WO2014051063A1 - 基板処理方法、コンピュータ記憶媒体及び基板処理システム - Google Patents

基板処理方法、コンピュータ記憶媒体及び基板処理システム Download PDF

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Publication number
WO2014051063A1
WO2014051063A1 PCT/JP2013/076288 JP2013076288W WO2014051063A1 WO 2014051063 A1 WO2014051063 A1 WO 2014051063A1 JP 2013076288 W JP2013076288 W JP 2013076288W WO 2014051063 A1 WO2014051063 A1 WO 2014051063A1
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Prior art keywords
resist pattern
resist
polymer
block copolymer
wafer
Prior art date
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Ceased
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PCT/JP2013/076288
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English (en)
French (fr)
Japanese (ja)
Inventor
村松　誠
北野　高広
忠利 冨田
啓士 田内
聡一郎 岡田
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Tokyo Electron Ltd
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Tokyo Electron Ltd
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Priority to KR1020157006644A priority Critical patent/KR101932804B1/ko
Priority to US14/430,988 priority patent/US9748101B2/en
Publication of WO2014051063A1 publication Critical patent/WO2014051063A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
    • H10P76/20—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials
    • H10P76/204—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials of organic photoresist masks
    • H10P76/2041—Photolithographic processes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/40—Treatment after imagewise removal, e.g. baking
    • G03F7/405—Treatment with inorganic or organometallic reagents after imagewise removal
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16—Coating processes; Apparatus therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J37/00—Discharge tubes with provision for introducing objects or material to be exposed to the discharge, e.g. for the purpose of examination or processing thereof
    • H01J37/32—Gas-filled discharge tubes
    • H01J37/32431—Constructional details of the reactor
    • H01J37/32798—Further details of plasma apparatus not provided for in groups H01J37/3244 - H01J37/32788; special provisions for cleaning or maintenance of the apparatus
    • H01J37/32889—Connection or combination with other apparatus
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P50/00—Etching of wafers, substrates or parts of devices
    • H10P50/20—Dry etching; Plasma etching; Reactive-ion etching
    • H10P50/28—Dry etching; Plasma etching; Reactive-ion etching of insulating materials
    • H10P50/286—Dry etching; Plasma etching; Reactive-ion etching of insulating materials of organic materials
    • H10P50/287—Dry etching; Plasma etching; Reactive-ion etching of insulating materials of organic materials by chemical means
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
    • H10P72/04—Apparatus for manufacture or treatment
    • H10P72/0448—Apparatus for applying a liquid, a resin, an ink or the like
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P72/00—Handling or holding of wafers, substrates or devices during manufacture or treatment thereof
    • H10P72/06—Apparatus for monitoring, sorting, marking, testing or measuring
    • H10P72/0604—Process monitoring, e.g. flow or thickness monitoring
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
    • H10P76/20—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P76/00—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography
    • H10P76/20—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials
    • H10P76/204—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising organic materials of organic photoresist masks

Definitions

  • the present invention relates to a substrate processing method, a computer storage medium, and a substrate processing system using a block copolymer including a hydrophilic polymer having hydrophilicity and a hydrophobic polymer having hydrophobicity.
  • a resist coating process for coating a resist solution on a semiconductor wafer to form a resist film
  • an exposure process for exposing a predetermined pattern on the resist film A photolithography process for sequentially performing a development process for developing the exposed resist film is performed to form a predetermined resist pattern on the wafer.
  • an etching process is performed on the film to be processed on the wafer, and then a resist film removing process is performed to form a predetermined pattern on the film to be processed.
  • Patent Document 1 a wafer processing method using a block copolymer composed of two types of block chains (polymer), hydrophilic and hydrophobic, has been proposed (Patent Document 1).
  • a neutral layer having an intermediate affinity for two types of polymers is formed on a wafer, and a guide pattern is formed on the neutral layer by using, for example, a resist.
  • a block copolymer is applied onto the neutral layer, and the block copolymer is phase-separated into two types of polymers, hydrophilic and hydrophobic, to form a lamella structure.
  • a fine pattern is formed on the wafer by the other polymer.
  • the processing target film is etched using the polymer pattern as a mask to form a predetermined pattern on the processing target film.
  • a block copolymer when a block copolymer is applied on a neutral layer using a resist as a guide pattern as described above, and the block copolymer is phase-separated, it is separated into a lamellar structure in a desired pattern. It was confirmed that there were cases where it was not possible.
  • the resist pattern after development is hydrophobic, the hydrophobic polymer is arranged along the longitudinal direction of the resist pattern, thereby forming a lamella structure along the longitudinal direction of the resist pattern.
  • the hydrophilic polymer and the hydrophobic polymer may not be arranged along the longitudinal direction of the resist pattern, and a lamellar structure may be randomly formed with respect to the resist pattern.
