamber is formed inside the casing.
  • the sulfuric acid pipe 17 is connected to a sulfuric acid introduction port arranged on the side wall of the casing of the SPM nozzle 14.
  • the mixed liquid pipe 27 is connected to a mixed liquid inlet disposed on the side wall of the casing of the SPM nozzle 14.
  • the liquid mixture inlet is disposed above the sulfuric acid inlet.
  • H 2 SO 4 from the sulfuric acid pipe 17 is supplied to the SPM nozzle 14. While being supplied from the sulfuric acid inlet to the mixing chamber, H 2 O 2 and HF from the mixed liquid pipe 27 are supplied from the mixed liquid inlet of the SPM nozzle 14 to the mixing chamber.
  • H 2 SO 4 , H 2 O 2 , and HF that have flowed into the mixing chamber of the SPM nozzle 14 are sufficiently stirred and mixed in the mixing chamber.
  • This mixture H 2 SO 4 and H 2 O 2 and is mingled evenly, a mixed solution of H 2 SO 4 and H 2 O 2 by reaction of H 2 SO 4 and H 2 O 2 (SPM) is generated Is done.
  • SPM containing HF that is, HF mixed SPM is generated.
  • SPM contains peroxymonosulfuric acid (H 2 SO 5 ) having a strong oxidizing power, and is higher than the temperature of H 2 SO 4 and H 2 O 2 before mixing (100 ° C. or higher, for example, 160 ° C.). Until heated.
  • the high-temperature HF mixed SPM generated in the mixing chamber of the SPM nozzle 14 is discharged from a discharge port opened at the front end (lower end) of the casing.
  • FIG. 3 is a block diagram showing the control device 3.
  • FIG. 4 is a flowchart showing an example of the resist removal process performed by the processing unit 2.
  • the control device 3 is constituted by, for example, a microcomputer.
  • the control device 3 controls the operations of the spin motor 13, the nozzle moving unit 16, the heater 21 and the like according to a predetermined program.
  • the control device 3 controls the opening and closing of the sulfuric acid valve 19, the hydrogen peroxide water valve 22, the micropump 31, the rinse liquid valve 37 and the like, and controls the actuators of the flow rate adjusting valves 20, 23, 33 to The opening degree of the flow regulating valves 20 and 23 is controlled.
  • the control device 3 includes a storage unit 3b that stores information such as a program and an arithmetic unit 3a that controls the substrate processing apparatus 1 according to the information stored in the storage unit 3b.
  • a recipe indicating the processing procedure and processing steps of the substrate W is stored in the storage unit 3b.
  • the control device 3 is programmed to cause the substrate processing apparatus 1 to execute each process described below by controlling the substrate processing apparatus 1 based on the recipe stored in the storage unit 3b.
  • the substrate W to be processed is a substrate that has been subjected to ion implantation at a high dose. It is assumed that this substrate W has not undergone a process for ashing the resist.
  • a loading process for loading the substrate W into the chamber 4 is performed (step S1). Specifically, the control device 3 moves the hand of the substrate transport robot CR (see FIG. 1) holding the substrate W in the chamber 4 in a state where all the nozzles and the like are retracted from above the spin chuck 5. By entering the inside, the substrate W is placed on the spin chuck 5 with the surface thereof directed upward. Thereafter, the control device 3 starts the rotation of the substrate W by the spin motor 13 (step S2). The rotational speed of the substrate W is increased to a predetermined processing rotational speed (in the range of 100 to 500 rpm, for example, about 300 rpm), and is maintained at the processing rotational speed.
  • a predetermined processing rotational speed in the range of 100 to 500 rpm, for example, about 300 rpm
  • step S3 When the rotational speed of the substrate W reaches the processing rotational speed, the control device 3 then performs an SPM processing step (step S3) for supplying SPM to the substrate W. Specifically, the control device 3 moves the SPM nozzle 14 from the home position to the processing position by controlling the first nozzle moving unit 16. Thereby, the SPM nozzle 14 is disposed above the substrate W.
  • the control device 3 opens the sulfuric acid valve 19 and the hydrogen peroxide water valve 22 and further drives the micropump 31.
  • the H 2 O 2 flowing hydrogen peroxide water pipe 18, and the HF flowing through the hydrofluoric acid pipe 28 flows into the mixing portion 30, a mixed solution (HF mixture H 2 O 2) is generated ( Mixing step).
