WO2024101166A1 - 基板処理方法、金属含有レジスト形成用組成物、金属含有レジスト及び基板処理システム - Google Patents

基板処理方法、金属含有レジスト形成用組成物、金属含有レジスト及び基板処理システム Download PDF

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Publication number
WO2024101166A1
WO2024101166A1 PCT/JP2023/038633 JP2023038633W WO2024101166A1 WO 2024101166 A1 WO2024101166 A1 WO 2024101166A1 JP 2023038633 W JP2023038633 W JP 2023038633W WO 2024101166 A1 WO2024101166 A1 WO 2024101166A1
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Prior art keywords
metal
group
substrate
film
compound
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PCT/JP2023/038633
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English (en)
French (fr)
Japanese (ja)
Inventor
健太 小野
由太 中根
翔 熊倉
哲也 西塚
昌伸 本田
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Tokyo Electron Ltd
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Tokyo Electron Ltd
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Priority to JP2024557314A priority Critical patent/JPWO2024101166A1/ja
Priority to EP23888514.9A priority patent/EP4617777A1/en
Priority to KR1020257018129A priority patent/KR20250107207A/ko
Priority to CN202380076750.4A priority patent/CN120153326A/zh
Publication of WO2024101166A1 publication Critical patent/WO2024101166A1/ja
Priority to US19/199,672 priority patent/US20250264805A1/en
Anticipated expiration legal-status Critical
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    • 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
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • 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
    • G03F7/004—Photosensitive materials
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    • 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
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    • G03F7/004—Photosensitive materials
    • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
    • G03F7/0043—Chalcogenides; Silicon, germanium, arsenic or derivatives thereof; Metals, oxides or alloys thereof
    • 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
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    • G03F7/094—Multilayer resist systems, e.g. planarising layers
    • G—PHYSICS
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    • 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
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/095—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having more than one photosensitive layer
    • G—PHYSICS
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    • 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
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • 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
    • 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
    • G03F7/162—Coating on a rotating support, e.g. using a whirler or a spinner
    • 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
    • G03F7/167—Coating processes; Apparatus therefor from the gas phase, by plasma deposition
    • 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
    • G03F7/168—Finishing the coated layer, e.g. drying, baking, soaking
    • 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
    • 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
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G03F7/325—Non-aqueous compositions
    • 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
    • G03F7/38—Treatment before imagewise removal, e.g. prebaking
    • 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
    • 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
    • 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
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/60—Formation of materials, e.g. in the shape of layers or pillars of insulating 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
    • 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
    • H10P76/40—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising inorganic materials
    • H10P76/408—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising inorganic materials characterised by their sizes, orientations, dispositions, behaviours or shapes
    • H10P76/4085—Manufacture or treatment of masks on semiconductor bodies, e.g. by lithography or photolithography of masks comprising inorganic materials characterised by their sizes, orientations, dispositions, behaviours or shapes characterised by the processes involved to create the masks

Definitions

  • Exemplary embodiments of the present disclosure relate to a substrate processing method, a composition for forming a metal-containing resist, a metal-containing resist, and a substrate processing system.
  • Patent Document 1 discloses a technology for forming a thin film that can be patterned on a semiconductor substrate using extreme ultraviolet light (hereinafter referred to as EUV).
  • EUV extreme ultraviolet light
  • This disclosure provides a technique for adjusting the composition of a metal-containing resist film formed on a substrate.
  • a substrate processing method including the steps of: (a) providing a substrate having an undercoat film; and (b) forming a metal-containing resist film on the undercoat film using a metal-containing precursor having a photosensitive group and a polyfunctional compound.
  • a technique can be provided for adjusting the composition of a metal-containing resist film formed on a substrate.
  • FIG. 1 is a diagram for explaining a configuration example of a heat treatment system.
  • FIG. 1 is a diagram for explaining a configuration example of a plasma processing system.
  • FIG. 1 is a diagram for explaining a configuration example of a capacitively coupled plasma processing apparatus.
  • FIG. 1 is a diagram for explaining a configuration example of a liquid processing system.
  • 3 is a flowchart showing the present processing method.
  • 2 is a diagram showing an example of an undercoat film UF of a substrate W.
  • FIG. 2 is a diagram showing an example of an undercoat film UF of a substrate W.
  • FIG. 2 is a diagram showing an example of a cross-sectional structure of a substrate W on which a metal-containing resist film RM is formed.
  • 11 is a flowchart showing an example of a process ST2 using an ALD method.
  • 11 is a flowchart showing an example of a process ST2 using an ALD method.
  • 1A to 1C are diagrams illustrating an example of a phenomenon that occurs on the surface of a substrate W in a process ST2 using an ALD method.
  • FIG. 2 is a block diagram for explaining an example of the configuration of a substrate processing system SS.
  • 1 is a flowchart showing a method MT.
  • a substrate processing method includes the steps of: (a) providing a substrate having an undercoat film; and (b) forming a metal-containing resist film on the undercoat film using a metal-containing precursor having a photosensitive group and a polyfunctional compound.
  • the metal-containing precursor comprises a compound ( ⁇ ) having an amine group and/or an alkoxy group.
  • compound ( ⁇ ) includes compound ( ⁇ 1) containing at least one metal selected from the group consisting of Sn, Ti, Hf, Zr, and In.