  • symbol 604 in FIG. 19 is a neutral layer with intermediate
  • the resist film in the intermediate exposure region 603 is not developed and remains on the entire surface of the resist pattern, or the intermediate exposure region 603 and the unexposed region 602 are mixed on the resist pattern surface. I will. As a result, the hydrophilic polymer and the hydrophobic polymer are randomly arranged with respect to the resist pattern.
  • the present invention has been made in view of such points, and an object of the present invention is to appropriately form a predetermined pattern on a substrate in substrate processing using a block copolymer containing a hydrophilic polymer and a hydrophobic polymer.
  • the present invention provides a method for treating a substrate using a block copolymer comprising a hydrophilic polymer and a hydrophobic polymer, wherein the hydrophilic polymer and the hydrophobic polymer are treated with respect to the substrate.
  • a neutral layer forming step for forming a neutral layer having an intermediate affinity on the substrate, and a resist film formed on the neutral layer is exposed to light, and then the resist film after the exposure is developed to form a resist.
  • a resist pattern forming step of forming a pattern a resist pattern processing step of supplying a polar organic solvent to the resist pattern to surface-treat the resist pattern, and applying the block copolymer onto the neutral layer
  • a block copolymer coating step and a polymer separation step for phase-separating the block copolymer on the neutral layer into the hydrophilic polymer and the hydrophobic polymer; Having.
  • the resist pattern is surface-treated by supplying a polar organic solvent in the resist pattern processing step, the resist remaining on the surface of the resist pattern is altered and not necessarily hydrophobic (hydrophobicity) Can be removed to expose unexposed areas with sufficient hydrophobicity. Therefore, it becomes easy to attract the hydrophobic polymer to the resist pattern having hydrophobicity, and when the block copolymer is phase-separated, each polymer can be prevented from being randomly arranged to form a desired pattern. . Since a predetermined fine pattern can be appropriately formed on the substrate in this way, the film to be processed can be appropriately etched using the hydrophilic polymer or hydrophobic polymer pattern as a mask. A predetermined pattern can be formed on the treatment film.
  • Another aspect of the present invention is a readable computer storage medium storing a program that operates on a computer of a control unit that controls the substrate processing system in order to cause the substrate processing system to execute the substrate processing method. .
  • the present invention provides a system for treating a substrate using a block copolymer including a hydrophilic polymer and a hydrophobic polymer, wherein the system is intermediate between the hydrophilic polymer and the hydrophobic polymer.
  • a neutral layer forming apparatus for forming a neutral layer having affinity on a substrate; a developing apparatus for developing a resist film after exposure processing formed on the neutral layer to form a resist pattern; and the development
  • a resist pattern processing apparatus for surface-treating the resist pattern by supplying an organic solvent having polarity to a subsequent resist pattern; a block copolymer coating apparatus for coating the block copolymer on the neutral layer; A polymer separation device for phase-separating the block copolymer on the neutral layer into the hydrophilic polymer and the hydrophobic polymer.
  • a predetermined pattern can be appropriately formed on a substrate in substrate processing using a block copolymer containing a hydrophilic polymer and a hydrophobic polymer.
  • FIG. 1 is an explanatory diagram showing an outline of a configuration of a substrate processing system 1 according to the present embodiment.
  • the substrate processing system 1 includes a coating and developing apparatus 2 that performs photolithography processing on a wafer as a substrate, and an etching processing apparatus 3 that performs etching processing on the wafer.
  • a film to be processed (not shown) is formed in advance on the wafer processed by the substrate processing system 1.
  • the coating / developing apparatus 2 includes, for example, a cassette station 10 in which a cassette C containing a plurality of wafers W is carried in and out of the outside, and a predetermined type of sheet processing in a photolithography process.
  • a processing station 11 having a plurality of various processing apparatuses for processing and an interface station 13 for transferring the wafer W between the exposure apparatus 12 adjacent to the processing station 11 are integrally connected. .
  • the cassette station 10 is provided with a cassette mounting table 20.
  • the cassette mounting table 20 is provided with a plurality of, for example, four cassette mounting plates 21.
  • the cassette mounting plates 21 are arranged in a line in the horizontal X direction (vertical direction in FIG. 2).
  • the cassette C can be placed on these cassette placement plates 21 when the cassette C is carried in and out of the coating and developing treatment apparatus 2.
  • the cassette station 10 is provided with a wafer transfer device 23 that is movable on a transfer path 22 extending in the X direction.
  • the wafer transfer device 23 is also movable in the vertical direction and the vertical axis direction ( ⁇ direction), and includes a cassette C on each cassette mounting plate 21 and a delivery device for a third block G3 of the processing station 11 described later.
  • the wafer W can be transferred between the two.
  • the processing station 11 is provided with a plurality of, for example, four blocks G1, G2, G3, and G4 having various devices.