  • the mixed solution that has passed through the mixing unit 30 and H 2 SO 4 that flows through the sulfuric acid pipe 17 are supplied to the SPM nozzle 14, and H 2 SO 4 , H 2 O 2, and HF are mixed in the mixing chamber of the SPM nozzle 14.
  • HF mixed SPM at a high temperature for example, 160 ° C.
  • the HF mixed SPM is discharged from the discharge port of the SPM nozzle 14 and is deposited on the upper surface of the substrate W (supply process).
  • the control device 3 controls the first nozzle moving unit 16 to move the liquid deposition position of the HF mixed SPM with respect to the upper surface of the substrate W in this state between the central portion and the peripheral portion.
  • the HF mixed SPM discharged from the SPM nozzle 14 lands on the upper surface of the substrate W rotating at a processing rotation speed (for example, 300 rpm), and then flows outward along the upper surface of the substrate W by centrifugal force. Therefore, the HF mixed SPM is supplied to the entire upper surface of the substrate W, and a liquid film of the HF mixed SPM that covers the entire upper surface of the substrate W is formed on the substrate W.
  • a processing rotation speed for example, 300 rpm
  • the cured layer on the resist surface is obtained by curing an organic substance mainly composed of carbon by ion implantation.
  • the reason why the resist is effectively removed is that HF has a function of dissolving a group 14 element oxide (such as SiO 2 ), and HF contained in the HF mixed SPM effectively removes the organic oxide on the resist surface. This is probably because
  • HF that has penetrated into the non-hardened layer of the resist slightly etches Si and SiO 2 constituting the surface of the substrate W at the boundary between the resist and the surface of the substrate W, thereby improving the resist peeling performance. It is also possible to do.
  • control device 3 moves the liquid deposition position of the HF mixed SPM with respect to the upper surface of the substrate W between the central portion and the peripheral edge while the substrate W is rotating, the liquid deposition position of the HF mixed SPM is Passes through the entire upper surface of the substrate W, and the entire upper surface of the substrate W is scanned. Therefore, the HF mixed SPM discharged from the SPM nozzle 14 is supplied to the entire upper surface of the substrate W, and the entire upper surface of the substrate W is processed uniformly.
  • step S3 When a predetermined HF mixing SPM processing time has elapsed from the start of discharging the HF mixing SPM, the SPM processing step (step S3) ends. Subsequent to the end of the SPM processing step (step S3), a hydrogen peroxide solution supplying step (step S4) for supplying H 2 O 2 to the substrate W is performed.
  • the control device 3 controls the first nozzle moving unit 16 to dispose the SPM nozzle 14 above the center of the upper surface of the substrate W, and then opens the hydrogen peroxide solution valve 22.
  • the sulfuric acid valve 19 is closed while maintaining the state.
  • the control device 3 stops the micropump 31.
  • only H 2 O 2 flows through the hydrogen peroxide solution pipe 18 and the mixed solution pipe 27 and is supplied to the SPM nozzle 14.
  • the hydrogen peroxide solution supplied to the SPM nozzle 14 passes through the inside of the SPM nozzle 14 and is discharged from the discharge port of the SPM nozzle 14.
  • the H 2 O 2 is deposited on the center of the upper surface of the substrate W rotating at the processing rotation speed. That is, the processing liquid discharged from the SPM nozzle 14 is switched from the HF mixed SPM to H 2 O 2 .
  • the H 2 O 2 deposited on the center of the upper surface of the substrate W flows outward on the substrate W toward the peripheral edge of the substrate W.
  • the SPM on the substrate W is replaced with H 2 O 2 , and eventually, the entire upper surface of the substrate W is covered with a liquid film of H 2 O 2 .
  • the control device 3 closes the hydrogen peroxide solution valve 22 and stops the discharge of H 2 O 2 from the SPM nozzle 14. Further, the control device 3 controls the first nozzle moving unit 16 to move the SPM nozzle 14 from the processing position to the home position. As a result, the SPM nozzle 14 is retracted from above the substrate W.
  • a rinsing liquid supply step (step S5) for supplying the rinsing liquid to the substrate W is performed.
  • the control device 3 opens the rinse liquid valve 37 and discharges the rinse liquid from the rinse liquid nozzle 35 toward the center of the upper surface of the substrate W.