  • compound ( ⁇ 1) contains Sn.
  • the photosensitive group comprises at least one group selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an i-propyl group, a t-butyl group, and -CH x F y (wherein x represents an integer of 0 to 2, and y represents an integer of 1 to 3).
  • the polyfunctional compound includes at least one compound ( ⁇ ) selected from the group consisting of polyalcohols, polythiols, polycarboxylic acids, polyisocyanates, and polyisothiocyanates.
  • step (b) further includes at least one selected from the group consisting of H 2 O, H 2 O 2 , O 3 , and O 2 .
  • step (b) includes the steps of (b1) supplying a gas containing a metal-containing precursor onto the base film to form a metal-containing precursor film, and (b2) supplying a gas containing a polyfunctional compound to the metal-containing precursor film to form a metal-containing resist film from the metal-containing precursor film.
  • steps (b1) and (b2) are repeated multiple times.
  • step (b) includes forming a metal-containing resist film using a mixed gas containing a metal-containing precursor and a multifunctional compound.
  • the metal-containing precursor comprises a metal complex containing at least one metal selected from the group consisting of Sn, Ti, Hf, Zr, and In.
  • the polyfunctional compound includes at least one compound ( ⁇ ) selected from the group consisting of polyalcohols, polythiols, polycarboxylic acids, polyisocyanates, and polyisothiocyanates.
  • step (b) includes applying a solution containing a metal-containing precursor and a polyfunctional compound onto the base film, and heating the applied solution to form a metal-containing resist film.
  • the substrate processing method further includes (c) exposing the substrate after step (b) to form an exposed first region and an unexposed second region in the metal-containing resist film, and (d) developing the substrate to selectively remove the second region from the metal-containing resist film.
  • step (d) the second region is removed using a developing gas or liquid containing a weak acid.
  • the weak acid comprises an organic acid with a pKa ⁇ 16.
  • the organic acid includes at least one selected from the group consisting of alcohols, thiols, carboxylic acids, sulfonic acids, ⁇ -diketones, alkyl carbonates, and azoles.
  • a metal-containing resist-forming composition includes a metal-containing precursor having a photosensitive group and a polyfunctional compound, where the metal-containing precursor includes a compound having a photosensitive group and an amine group and/or an alkoxy group.
  • a metal-containing resist includes a compound having a repeat unit represented by the following formula (1) in the molecule: -(M-X-A-X)- (1)
  • M represents Sn, Ti, Hf, Zr, or In
  • X represents a divalent group derived from a terminal functional group of a polyalcohol, a polythiol, a polycarboxylic acid, a polyisocyanate, or a polyisothiocyanate
  • A represents a divalent organic group having 2 or more and 10 or less carbon atoms.
  • a substrate processing system has one or more substrate processing apparatuses and a controller, and the controller is configured to control the one or more substrate processing apparatuses to (a) provide a substrate having an undercoat film, and (b) form a metal-containing resist film on the undercoat film using a metal-containing precursor having a photosensitive group and a multifunctional compound.
  • a developing method includes the steps of: (a) providing a substrate having an undercoat film and a metal-containing resist on the undercoat film; (b) exposing the metal-containing resist through an exposure mask to form an exposed first region and an unexposed second region in the metal-containing resist; and (c) selectively removing one of the first region and the second region, wherein the metal-containing resist in the step (a) contains a compound having a repeating unit represented by the following formula (1) in its molecule: -(M-X-A-X)- (1) (In the above formula (1), M represents Sn, Ti, Hf, Zr, or In, X represents a divalent group derived from a terminal functional group of a polyalcohol, a polythiol, a polycarboxylic acid, a polyisocyanate, or a polyisothiocyanate, and A represents a divalent organic group having 2 or more and 10 or less carbon atoms.) is provided.
  • an etching method includes the steps of: (a) providing a substrate having an undercoat film and a metal-containing resist on the undercoat film, wherein the metal-containing resist has at least one opening; and (b) etching the undercoat film through the opening, wherein the metal-containing resist contains a compound having a repeating unit represented by the following formula (1) in its molecule: -(M-X-A-X)- (1)
  • M represents Sn, Ti, Hf, Zr, or In
  • X represents a divalent group derived from a terminal functional group of a polyalcohol, a polythiol, a polycarboxylic acid, a polyisocyanate, or a polyisothiocyanate
  • A represents a divalent organic group having 2 or more and 10 or less carbon atoms.
  • the substrate processing method according to the present disclosure may be performed by a substrate processing system.
  • the substrate processing system has one or more substrate processing apparatuses and a controller, and the controller is configured to control the one or more substrate processing apparatuses to (a) provide a substrate having an undercoat film, and (b) form a metal-containing resist film on the undercoat film using a metal-containing precursor having a photosensitive group and a multifunctional compound.
  • the substrate processing system according to the present disclosure may include a heat processing system, a plasma processing system, a liquid processing system, etc.
  • ⁇ Example of heat treatment system configuration> 1 is a diagram for explaining an example of the configuration of a heat treatment system.
  • the heat treatment system includes a heat treatment device 100 and a control unit 200.
  • the heat treatment system is an example of a substrate treatment system
  • the heat treatment device 100 is an example of a substrate treatment device.