  • the first block G1 is provided on the front side of the processing station 11 (X direction negative direction side in FIG. 2), and the second side is provided on the back side of the processing station 11 (X direction positive direction side in FIG. 2).
  • Block G2 is provided.
  • a third block G3 is provided on the cassette station 10 side (Y direction negative direction side in FIG. 1) of the processing station 11, and the interface station 13 side (Y direction positive direction side in FIG. 2) of the processing station 11 is provided. Is provided with a fourth block G4.
  • a resist pattern is formed by supplying a plurality of liquid processing apparatuses, for example, a developing apparatus 30 for developing the wafer W, and supplying an organic solvent having polarity to the developed resist pattern.
  • An organic solvent supply device 31 as a resist pattern processing device for surface treatment, an antireflection film forming device 32 for forming an antireflection film on the wafer W, and forming a neutral layer by applying a neutral agent on the wafer W
  • the resist layer forming device 33, the resist coating device 34 for coating a resist solution on the wafer W to form a resist film, and the block copolymer coating device 35 for coating a block copolymer on the wafer W are stacked in order from the bottom. ing.
  • an ArF resist which is a positive resist is used as the resist in this embodiment.
  • the developing device 30, the organic solvent supply device 31, the antireflection film forming device 32, the neutral layer forming device 33, the resist coating device 34, and the block copolymer coating device 35 are arranged side by side in the horizontal direction. .
  • the number and arrangement of the developing device 30, the organic solvent supply device 31, the antireflection film forming device 32, the neutral layer forming device 33, the resist coating device 34, and the block copolymer coating device 35 can be arbitrarily selected.
  • the organic solvent supply device 31 the antireflection film forming device 32, the neutral layer forming device 33, the resist coating device 34, and the block copolymer coating device 35, for example, a predetermined coating solution is applied onto the wafer W.
  • a predetermined coating solution is applied onto the wafer W.
  • Spin coating is performed.
  • a coating liquid is discharged onto the wafer W from a coating nozzle, and the wafer W is rotated to diffuse the coating liquid to the surface of the wafer W.
  • the block copolymer applied on the wafer W by the block copolymer coating device 35 is hydrophobic (non-polar) hydrophobic (nonpolar) polymer and hydrophilic (polar) hydrophilic.
  • (Polar) polymer for example, polymethyl methacrylate (PMMA) is used as the hydrophilic polymer, and for example, polystyrene (PS) is used as the hydrophobic polymer.
  • PMMA polymethyl methacrylate
  • PS polystyrene
  • the ratio of the molecular weight of the hydrophilic polymer in the block copolymer is 40% to 60%, and the ratio of the molecular weight of the hydrophobic polymer in the block copolymer is 60% to 40%.
  • the block copolymer is a polymer obtained by linearly combining these hydrophilic polymer and hydrophobic polymer.
  • the neutral layer formed on the wafer W by the neutral layer forming apparatus 33 has an intermediate affinity for the hydrophilic polymer and the hydrophobic polymer.
  • a random copolymer or an alternating copolymer of polymethyl methacrylate and polystyrene is used as the neutral layer.
  • neutral means having an intermediate affinity for the hydrophilic polymer and the hydrophobic polymer.
  • a heat treatment apparatus 40 for performing heat treatment of the wafer W, a resist modification for modifying the surface of the resist pattern by irradiating the resist pattern on the wafer W with ultraviolet rays.
  • An ultraviolet irradiation device 41 as a processing device, an adhesion device 42 that hydrophobizes the wafer W, a peripheral exposure device 43 that exposes the outer periphery of the wafer W, and a block copolymer coating device 35 that are applied onto the wafer W.
  • a polymer separator 44 for phase-separating the polymer into a hydrophilic polymer and a hydrophobic polymer is provided side by side in the vertical direction and the horizontal direction.
  • the heat treatment apparatus 40 includes a hot plate for placing and heating the wafer W and a cooling plate for placing and cooling the wafer W, and can perform both heat treatment and cooling treatment.
  • the polymer separation device 44 is also a device that performs heat treatment on the wafer W, and the configuration thereof is the same as that of the heat treatment device 40.
  • the ultraviolet irradiation device 41 includes a mounting table on which the wafer W is mounted, and an ultraviolet irradiation unit that irradiates the wafer W on the mounting table with, for example, ultraviolet light having a wavelength of 172 nm or 222 nm. Further, the number and arrangement of the heat treatment apparatus 40, the ultraviolet irradiation apparatus 41, the adhesion apparatus 42, the peripheral exposure apparatus 43, and the polymer separation apparatus 44 can be arbitrarily selected.
  • a plurality of delivery devices 50, 51, 52, 53, 54, 55, 56 are provided in order from the bottom.
  • the fourth block G4 is provided with a plurality of delivery devices 60, 61, 62 in order from the bottom.