  • the rinse liquid discharged from the rinse liquid nozzle 35 is deposited on the center of the upper surface of the substrate W covered with H 2 O 2 .
  • the rinse liquid deposited on the center of the upper surface of the substrate W flows outward on the substrate W toward the peripheral edge of the substrate W. As a result, H 2 O 2 on the substrate W is pushed outward by the rinse liquid and discharged around the substrate W.
  • the liquid film of H 2 O 2 on the substrate W is replaced with the liquid film of the rinsing liquid that covers the entire upper surface of the substrate W.
  • H 2 O 2 is washed away in the entire upper surface of the substrate W.
  • a drying process for drying the substrate W is performed.
  • the control device 3 controls the spin motor 13 to accelerate the substrate W to a drying rotation speed (for example, several thousand rpm) and rotate the substrate W at the drying rotation speed. Thereby, a large centrifugal force is applied to the liquid on the substrate W, and the liquid adhering to the substrate W is shaken off around the substrate W. In this way, the liquid is removed from the substrate W, and the substrate W is dried.
  • the control device 3 controls the spin motor 13 to stop the rotation of the substrate W by the spin chuck 5 (step S7).
  • step S8 an unloading process for unloading the substrate W from the chamber 4 is performed (step S8).
  • the control device 3 causes the hand of the substrate transport robot CR to enter the chamber 4 in a state where all the nozzles and the like are retracted from above the spin chuck 5. Then, the control device 3 holds the substrate W on the spin chuck 5 by the hand of the substrate transport robot CR. Thereafter, the control device 3 retracts the hand of the substrate transport robot CR from the chamber 4. Thereby, the processed substrate W is unloaded from the chamber 4.
  • the hydrogen peroxide solution supply step (step S4) is executed after the SPM treatment step (step S3), but the hydrogen peroxide solution supply step (step S4) can be omitted. .
  • the substrate W may be in a paddle state.
  • the paddle state means a state in which the upper surface of the substrate W is covered with a liquid film and the substrate is stationary in the rotation direction or rotating at a low rotation speed (50 rpm or less).
  • the discharge of SPM from the substrate W is suppressed, and the SPM liquid film is held on the upper surface of the substrate W.
  • the supply of SPM (discharge of SPM) to the substrate W may be stopped.
  • FIG. 5 is a diagram showing conditions and results of a resist removal test. This resist removal test is for confirming the relationship between the concentration of HF in the SPM and the resist removal performance.
  • the substrate processing apparatus 1 was used to carry out resist removal processing of Examples and Comparative Examples described below. Then, the presence or absence of the remaining resist after the resist removal treatment and the degree of damage to other than the resist were observed using an electron microscope.
  • the mixing ratio (flow rate ratio) of H 2 SO 4 and H 2 O 2 in the SPM used in the SPM processing step of Step S3 is 2: 1, and the processing time of the SPM processing step of Step S3 is 1 minute. did.
  • the concentration of HF was changed from 0 (comparative example) to 10000 ppm (data 3).
  • flow rate of H 2 O 2 means the flow rate of the mixed solution of HF and H 2 O 2.
  • Example> The same treatment was performed with HF mixed SPM having different HF concentrations.
  • the HF concentration in the HF mixed SPM at this time is as follows.
  • FIG. 5 The results of this resist removal test are shown in FIG. In FIG. 5, “ ⁇ ” indicates that there is no resist residue and no damage to the substrate surface, and “ ⁇ 1” indicates that a small amount of resist residue is generated. The case where there is damage is indicated by “ ⁇ 2”, the case where a large amount of resist remains, or the case where the resist is not peeled off at all, is indicated by “X”.
  • the resist stripping performance is improved as the HF concentration increases.
  • damage to the substrate surface that is, etching of the substrate surface was confirmed even when the HF concentration was 1000 ppm.
  • the HF concentration was 10,000 ppm, damage to the substrate surface was confirmed in all pattern shapes.
  • the comparative example almost no resist peeling was observed with respect to the silicon wafer W on which high-dose ion implantation was performed.
  • the resist stripping performance can be improved by mixing HF with SPM.