  • the heat treatment apparatus 100 has a processing chamber 102 configured to be able to form an enclosed space.
  • the processing chamber 102 is, for example, an airtight cylindrical container, and is configured to be able to adjust the atmosphere inside.
  • a side wall heater 104 is provided on the side wall of the processing chamber 102.
  • a ceiling heater 130 is provided on the ceiling wall (top plate) of the processing chamber 102.
  • the ceiling surface 140 of the ceiling wall (top plate) of the processing chamber 102 is formed as a horizontal flat surface, and its temperature is adjusted by the ceiling heater 130.
  • a substrate support 121 is provided at the lower side of the processing chamber 102.
  • the substrate support 121 has a substrate support surface on which the substrate W is supported.
  • the substrate support 121 is formed, for example, in a circular shape in a plan view, and the substrate W is placed on its horizontally formed surface (upper surface).
  • a stage heater 120 is embedded in the substrate support 121. This stage heater 120 can heat the substrate W placed on the substrate support 121.
  • a ring assembly (not shown) may be arranged in the substrate support 121 to surround the substrate W.
  • the ring assembly may include one or more annular members. By arranging the ring assembly around the substrate W, the temperature controllability of the outer peripheral region of the substrate W can be improved.
  • the ring assembly may be made of an inorganic material or an organic material depending on the intended heat treatment.
  • the substrate support 121 is supported within the processing chamber 102 by pillars 122 provided on the bottom surface of the processing chamber 102.
  • a plurality of lift pins 123 that can be raised and lowered vertically are provided on the circumferential outer side of the pillars 122.
  • Each of the lift pins 123 is inserted into a through hole provided in the substrate support 121.
  • the lift pins 123 are arranged at intervals in the circumferential direction.
  • the lifting and lowering operation of the lift pins 123 is controlled by a lifting mechanism 124.
  • the side wall of the processing chamber 102 is provided with an exhaust port 131 having an opening.
  • the exhaust port 131 is connected to an exhaust mechanism 132 via an exhaust pipe.
  • the exhaust mechanism 132 is composed of a vacuum pump, a valve, etc., and adjusts the exhaust flow rate from the exhaust port 131.
  • the pressure inside the processing chamber 102 is adjusted by adjusting the exhaust flow rate, etc., using the exhaust mechanism 132.
  • a transfer port for a substrate W (not shown) is formed in the side wall of the processing chamber 102 at a position different from the position where the exhaust port 131 opens, so as to be freely opened and closed.
  • a gas nozzle 141 is provided on the sidewall of the processing chamber 102 at a position different from the exhaust port 131 and the transfer port for the substrate W.
  • the gas nozzle 141 supplies processing gas into the processing chamber 102.
  • the gas nozzle 141 is provided on the sidewall of the processing chamber 102 on the opposite side of the exhaust port 131 when viewed from the center of the substrate support part 121.
  • the gas nozzle 141 is provided on the sidewall of the processing chamber 102 symmetrically to the exhaust port 131 with respect to a vertical imaginary plane that passes through the center of the substrate support part 121.
  • the gas nozzle 141 is formed in a rod shape that protrudes from the sidewall of the processing chamber 102 toward the center of the processing chamber 102.
  • the tip of the gas nozzle 141 extends, for example, horizontally from the sidewall of the processing chamber 102.
  • the processing gas is discharged into the processing chamber 102 from a discharge port that opens at the tip of the gas nozzle 141, flows in the direction of the dashed arrow shown in FIG. 1, and is exhausted from the exhaust port 131.
  • the tip of the gas nozzle 141 may have a shape that extends diagonally downward toward the substrate W, or may have a shape that extends diagonally upward toward the ceiling surface 140 of the processing chamber 102.
  • the gas nozzle 141 may be provided, for example, in the ceiling wall of the processing chamber 102.
  • the exhaust port 131 may be provided in the bottom surface of the processing chamber 102.
  • the heat treatment apparatus 100 has a gas supply pipe 152 that is connected to a gas nozzle 141 from the outside of the processing chamber 102.
  • a piping heater 160 for heating the gas in the gas supply pipe is provided around the gas supply pipe 152.
  • the gas supply pipe 152 is connected to a gas supply unit 170.
  • the gas supply unit 170 includes at least one gas source and at least one flow rate controller.
  • the gas supply unit may include a vaporizer that vaporizes a material in a liquid state.
  • the control unit 200 processes computer-executable instructions that cause the heat treatment device 100 to perform the various steps described in this disclosure.
  • the control unit 200 may be configured to control each element of the heat treatment device 100 to perform the various steps described herein. In one embodiment, a part or all of the control unit 200 may be included in the heat treatment device 100.
  • the control unit 200 may include a processing unit 200a1, a storage unit 200a2, and a communication interface 200a3.
  • the control unit 200 is realized, for example, by a computer 200a.
  • the processing unit 200a1 may be configured to perform various control operations by reading a program from the storage unit 200a2 and executing the read program. This program may be stored in the storage unit 200a2 in advance, or may be acquired via a medium when necessary.
  • the acquired program is stored in the storage unit 200a2 and is read from the storage unit 200a2 by the processing unit 200a1 and executed.