  • a wafer transfer area D is formed in an area surrounded by the first block G1 to the fourth block G4.
  • a wafer transfer device 70 is disposed in the wafer transfer region D.
  • the wafer transfer device 70 has, for example, a transfer arm that is movable in the Y direction, the X direction, the ⁇ direction, and the vertical direction.
  • the wafer transfer device 70 moves in the wafer transfer area D and transfers the wafer W to a predetermined device in the surrounding first block G1, second block G2, third block G3, and fourth block G4. it can.
  • a plurality of wafer transfer apparatuses 70 are arranged in the vertical direction, and can transfer the wafer W to a predetermined apparatus having the same height of each of the blocks G1 to G4, for example.
  • a shuttle transfer device 80 that transfers the wafer W linearly between the third block G3 and the fourth block G4 is provided.
  • the shuttle transport device 80 is linearly movable in the Y direction, for example.
  • the shuttle transfer device 80 moves in the Y direction while supporting the wafer W, and can transfer the wafer W between the transfer device 52 of the third block G3 and the transfer device 62 of the fourth block G4.
  • a wafer transfer device 100 is provided next to the third block G3 on the positive side in the X direction.
  • the wafer transfer apparatus 100 has a transfer arm that is movable in the X direction, the ⁇ direction, and the vertical direction, for example.
  • the wafer transfer device 100 can move up and down while supporting the wafer W, and can transfer the wafer W to each delivery device in the third block G3.
  • the interface station 13 is provided with a wafer transfer device 110 and a delivery device 111.
  • the wafer transfer device 110 has a transfer arm that is movable in the Y direction, the ⁇ direction, and the vertical direction, for example.
  • the wafer transfer device 110 can transfer the wafer W between each transfer device, the transfer device 111, and the exposure device 12 in the fourth block G4, for example, by supporting the wafer W on a transfer arm.
  • the etching processing apparatus 3 includes a cassette station 200 that carries the wafer W into and out of the etching processing apparatus 3, a common transport unit 201 that transports the wafer W, and a block copolymer that is phase-separated on the wafer W.
  • the cassette station 200 has a transfer chamber 211 in which a wafer transfer mechanism 210 for transferring the wafer W is provided.
  • the wafer transfer mechanism 210 has two transfer arms 210a and 210b that hold the wafer W substantially horizontally, and is configured to transfer the wafer W while holding it by either of the transfer arms 210a and 210b.
  • a cassette mounting table 212 on which a cassette C capable of accommodating a plurality of wafers W arranged side by side is mounted on the side of the transfer chamber 211. In the illustrated example, a plurality of, for example, three cassettes C can be mounted on the cassette mounting table 212.
  • the transfer chamber 211 and the common transfer unit 201 are connected to each other via two load lock devices 213a and 213b that can be evacuated.
  • the common transfer unit 201 includes a transfer chamber chamber 214 having a sealable structure formed to have a substantially polygonal shape (in the illustrated example, a hexagonal shape) as viewed from above, for example.
  • a wafer transfer mechanism 215 for transferring the wafer W is provided in the transfer chamber 214.
  • the wafer transfer mechanism 215 has two transfer arms 215a and 215b that hold the wafer W substantially horizontally, and is configured to transfer the wafer W while holding the wafer W by either of the transfer arms 215a and 215b. .
  • Etching devices 202, 203, 204, 205 and load lock devices 213 b, 213 a are arranged outside the transfer chamber chamber 214 so as to surround the periphery of the transfer chamber chamber 214.
  • the etching devices 202, 203, 204, 205 and the load lock devices 213b, 213a are arranged in this order in the clockwise direction when viewed from above, for example, and face the six side portions of the transfer chamber 214, respectively. Are arranged.
  • etching apparatuses 202 to 205 for example, a RIE (Reactive Ion Etching) apparatus is used, for example. That is, in the etching apparatuses 202 to 205, dry etching for etching a hydrophobic polymer or a film to be processed is performed by a reactive gas (etching gas) such as oxygen (O 2 ), ions, or radicals, for example.
  • etching gas reactive gas
  • oxygen (O 2 ) oxygen
  • ions oxygen (O 2 )
  • radicals for example.
  • the developing device 30 has a processing container 130 in which a loading / unloading port (not shown) for the wafer W is formed on the side surface.
  • a spin chuck 140 that holds and rotates the wafer W is provided.
  • a suction port (not shown) for sucking the wafer W is provided. By suction from the suction port, the wafer W is sucked and held on the spin chuck 140.
  • the spin chuck 140 can be rotated at a predetermined speed by a chuck driving unit 141 such as a motor.
  • the chuck driving unit 141 is provided with an elevating drive source (not shown) such as a cylinder, and the spin chuck 140 is movable up and down.
  • a cup 142 that receives and collects the liquid scattered or dropped from the wafer W.