  • the SPM supply unit 6 includes the mixed solution pipe 27 that guides the mixed solution mixed by the mixing unit 30 to the SPM nozzle 14, but is not limited thereto.
  • FIG. 6 is a diagram showing an SPM supply unit 6a according to another embodiment. In FIG. 6, the same devices as those in FIG.
  • a mixed liquid pipe 27 of the SPM supply unit 6 a shown in FIG. 6 is connected to the mixing tank 130 instead of the mixing unit 30.
  • the mixed liquid pump 131 is interposed in the mixed liquid pipe 27.
  • Connected to the mixing tank 130 are a hydrogen peroxide pipe 18 to which H 2 O 2 is supplied from a hydrogen peroxide supply source and a hydrofluoric acid pipe 28 to which HF is supplied from a hydrofluoric acid supply source.
  • the hydrofluoric acid pipe 28 is provided with a hydrofluoric acid valve 32 for opening and closing the hydrofluoric acid pipe 28 and a hydrofluoric acid flow rate adjusting valve 33 for changing the flow rate of HF in this order from the mixing tank 130 side.
  • the mixing tank 130 is supplied with HF at room temperature (about 23 ° C.) whose temperature is not adjusted through the hydrofluoric acid pipe 28.
  • the control device 3 Prior to the SPM processing step (step S3), the control device 3 executes a blending step of blending the mixed solution (HF mixed H 2 O 2 ) in the mixing tank 130. Specifically, the control device 3 supplies 30 L of a predetermined concentration of H 2 O 2 to the mixing tank 130 by opening the hydrogen peroxide solution valve 22. Thereafter, the control device 3 opens the hydrofluoric acid valve 32 to supply 10 ml to 100 ml of HF having a predetermined concentration to the mixing tank 130. The supply of HF to the mixing tank 130 may be started before or after the supply of H 2 O 2 is started, or may be started simultaneously with the supply of H 2 O 2 .
  • the SPM supply unit 6 a may further include a stirring unit that stirs the H 2 O 2 and HF in the mixing tank 130.
  • the stirring unit is, for example, a bubbling unit 132 that generates bubbles in the liquid mixture by discharging a gas such as nitrogen gas from a gas discharge port 132a disposed in the liquid mixture in the mixing tank 130.
  • a stirring unit When a stirring unit is provided, H 2 O 2 and HF in the mixing tank 130 are mixed more uniformly.
  • the HF mixed H 2 O 2 generated in the mixing tank 130 is supplied to the SPM nozzle 14 by the mixed liquid pump 131.
  • H 2 SO 4 is supplied from the sulfuric acid pipe 17 to the SPM nozzle 14.
  • the H 2 SO 4 , H 2 O 2 , and HF that have flowed into the mixing chamber of the SPM nozzle 14 are sufficiently stirred and mixed in the mixing chamber, thereby generating an HF mixed SPM.
  • the HF mixed SPM is discharged from the SPM nozzle 14 and supplied onto the substrate W.
  • the SPM supply unit 6a it is possible to generate a H 2 O 2 / HF mixed liquid having a HF concentration lower than that in the above-described embodiment. The reason is that the ratio of H 2 O 2 and HF can be freely changed as compared with the case where H 2 O 2 and HF are mixed in a pipe or a valve.
  • FIG. 7 is a diagram showing an SPM supply unit 6b according to another embodiment.
  • the SPM supply unit 6b includes a sulfuric acid nozzle 14a and an H 2 O 2 / HF nozzle 14b.
  • the sulfuric acid nozzle 14 a discharges H 2 SO 4 toward the substrate W.
  • the H 2 O 2 / HF nozzle 14 b discharges the H 2 O 2 / HF mixed solution supplied from the mixing unit 30 toward the substrate W.
  • the H 2 O 2 / HF nozzle 14 b may discharge the H 2 O 2 / HF mixed solution supplied from the mixing tank 130 toward the substrate W.
  • the sulfuric acid from the sulfuric acid nozzle 14a and the H 2 O 2 / HF mixed solution from the H 2 O 2 / HF nozzle 14b are supplied to the rotating substrate W, whereby H 2 SO 4 , H 2 O 2 , And HF are stirred and mixed on the substrate W. Thereby, HF mixing SPM is produced
  • the HF mixed SPM generating unit including the sulfuric acid nozzle 14 a and the H 2 O 2 / HF nozzle 14 b generates the HF mixed SPM on the substrate W.
  • the HF mixed SPM is generated in a region closer to the substrate W than in the above-described embodiment. Therefore, it becomes possible to process the substrate W while maintaining the chemical activity of the SPM at a high level.
  • the substrate processing apparatus 1 is an apparatus that processes the disk-shaped substrate W.
  • the substrate processing apparatus 1 is a polygonal substrate such as a substrate for a liquid crystal display device.
  • An apparatus for processing W may be used.