  • the medium may be various storage media readable by the computer 200a, or may be a communication line connected to the communication interface 200a3.
  • the processing unit 200a1 may be a CPU (Central Processing Unit).
  • the memory unit 200a2 may include a RAM (Random Access Memory), a ROM (Read Only Memory), a HDD (Hard Disk Drive), an SSD (Solid State Drive), or a combination thereof.
  • the communication interface 200a3 may communicate with the heat treatment device 100 via a communication line such as a LAN (Local Area Network).
  • FIG. 2 is a diagram for explaining a configuration example of a plasma processing system.
  • the plasma processing system includes a plasma processing device 1 and a control unit 2.
  • the plasma processing system is an example of a substrate processing system
  • the plasma processing device 1 is an example of a substrate processing device.
  • the plasma processing device 1 includes a plasma processing chamber (hereinafter, also simply referred to as a "processing chamber") 10, a substrate support unit 11, and a plasma generation unit 12.
  • the plasma processing chamber 10 has a plasma processing space.
  • the plasma processing chamber 10 also has at least one gas supply port for supplying at least one processing gas to the plasma processing space, and at least one gas exhaust port for exhausting gas from the plasma processing space.
  • the gas supply port is connected to a gas supply unit 20 described later, and the gas exhaust port is connected to an exhaust system 40 described later.
  • the substrate support unit 11 is disposed in the plasma processing space, and has a substrate support surface for supporting a substrate.
  • the plasma generating unit 12 is configured to generate plasma from at least one processing gas supplied into the plasma processing space.
  • the plasma formed in the plasma processing space may be capacitively coupled plasma (CCP), inductively coupled plasma (ICP), electron-cyclotron-resonance plasma (ECR plasma), helicon wave excited plasma (HWP), or surface wave plasma (SWP), etc.
  • various types of plasma generating units may be used, including an alternating current (AC) plasma generating unit and a direct current (DC) plasma generating unit.
  • the AC signal (AC power) used in the AC plasma generation unit has a frequency in the range of 100 kHz to 10 GHz.
  • the AC signal includes an RF (Radio Frequency) signal and a microwave signal.
  • the RF signal has a frequency in the range of 100 kHz to 150 MHz.
  • the control unit 2 processes computer-executable instructions that cause the plasma processing apparatus 1 to perform the various steps described in this disclosure.
  • the control unit 2 may be configured to control each element of the plasma processing apparatus 1 to perform the various steps described herein. In one embodiment, a part or all of the control unit 2 may be included in the plasma processing apparatus 1.
  • the control unit 2 is realized by, for example, a computer 2a.
  • the control unit 2 may include a processing unit 2a1, a memory unit 2a2, and a communication interface 2a3. Each component of the control unit 2 may be similar to each component of the control unit 200 (see FIG. 1) described above.
  • FIG. 3 is a diagram for explaining a configuration example of a capacitively coupled plasma processing device.
  • the capacitively coupled plasma processing apparatus 1 includes a plasma processing chamber 10, a gas supply unit 20, a power supply 30, and an exhaust system 40.
  • the plasma processing apparatus 1 also includes a substrate support unit 11 and a gas inlet unit.
  • the gas inlet unit is configured to introduce at least one processing gas into the plasma processing chamber 10.
  • the gas inlet unit includes a shower head 13.
  • the substrate support unit 11 is disposed in the plasma processing chamber 10.
  • the shower head 13 is disposed above the substrate support unit 11. In one embodiment, the shower head 13 constitutes at least a part of the ceiling of the plasma processing chamber 10.
  • the plasma processing chamber 10 has a plasma processing space 10s defined by the shower head 13, the sidewall 10a of the plasma processing chamber 10, and the substrate support unit 11.
  • the plasma processing chamber 10 is grounded.
  • the shower head 13 and the substrate support unit 11 are electrically insulated from the housing of the plasma processing chamber 10.
  • the substrate support 11 includes a main body 111 and a ring assembly 112.
  • the main body 111 has a central region 111a for supporting the substrate W and an annular region 111b for supporting the ring assembly 112.
  • a wafer is an example of a substrate W.
  • the annular region 111b of the main body 111 surrounds the central region 111a of the main body 111 in a plan view.
  • the substrate W is disposed on the central region 111a of the main body 111
  • the ring assembly 112 is disposed on the annular region 111b of the main body 111 so as to surround the substrate W on the central region 111a of the main body 111. Therefore, the central region 111a is also called a substrate support surface for supporting the substrate W, and the annular region 111b is also called a ring support surface for supporting the ring assembly 112.
  • the main body 111 includes a base 1110 and an electrostatic chuck 1111.
  • the base 1110 includes a conductive member.
  • the conductive member of the base 1110 may function as a lower electrode.
  • the electrostatic chuck 1111 is disposed on the base 1110.
  • the electrostatic chuck 1111 includes a ceramic member 1111a and an electrostatic electrode 1111b disposed within the ceramic member 1111a.
  • the ceramic member 1111a has a central region 111a. In one embodiment, the ceramic member 1111a also has an annular region 111b. Note that other members surrounding the electrostatic chuck 1111, such as an annular electrostatic chuck or an annular insulating member, may have the annular region 111b.