  • the cup 142 has an opening larger than the wafer W so that the spin chuck 140 can be moved up and down on the upper surface.
  • a discharge pipe 143 that discharges the collected liquid and an exhaust pipe 144 that exhausts the atmosphere in the cup 142 are connected to the lower surface of the cup 142.
  • a rail 150 extending along the Y direction is formed on the negative side of the cup 122 in the X direction (downward direction in FIG. 7).
  • the rail 150 is formed, for example, from the outside of the cup 142 on the Y direction negative direction (left direction of 7) to the outside of the Y direction positive direction (right direction of FIG. 7).
  • two arms 151 and 152 are attached to the rail 150.
  • the first arm 151 supports a supply nozzle 153 for supplying a developer as shown in FIGS.
  • the first arm 151 is movable on the rail 150 by a nozzle driving unit 154 shown in FIG.
  • the supply nozzle 153 can move from the standby unit 155 installed on the outer side of the cup 122 on the positive side in the Y direction to above the center of the wafer W in the cup 142, and further on the surface of the wafer W It can move in the radial direction of W.
  • the first arm 151 can be moved up and down by a nozzle driving unit 154, and the height of the supply nozzle 153 can be adjusted.
  • the supply nozzle 153 is connected to a developer supply pipe 157 communicating with the developer supply source 156 as shown in FIG.
  • the developer for example, an alkaline TMAH developer is used.
  • the second arm 152 supports a cleaning liquid nozzle 160 for supplying a cleaning liquid, for example, pure water.
  • the second arm 152 is movable on the rail 150 by the nozzle driving unit 161 shown in FIG. 7, and the cleaning liquid nozzle 160 is moved from the standby unit 162 provided outside the cup 142 on the Y direction negative direction side to the cup. 142 can be moved to above the center of the wafer W. Further, the second arm 152 can be moved up and down by the nozzle driving unit 161, and the height of the cleaning liquid nozzle 160 can be adjusted.
  • a cleaning liquid supply pipe 164 communicating with the cleaning liquid supply source 163 is connected to the cleaning liquid nozzle 160 as shown in FIG.
  • the cleaning liquid is stored in the cleaning liquid supply source 163.
  • the cleaning liquid supply pipe 164 is provided with a supply device group 165 including a valve for controlling the flow of the cleaning liquid, a flow rate adjusting unit, and the like.
  • the supply nozzle 153 for supplying the developer and the cleaning liquid nozzle 160 for supplying the cleaning liquid are supported by separate arms. However, the supply nozzle is supported by the same arm and controlled by movement of the arms. The movement and supply timing of 153 and the cleaning liquid nozzle 160 may be controlled.
  • the organic solvent supply device 31, the antireflection film forming device 32, the neutral layer forming device 33, the resist coating device 34, and the block copolymer coating device 35, which are other liquid processing devices, are configured by the liquid supplied from the nozzle. Except for the differences, the configuration is the same as that of the developing device 30 described above, and a description thereof will be omitted.
  • a TMAH developer mixed with 20 wt% of isopropyl alcohol (IPA) is used as the processing liquid supplied from the supply nozzle 153.
  • the substrate processing system 1 described above is provided with a control unit 300 as shown in FIG.
  • the control unit 300 is a computer, for example, and has a program storage unit (not shown).
  • the program storage unit stores a program for controlling the processing of the wafer W in the substrate processing system 1.
  • the program storage unit also stores a program for controlling the operation of driving systems such as the above-described various processing apparatuses and transfer apparatuses to realize a peeling process described later in the substrate processing system 1.
  • the program is recorded on a computer-readable storage medium such as a computer-readable hard disk (HD), flexible disk (FD), compact disk (CD), magnetic optical desk (MO), or memory card. Or installed in the control unit 300 from the storage medium.
  • HD computer-readable hard disk
  • FD flexible disk
  • CD compact disk
  • MO magnetic optical desk
  • FIG. 8 is a flowchart showing an example of main steps of such wafer processing.
  • a cassette C containing a plurality of wafers W is carried into the cassette station 10 of the coating and developing treatment apparatus 2 and placed on a predetermined cassette placing plate 21. Thereafter, the wafers W in the cassette C are sequentially taken out by the wafer transfer device 23 and transferred to the transfer device 53 of the processing station 11.
  • the wafer W is transferred to the heat treatment apparatus 40 by the wafer transfer apparatus 70 and the temperature is adjusted. Thereafter, the wafer W is transferred to the antireflection film forming apparatus 32 by the wafer transfer apparatus 70, and an antireflection film 400 is formed on the wafer W as shown in FIG. 9 (step S1 in FIG. 8). Thereafter, the wafer W is transferred to the heat treatment apparatus 40, heated, and the temperature is adjusted.
  • the wafer W is transferred to the neutral layer forming device 33 by the wafer transfer device 70.