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  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Cleaning Or Drying Semiconductors (AREA)

Abstract

Afin de résoudre le problème d'élimination de manière satisfaisante d'une réserve de la surface d'un substrat, la présente invention concerne un dispositif de traitement de substrat (1) comportant un mandrin rotatif (5) et une unité d'alimentation en SPM (6) pour injecter du SPM vers le substrat (W) maintenu par le mandrin rotatif (5), l'unité d'alimentation en SPM (6) comprenant une unité de mélange (30) pour mélanger une solution aqueuse de peroxyde d'hydrogène et de l'acide fluorhydrique (HF) et produire un mélange liquide de peroxyde d'hydrogène, d'eau et d'acide fluorhydrique, et une unité de production de SPM mélangé à HF (14) pour mélanger le mélange liquide et de l'acide sulfurique et produire du SPM mélangé à HF.
PCT/JP2016/055646 2015-03-24 2016-02-25 Procédé de traitement de substrat et dispositif de traitement de substrat WO2016152371A1 (fr)

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CN201680017231.0A CN107430987B (zh) 2015-03-24 2016-02-25 基板处理方法和基板处理装置
US15/559,076 US10668497B2 (en) 2015-03-24 2016-02-25 Substrate processing method and substrate processing device
KR1020177026290A KR101988848B1 (ko) 2015-03-24 2016-02-25 기판 처리 방법 및 기판 처리 장치

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CN112631089A (zh) * 2019-09-24 2021-04-09 株式会社斯库林集团 基板处理方法以及基板处理装置
WO2023127217A1 (fr) * 2021-12-27 2023-07-06 株式会社Ｓｃｒｅｅｎホールディングス Procédé de traitement de substrat et appareil de traitement de substrat

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JPH08250400A (ja) * 1995-03-14 1996-09-27 Mitsubishi Electric Corp シリコーン樹脂の除去法
JP2002313771A (ja) * 2001-02-07 2002-10-25 Matsushita Electric Ind Co Ltd 半導体装置の製造方法
JP2002343762A (ja) * 2001-04-17 2002-11-29 Internatl Business Mach Corp <Ibm> 湿式洗浄装置および方法
JP2011068937A (ja) * 2009-09-25 2011-04-07 Toshiba Corp 洗浄液、洗浄方法、洗浄システム及び微細構造体の製造方法
JP2013175592A (ja) * 2012-02-24 2013-09-05 Tokyo Electron Ltd 液処理装置、液処理方法および液処理方法を実行するためのコンピュータプログラムが記録された記録媒体

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JPH08250400A (ja) * 1995-03-14 1996-09-27 Mitsubishi Electric Corp シリコーン樹脂の除去法
JP2002313771A (ja) * 2001-02-07 2002-10-25 Matsushita Electric Ind Co Ltd 半導体装置の製造方法
JP2002343762A (ja) * 2001-04-17 2002-11-29 Internatl Business Mach Corp <Ibm> 湿式洗浄装置および方法
JP2011068937A (ja) * 2009-09-25 2011-04-07 Toshiba Corp 洗浄液、洗浄方法、洗浄システム及び微細構造体の製造方法
JP2013175592A (ja) * 2012-02-24 2013-09-05 Tokyo Electron Ltd 液処理装置、液処理方法および液処理方法を実行するためのコンピュータプログラムが記録された記録媒体

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112631089A (zh) * 2019-09-24 2021-04-09 株式会社斯库林集团 基板处理方法以及基板处理装置
WO2023127217A1 (fr) * 2021-12-27 2023-07-06 株式会社Ｓｃｒｅｅｎホールディングス Procédé de traitement de substrat et appareil de traitement de substrat

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