  • the ring assembly 112 may be disposed on the annular electrostatic chuck or the annular insulating member, or may be disposed on both the electrostatic chuck 1111 and the annular insulating member.
  • at least one RF/DC electrode coupled to an RF power source 31 and/or a DC power source 32 described later may be disposed in the ceramic member 1111a.
  • the at least one RF/DC electrode functions as a lower electrode.
  • the RF/DC electrode is also called a bias electrode.
  • the conductive member of the base 1110 and the at least one RF/DC electrode may function as multiple lower electrodes.
  • the electrostatic electrode 1111b may function as a lower electrode.
  • the substrate support 11 includes at least one lower electrode.
  • the ring assembly 112 includes one or more annular members.
  • the one or more annular members include one or more edge rings and at least one cover ring.
  • the edge rings are formed of a conductive or insulating material, and the cover rings are formed of an insulating material.
  • the substrate support 11 may also include a temperature adjustment module configured to adjust at least one of the electrostatic chuck 1111, the ring assembly 112, and the substrate to a target temperature.
  • the temperature adjustment module may include a heater, a heat transfer medium, a flow passage 1110a, or a combination thereof.
  • a heat transfer fluid such as brine or a gas flows through the flow passage 1110a.
  • the flow passage 1110a is formed in the base 1110, and one or more heaters are disposed in the ceramic member 1111a of the electrostatic chuck 1111.
  • the substrate support 11 may also include a heat transfer gas supply configured to supply a heat transfer gas to a gap between the back surface of the substrate W and the central region 111a.
  • the shower head 13 is configured to introduce at least one processing gas from the gas supply unit 20 into the plasma processing space 10s.
  • the shower head 13 has at least one gas supply port 13a, at least one gas diffusion chamber 13b, and multiple gas inlets 13c.
  • the processing gas supplied to the gas supply port 13a passes through the gas diffusion chamber 13b and is introduced into the plasma processing space 10s from the multiple gas inlets 13c.
  • the shower head 13 also includes at least one upper electrode.
  • the gas introduction unit may include, in addition to the shower head 13, one or more side gas injectors (SGI) attached to one or more openings formed in the side wall 10a.
  • SGI side gas injectors
  • the gas supply unit 20 may include at least one gas source 21 and at least one flow controller 22.
  • the gas supply unit 20 is configured to supply at least one process gas from a respective gas source 21 through a respective flow controller 22 to the showerhead 13.
  • Each flow controller 22 may include, for example, a mass flow controller or a pressure-controlled flow controller.
  • the gas supply unit 20 may include at least one flow modulation device that modulates or pulses the flow rate of the at least one process gas.
  • the power supply 30 includes an RF power supply 31 coupled to the plasma processing chamber 10 via at least one impedance matching circuit.
  • the RF power supply 31 is configured to supply at least one RF signal (RF power) to at least one lower electrode and/or at least one upper electrode. This causes a plasma to be formed from at least one processing gas supplied to the plasma processing space 10s.
  • the RF power supply 31 can function as at least a part of the plasma generating unit 12.
  • a bias RF signal to at least one lower electrode, a bias potential is generated on the substrate W, and ion components in the formed plasma can be attracted to the substrate W.
  • the RF power supply 31 includes a first RF generating unit 31a and a second RF generating unit 31b.
  • the first RF generating unit 31a is coupled to at least one lower electrode and/or at least one upper electrode via at least one impedance matching circuit and configured to generate a source RF signal (source RF power) for plasma generation.
  • the source RF signal has a frequency in the range of 10 MHz to 150 MHz.
  • the first RF generating unit 31a may be configured to generate multiple source RF signals having different frequencies. The generated one or more source RF signals are supplied to at least one lower electrode and/or at least one upper electrode.
  • the second RF generator 31b is coupled to at least one lower electrode via at least one impedance matching circuit and configured to generate a bias RF signal (bias RF power).
  • the frequency of the bias RF signal may be the same as or different from the frequency of the source RF signal.
  • the bias RF signal has a frequency lower than the frequency of the source RF signal.
  • the bias RF signal has a frequency in the range of 100 kHz to 60 MHz.
  • the second RF generator 31b may be configured to generate multiple bias RF signals having different frequencies.
  • the generated one or more bias RF signals are provided to at least one lower electrode. Also, in various embodiments, at least one of the source RF signal and the bias RF signal may be pulsed.
  • the power supply 30 may also include a DC power supply 32 coupled to the plasma processing chamber 10.
  • the DC power supply 32 includes a first DC generator 32a and a second DC generator 32b.
  • the first DC generator 32a is connected to at least one lower electrode and configured to generate a first DC signal.
  • the generated first DC signal is applied to the at least one lower electrode.
  • the second DC generator 32b is connected to at least one upper electrode and configured to generate a second DC signal.
  • the generated second DC signal is applied to the at least one upper electrode.
  • the first and second DC signals may be pulsed.
  • a sequence of voltage pulses is applied to at least one lower electrode and/or at least one upper electrode.
  • the voltage pulses may have a rectangular, trapezoidal, triangular or combination thereof pulse waveform.
  • a waveform generator for generating a sequence of voltage pulses from the DC signal is connected between the first DC generator 32a and at least one lower electrode.
  • the first DC generator 32a and the waveform generator constitute a voltage pulse generator.