  • the neutral layer forming apparatus 33 as shown in FIG. 9, a neutral agent is applied on the antireflection film 400 of the wafer W to form a neutral layer 401 (step S2 in FIG. 8).
  • the wafer W is transferred to the heat treatment apparatus 40, heated, temperature-controlled, and then returned to the delivery apparatus 53.
  • the wafer W is transferred to the delivery device 54 by the wafer transfer device 100. Thereafter, the wafer W is transferred to the adhesion device 42 by the wafer transfer device 70 and subjected to an adhesion process. Thereafter, the wafer W is transferred to the resist coating device 34 by the wafer transfer device 70, and a resist solution is applied onto the neutral layer 401 of the wafer W to form a resist film. Thereafter, the wafer W is transferred to the heat treatment apparatus 40 by the wafer transfer apparatus 70 and pre-baked. Thereafter, the wafer W is transferred to the delivery device 55 by the wafer transfer device 70.
  • the wafer W is transferred to the peripheral exposure device 43 by the wafer transfer device 70 and subjected to peripheral exposure processing. Thereafter, the wafer W is transferred to the delivery device 56 by the wafer transfer device 70.
  • the wafer W is transferred to the transfer device 52 by the wafer transfer device 100 and transferred to the transfer device 62 by the shuttle transfer device 80.
  • the wafer W is transferred to the exposure apparatus 12 by the wafer transfer apparatus 110 of the interface station 13 and subjected to exposure processing.
  • the wafer W is transferred from the exposure apparatus 12 to the delivery apparatus 60 by the wafer transfer apparatus 110. Thereafter, the wafer W is transferred to the heat treatment apparatus 40 by the wafer transfer apparatus 70 and subjected to post-exposure baking. Thereafter, the wafer W is transferred to the developing device 30 by the wafer transfer device 70 and developed. After the development is completed, the wafer W is transferred to the heat treatment apparatus 40 by the wafer transfer apparatus 70 and subjected to a post-bake process. Thus, a predetermined resist pattern 402 is formed on the neutral layer 401 of the wafer W as shown in FIG. 10 (step S3 in FIG. 8).
  • an altered portion RM which is a portion where the physical properties of the resist film have changed, is present on the side wall of the surface of the resist pattern 402 at the stage of completing the development process.
  • the intermediate exposure area which is an intermediate area between the area exposed by the exposure process (exposure area) and the area where light is blocked by the mask and not exposed (unexposed area)
  • the following states This is because the resist film is formed. That is, firstly, the exposure is sufficient and originally sufficiently dissolved in the developer, but remains undissolved because it is an interface with the unexposed region, and secondly, the exposure However, the amount of exposure is not sufficient, and it remains without being sufficiently dissolved in the developer. Third, the exposure is hardly performed and it remains without being dissolved in the developer.
  • the altered portion RM is a mixture of the resist films in these states. In the altered portion RM, the hydrophobicity varies depending on the state of the resist film.
  • the resist pattern 402 is a so-called line-and-space resist pattern having a straight line portion 402a and a straight space portion 402b in plan view. Further, the width of the space portion 402b is set so that the hydrophilic polymer 405 and the hydrophobic polymer 406 are alternately arranged in the odd number layers along the longitudinal direction of the resist pattern 402 in the space portion 402b as described later.
  • the wafer W on which the resist pattern 402 is formed is transferred to the ultraviolet irradiation device 41 by the wafer transfer device 70.
  • the ultraviolet irradiation device 41 the resist pattern 402 is irradiated with ultraviolet rays.
  • ultraviolet rays having a wavelength of 172 nm are irradiated for 5 seconds, for example.
  • the modification process including the part where the exposure amount in the altered portion RM generated in the intermediate exposure region is not sufficient and the part where the exposure is hardly performed is performed and the negative result is obtained. (Step S4 in FIG. 8).
  • the wafer W is transferred to the organic solvent supply device 31 by the wafer transfer device 70.
  • a processing solution in which 20 wt% of isopropyl alcohol is mixed with TMAH developer is supplied onto the wafer W, and the surface treatment of the resist pattern 402 is performed.
  • the altered portion RM remaining on the surface of the resist pattern 402 as shown in FIG. 11 is removed (step S5 in FIG. 8).
  • the wafer W is transferred to the delivery device 50 by the wafer transfer device 70.
  • the wafer W is transferred to the delivery device 55 by the wafer transfer device 100. Thereafter, the wafer W is transferred to the block copolymer coating device 35 by the wafer transfer device 70. In the block copolymer coating device 35, the block copolymer 404 is coated on the neutral layer 401 of the wafer W as shown in FIG. 12 (step S6 in FIG. 8).
  • the wafer W is transferred to the polymer separation device 44 by the wafer transfer device 70.
  • the wafer W is heat-treated at a predetermined temperature.
  • the block copolymer 404 on the wafer W is phase-separated into the hydrophilic polymer 405 and the hydrophobic polymer 406 (step S7 in FIG. 8).
  • the molecular weight ratio of the hydrophilic polymer 405 is 40% to 60%
  • the molecular weight ratio of the hydrophobic polymer 406 is 60% to 40%.
  • the hydrophobicity does not vary on the sidewall of the resist pattern 402 surface. Therefore, the resist pattern 402 has sufficiently high hydrophobicity over the entire side wall. Therefore, the hydrophobic polymer 406 is easily attracted to the resist pattern 402, and the hydrophobic polymer 406 is disposed adjacent to the resist pattern 402.
  • the hydrophilic polymer 405 and the hydrophobic polymer 406 are alternately arranged next to each other, and the hydrophilic polymer 405 and the hydrophobic polymer 406 are also alternately arranged on other regions of the neutral layer 401.
  • the wafer W is transferred to the delivery device 50 by the wafer transfer device 70, and then transferred to the cassette C of the predetermined cassette mounting plate 21 by the wafer transfer device 23 of the cassette station 10.
  • the cassette C containing the wafer W is unloaded from the coating and developing treatment apparatus 2 and then loaded into the etching processing apparatus 3.
  • the etching processing apparatus 3 first, one wafer W is taken out from the cassette C on the cassette mounting table 212 by the wafer transfer mechanism 210 and loaded into the load lock apparatus 213 a.
  • the inside of the load lock device 213a is sealed and decompressed.
  • the inside of the load lock device 213a and the inside of the transfer chamber chamber 214 evacuated to a predetermined degree of vacuum are communicated.
  • the wafer transfer mechanism 215 unloads the wafer W from the load lock device 213a and loads it into the transfer chamber 214.
  • the wafer W carried into the transfer chamber 214 is then transferred to the etching apparatus 202 by the wafer transfer mechanism 215.
  • the wafer W is etched, and the hydrophilic polymer 405 and the resist pattern 402 are selectively removed as shown in FIG. 15 to form a predetermined pattern of the hydrophobic polymer 406 (FIG. 8). Step S8).
  • the wafer W is transferred to the etching apparatus 204 by the wafer transfer mechanism 215.
  • the film to be processed on the wafer W is etched using the hydrophobic polymer 406 on the wafer W as a mask.
  • the hydrophobic polymer 406 and the antireflection film are removed, and a predetermined pattern is formed on the film to be processed (step S9 in FIG. 8).
  • the wafer W is returned again into the transfer chamber 214 by the wafer transfer mechanism 215. Then, the wafer is transferred to the wafer transfer mechanism 210 via the load lock device 213b and stored in the cassette C. Thereafter, the cassette C containing the wafers W is unloaded from the etching processing apparatus 3 and a series of wafer processing ends.
  • isopropyl alcohol is supplied as an organic solvent having polarity in step S5 to remove the altered portion RM on the surface of the resist pattern 402, and an unexposed region, that is, a hydrophobic region over the entire sidewall of the resist pattern 402. Since the surface of the resist pattern 402 after development is exposed, it is possible to prevent the polymers 405 and 406 from being randomly arranged when the block copolymer 404 is phase-separated in step S7, thereby forming a desired pattern. it can. As a result, in the process S9, the processing target film can be appropriately etched using the pattern as a mask, and a predetermined pattern can be formed on the processing target film.
  • 172 nm ultraviolet rays were irradiated to modify the altered portion RM.
  • the inventors confirmed that ultraviolet irradiation is not always necessary, and 20 wt% of isopropyl alcohol is mixed with the TMAH developer. It was found that the altered portion RM can be removed by supplying the treated liquid.
  • the above-mentioned resist in the region that is hardly exposed is insoluble in TMAH developer but is soluble in isopropyl alcohol, and the resist in the region that is exposed but not sufficiently exposed is TMAH developed. It is assumed that it is slightly soluble in both liquid and isopropyl alcohol.
  • the wavelength of the ultraviolet rays used for the modification of the altered portion RM may not be 172 nm, for example, a wavelength of 222 nm.
  • the altered part RM was modified by ultraviolet rays having a wavelength of 222 nm, it was confirmed that the altered part RM can be removed by supplying the TMAH developer to the wafer W. This is considered to be because, by irradiating the resist pattern 402 with ultraviolet light having a wavelength of 222 nm, the altered portion RM is reliably modified from positive to negative, and the altered portion RM that has been converted into negative is washed away by the TMAH developer. It is done.
  • the organic solvent is supplied to the wafer W after the development processing of the resist pattern 402 to remove the altered portion RM.
  • 20 wt% of isopropyl alcohol is added to the TMAH developer.