  • the second DC generator 32b and the waveform generator constitute a voltage pulse generator
  • the voltage pulse generator is connected to at least one upper electrode.
  • the voltage pulses may have a positive polarity or a negative polarity.
  • the sequence of voltage pulses may also include one or more positive polarity voltage pulses and one or more negative polarity voltage pulses within one period.
  • the first and second DC generating units 32a and 32b may be provided in addition to the RF power source 31, or the first DC generating unit 32a may be provided in place of the second RF generating unit 31b.
  • the exhaust system 40 may be connected to, for example, a gas exhaust port 10e provided at the bottom of the plasma processing chamber 10.
  • the exhaust system 40 may include a pressure regulating valve and a vacuum pump. The pressure in the plasma processing space 10s is adjusted by the pressure regulating valve.
  • the vacuum pump may include a turbomolecular pump, a dry pump, or a combination thereof.
  • ⁇ Configuration example of liquid processing system> 4 is a diagram for explaining an example of the configuration of a liquid processing system.
  • the liquid processing system includes a liquid processing apparatus 300 and a control unit 400.
  • the liquid processing system is an example of a substrate processing system
  • the liquid processing apparatus 300 is an example of a substrate processing apparatus.
  • the liquid processing apparatus 300 has a spin chuck 311 as a substrate support within a processing chamber 310.
  • the spin chuck 311 holds the substrate W horizontally.
  • the spin chuck 311 is connected to a rotating part 312 that can be raised and lowered, and the rotating part 312 is connected to a rotation drive part 313 constituted by a motor or the like.
  • the substrate W held by the spin chuck 311 can be rotated by driving the rotation drive part 313.
  • a cup 321 is placed on the outside of the spin chuck 311 to prevent processing liquid (resist liquid, developer, cleaning liquid, etc.) and mist of processing liquid from scattering around the cup 321.
  • a drain pipe 323 and an exhaust pipe 324 are provided at the bottom 322 of the cup 321.
  • the drain pipe 323 is connected to a drainage device 325 such as a drainage pump.
  • the exhaust pipe 324 is connected via a valve 326 to an exhaust device 327 such as an exhaust pump.
  • a blower 314 is provided at the top of the treatment chamber 310 of the liquid treatment device 300 to supply air of the required temperature and humidity as a downflow into the cup 321.
  • a processing liquid supply nozzle 331 When forming a puddle of processing liquid on the substrate W, a processing liquid supply nozzle 331 is used.
  • This processing liquid supply nozzle 331 is provided on a nozzle support 332, such as an arm, and the nozzle support 332 can be raised and lowered by a drive mechanism as indicated by the dashed reciprocating arrow A in the figure, and can also be moved horizontally as indicated by the dashed reciprocating arrow B.
  • Processing liquid (resist liquid, developer, etc.) is supplied to the processing liquid supply nozzle 331 from a processing liquid supply source 334 via a supply pipe 333.
  • a paddle of the processing liquid can be formed on the substrate W by scanning from one end to the other end.
  • the outlet is positioned above the center of the substrate W, and the processing liquid is ejected while the substrate W is rotating, thereby spreading the processing liquid over the entire surface of the substrate W and forming a paddle of the processing liquid on the substrate W.
  • the paddle of the processing liquid can also be formed by scanning a straight type nozzle over the substrate W in the same way as a long nozzle, or by arranging multiple outlets for ejecting liquid like a straight type nozzle over the substrate W and supplying the processing liquid from each outlet.
  • Gas nozzle 341 has nozzle body 342.
  • Nozzle body 342 is attached to a nozzle support such as an arm, and the nozzle support can be moved up and down by a drive mechanism as indicated by the dashed arrow C in the figure, and can also move horizontally as indicated by the dashed arrow D.
  • Gas nozzle 341 has two nozzle outlets 343, 344. Nozzle outlets 343, 344 are formed by branching off from gas flow path 345. Gas flow path 345 is connected to gas supply source 347 via gas supply pipe 346. In gas supply source 347, an inert gas or non-oxidizing gas, such as nitrogen gas, is prepared. When nitrogen gas, for example, is supplied from gas flow path 345 to gas nozzle 341, nitrogen gas is discharged from each of nozzle outlets 343, 344.
  • nitrogen gas for example, is supplied from gas flow path 345 to gas nozzle 341, nitrogen gas is discharged from each of nozzle outlets 343, 344.
  • the gas nozzle 341 is also provided with a cleaning liquid supply nozzle 351 that cleans the substrate W with the processing liquid after liquid processing.
  • the cleaning liquid supply nozzle 351 is connected to a cleaning liquid supply source 353 via a cleaning liquid supply pipe 352.
  • a cleaning liquid supply pipe 352 For example, pure water is used as the cleaning liquid.
  • the cleaning liquid supply nozzle 351 is located between the two nozzle outlets 343, 344 described above, but the position is not limited to this.
  • the cleaning liquid supply nozzle 351 may be configured independent of the gas nozzle 341.
  • the control unit 400 processes computer-executable instructions that cause the liquid treatment device 300 to perform the various steps described in this disclosure.
  • the control unit 400 may be configured to control each element of the liquid treatment device 300 to perform the various steps described herein. In one embodiment, some or all of the control unit 400 may be included in the liquid treatment device 300.
  • the control unit 400 is realized, for example, by a computer 400a.
  • the computer 400a may include a processing unit 400a1, a storage unit 400a2, and a communication interface 400a3.
  • Each component of the control unit 400 may be similar to each component of the control unit 200 (see FIG. 1) described above.
  • FIG. 5 is a flowchart showing a substrate processing method (hereinafter also referred to as "this processing method”) according to an exemplary embodiment.
  • This processing method includes a step ST1 of providing a substrate having an undercoat film, and a step ST2 of forming a metal-containing resist film on the undercoat film.
  • the formation process of the metal-containing resist film (hereinafter also referred to as "film formation process”) in the step ST2 is performed by a dry process (hereinafter also referred to as "dry film formation”) using a process gas.
  • the film formation process in the step ST2 is performed by a wet process (hereinafter also referred to as "wet film formation”) using a solution.
  • the film formation process in the step ST2 is performed using both wet film formation and dry film formation.
  • This processing method can include (a) a step of providing a substrate having an undercoat film (corresponding to "step ST1" described later), and (b) a step of forming a metal-containing resist film on the undercoat film using a metal-containing precursor having a photosensitive group and a polyfunctional compound (corresponding to "step ST2" described later).
  • Each step may be performed using any one of the above-mentioned substrate processing systems (see Figures 1 to 4), or may be performed using two or more of these substrate processing systems.
  • this processing method may be performed in a heat treatment system (see Figure 1).
  • Step ST1 Providing a substrate
  • the substrate W is provided in the processing chamber 102 of the heat treatment apparatus 100.
  • the substrate W is provided on the substrate support 121 via the lift pins 123.
  • the temperature of the substrate support 121 is adjusted to a set temperature.
  • the set temperature may be, for example, 350° C. or less, and may be 25° C. or more and 350° C. or less.
  • the temperature of the substrate support 121 may be adjusted by controlling the output of one or more heaters among the sidewall heater 104, the stage heater 120, the ceiling heater 130, and the piping heater 160 (hereinafter collectively referred to as "each heater").
  • the temperature of the substrate support 121 may be adjusted to a set temperature before step ST1. That is, the substrate W may be provided to the substrate support 121 after the temperature of the substrate support 121 is adjusted to the set temperature.
  • the substrate W may be used in the manufacture of semiconductor devices.
  • the semiconductor devices include, for example, semiconductor memory devices such as DRAMs and 3D-NAND flash memories, and logic devices.
  • the substrate W has an undercoat film UF.
  • the undercoat film UF may be an organic film, a dielectric film, a metal film, or a semiconductor film, or a laminated film thereof, formed on a silicon wafer.
  • the undercoat film UF includes, for example, at least one selected from the group consisting of a silicon-containing film, a carbon-containing film, and a metal-containing film.
  • FIGS. 6 and 7 are diagrams showing an example of an undercoat film UF of a substrate W.
  • the undercoat film UF may be composed of a first film UF1, a second film UF2, and a third film UF3.
  • the undercoat film UF may be composed of a second film UF2 and a third film UF3.
  • the undercoat film UF may be subjected to a surface modification treatment.
  • the first film UF1 is, for example, a spin-on-glass (SOG) film, a SiC film, a SiON film, a Si-containing antireflective film (SiARC), or an organic film.
  • the second film UF2 is, for example, a spin-on-carbon (SOC) film, an amorphous carbon film, or a silicon-containing film.
  • the third film UF3 is, for example, a silicon-containing film.
  • the silicon-containing film is, for example, a silicon oxide film, a silicon nitride film, a silicon oxynitride film, a silicon carbonitride film, a polycrystalline silicon film, or a carbon-containing silicon film.
  • the third film UF3 may be composed of a plurality of types of stacked silicon-containing films.
  • the third film UF3 may be composed of a silicon oxide film and a silicon nitride film that are alternately stacked.
  • the third film UF3 may also be composed of a stacked silicon oxide film and a polycrystalline silicon film.
  • the third film UF3 may also be a stacked film including a silicon nitride film, a silicon oxide film, and a polycrystalline silicon film.
  • the third film UF3 may also be composed of a stacked silicon oxide film and a silicon carbonitride film.
  • the third film UF3 may also be a laminated film including a silicon oxide film, a silicon nitride film, and a silicon carbonitride film.
  • Part or all of the base film UF may be formed within the processing chamber 102 of the thermal processing apparatus 100, or may be formed using other systems, such as a plasma processing system (see Figures 2 and 3) or a liquid processing system (see Figure 4).
  • Step ST2 Formation of metal-containing resist film
  • a metal-containing resist film RM is formed on the undercoat film UF of the substrate W.
  • a metal-containing precursor having a photosensitive group and a polyfunctional compound can be used to form the metal-containing resist film RM on the undercoat film UF.
  • the photosensitive group means a group that can be eliminated by exposure due to the photosensitivity of an adjacent metal atom. Examples of the photosensitive group include a hydrogen atom and a hydrocarbon group g1 which may be substituted with a halogen or the like.
  • hydrocarbon group g1 which may be substituted include linear or branched alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an i-propyl group, and a t-butyl group, and halogen-substituted alkyl groups such as -CH x F y (wherein x represents an integer of 0 to 2, and y represents an integer of 1 to 3).