  • the resist pattern 402 may be developed by supplying a mixed processing solution. According to the inventors, when a processing solution in which 20 wt% of isopropyl alcohol is mixed with a TMAH developer is supplied to the resist pattern 402 irradiated with ultraviolet rays after development, the processing solution is applied to the wafer W after the exposure processing and before development. No difference was observed regarding the removal of the altered portion RM between the case where the slag was supplied.
  • the wafer W after the development processing of the resist pattern 402 is supplied in a state where 20 wt% of isopropyl alcohol is mixed with the TMAH developer.
  • isopropyl alcohol is applied to the resist pattern 402 after the development processing.
  • a TMAH developer may be further supplied. Even in such a case, it was confirmed that the altered portion RM can be removed in the same manner as when a processing solution in which 20 wt% of isopropyl alcohol is mixed with the TMAH developer is supplied.
  • a portion soluble in the TMAH developer and a portion soluble in isopropyl alcohol are mixed, so that the TMAH development is performed from the viewpoint of dissolving both portions in parallel. More preferably, the liquid and isopropyl alcohol are mixed and supplied.
  • the so-called dry etching process is performed in the etching processing apparatus 3 to selectively remove the hydrophilic polymer 405, but the hydrophilic polymer 405 may be removed by a wet etching process.
  • the wafer W obtained by phase separation of the block copolymer 404 in step S7 is transferred to the ultraviolet irradiation device 41 in place of the etching processing apparatus 3 in step S8. Then, by irradiating the wafer W with ultraviolet rays, the bonding chain of polymethyl methacrylate, which is the hydrophilic polymer 405, is cut, and the polystyrene, which is the hydrophobic polymer 406, is crosslinked. Thereafter, the wafer W is transferred again to the organic solvent supply device 31, and isopropyl alcohol (IPA), which is a polar organic solvent, is supplied to the wafer W in the organic solvent supply device 31. As a result, the hydrophilic polymer 405 having the bond chain cleaved by ultraviolet irradiation is dissolved and removed.
  • IPA isopropyl alcohol
  • the selective ratio between the hydrophilic polymer 405 and the hydrophobic polymer 406 is, for example, about 3 to 7: 1.
  • the hydrophilic polymer 405 is removed by so-called wet etching using an organic solvent, since the hydrophobic polymer 406 has no polarity, it hardly dissolves in the organic solvent, and film slippage can be avoided. As a result, a sufficient film thickness as a mask can be ensured when etching the film to be processed using the pattern of the hydrophobic polymer 406 as a mask in subsequent steps.
  • the transfer of the wafer W from the coating and developing treatment apparatus 2 to the etching treatment apparatus 3 can be omitted. Therefore, the throughput of wafer processing in the substrate processing system 1 can be improved.
  • the film to be processed on the wafer W is etched in step S9, but the wafer processing method of the present invention can also be applied when etching the wafer W itself.
  • the block copolymer 404 on the wafer W is phase-separated into the hydrophilic polymer 405 having a lamellar structure and the hydrophobic polymer 406 has been described.
  • the present invention can also be applied to the case where the copolymer 404 is phase-separated into a hydrophilic polymer 405 having a cylindrical structure and a hydrophobic polymer 406.
  • the ratio of the molecular weight of the hydrophilic polymer 405 is 20% to 40%, and the ratio of the molecular weight of the hydrophobic polymer 406 is Is 80% to 60%.
  • a resist pattern 402 having a circular space portion 402c in plan view is formed on the wafer W as shown in FIGS.
  • the altered portion RM also exists on the side wall of the surface of the resist pattern 402. Therefore, the modified portion RM is modified and removed in steps S4 to S5.
  • step S6 the block copolymer 404 is applied to the space part 402c of the resist pattern 402 from which the altered part RM has been removed. Thereafter, in step S7, the block copolymer 404 is phase-separated. At this time, since the altered portion RM is already removed, it is possible to prevent the hydrophilic polymer 405 and the hydrophobic polymer 406 from being randomly arranged with respect to the resist pattern 402. Since the hydrophobic polymer 406 is easily attracted to the resist pattern 402 having hydrophobicity, as shown in FIG. 18, the hydrophobic polymer 406 is arranged in a cylindrical shape on the side wall side of the resist pattern 402 in the space portion 402c. A cylindrical hydrophilic polymer 405 is arranged in the center of the space portion 402c.
  • the present invention is not limited to such examples. It is obvious for those skilled in the art that various changes or modifications can be conceived within the scope of the idea described in the claims, and these are naturally within the technical scope of the present invention. It is understood.
  • the present invention is not limited to this example and can take various forms.
  • the present invention can also be applied to a case where the substrate is another substrate such as an FPD (flat panel display) other than a wafer or a mask reticle for a photomask.
  • FPD flat panel display
  • the present invention is useful when a substrate is treated with a block copolymer containing, for example, a hydrophilic polymer having hydrophilicity and a hydrophobic polymer having hydrophobicity.

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