  • FIG. 8 is a diagram showing an example of the cross-sectional structure of a substrate W on which a metal-containing resist film RM is formed in step ST2.
  • the metal-containing resist film RM is formed on the surface of the base film UF.
  • the metal-containing resist film RM is a film containing a metal.
  • the metal-containing resist film RM contains at least one metal selected from the group consisting of Sn, Ti, Hf, Zr, and In.
  • the metal-containing resist film RM may contain Sn.
  • the metal-containing resist film RM contains a compound having a repeating unit represented by the following formula (1) in the molecule.
  • -(M-X-A-X)- (1) (In formula (1), M represents Sn, Ti, Hf, Zr or In, X represents a divalent group derived from a terminal functional group of a polyalcohol, a polythiol, a polycarboxylic acid, a polyisocyanate or a polyisothiocyanate, and A represents a divalent organic group having 2 to 10 carbon atoms.)
  • the divalent group derived from the terminal of the polyalcohol contains an alkoxy bond.
  • the divalent group derived from the terminal of the polythiol contains a sulfide bond.
  • the divalent group derived from the terminal of the polycarboxylic acid contains an ester bond.
  • the divalent group derived from the terminal of the polyisocyanate contains a urethane bond.
  • the divalent group derived from the terminal of the polyisothiocyanate contains a thiourethane bond.
  • An example of a divalent organic group that can provide A in formula (1) includes an optionally substituted hydrocarbon group g2 having 2 to 10 carbon atoms.
  • An example of the optionally substituted hydrocarbon group g2 includes a linear, branched, or cyclic divalent hydrocarbon group.
  • An example of the linear, branched, or cyclic divalent hydrocarbon group may include a linear, branched, or cyclic alkylene group or arylene group.
  • at least one hydrogen atom in the molecule may be substituted with a halogen or the like.
  • the metal-containing precursor having a photosensitive group is n-butyltris(dimethylamino)tin
  • the polyfunctional compound is ethanedithiol. That is, in the example of Figure 9, n-butyltris(dimethylamino)tin reacts with ethanedithiol to obtain a compound having a repeating unit represented by -(Sn-S-CH 2 CH 2 -S)-.
  • the step ST2 can be performed by dry deposition.
  • the metal-containing precursor can include a compound ( ⁇ ) having an amine group and/or an alkoxy group;
  • the compound ( ⁇ ) may include a compound ( ⁇ 1) containing at least one metal selected from the group consisting of Sn, Ti, Hf, Zr, and In;
  • the compound ( ⁇ 1) may contain Sn;
  • the photosensitive group in the metal-containing precursor can include at least one group selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an i-propyl group, a t-butyl group, and —CH x F y (wherein x represents an integer from 0 to 2, and y represents an integer from 1 to 3);
  • the polyfunctional compound can include at least one compound ( ⁇ ) selected from the group consisting of polyalcohols,
  • the formation of the metal-containing resist film RM in step ST2 may be performed using various methods such as atomic layer deposition (hereinafter referred to as "ALD") and CVD.
  • ALD atomic layer deposition
  • CVD chemical vapor deposition
  • Various methods for forming the metal-containing resist film RM are described below.
  • a metal-containing resist film RM is formed by self-controllingly adsorbing and reacting a predetermined material on an undercoat film UF of a substrate W.
  • the step (b) can include a step of (b1) supplying a gas containing a metal-containing precursor onto the undercoat film to form a metal-containing precursor film, and a step of (b2) supplying a gas containing a polyfunctional compound to the metal-containing precursor film to form a metal-containing resist film from the metal-containing precursor film.
  • the steps (b1) and (b2) can be repeated multiple times.
  • FIG. 10 is a flow chart showing an example of process ST2 using the ALD method.
  • process ST2 using the ALD method includes a process ST211 of forming a metal-containing precursor film, a first purge process ST212, a process ST213 of forming a metal-containing film from the metal-containing precursor film, a second purge process ST214, and a determination process ST215.
  • the first purge process ST212 and the second purge process ST214 may or may not be performed.
  • FIG. 11 is a schematic diagram showing an example of a phenomenon that occurs on the surface of the substrate W in process ST21 using the ALD method.
  • a first gas G1 containing a metal-containing precursor is supplied to the surface of the undercoat film UF to form a metal-containing precursor film PF.
  • the metal-containing precursor contains a compound ( ⁇ ) having an amine group and/or an alkoxy group.
  • the amine group is a monovalent group represented by -NR a R b , where R a and R b each independently represent an alkyl group having 1 to 2 carbon atoms. Examples of the amine group include a dimethylamino group, a diethylamino group, an ethylmethylamino group, and the like.
  • the alkoxy group examples include a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an i-propoxy group, a t-butoxy group, and the like.
  • the compound ( ⁇ ) may contain a compound ( ⁇ 1) containing at least one metal selected from the group consisting of Sn, Ti, Hf, Zr, and In.
  • the compound ( ⁇ 1) may contain Sn.
  • the photosensitive group in the metal-containing precursor may include at least one group selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an i-propyl group, a t-butyl group, and a -CH x F y group (wherein x is an integer from 0 to 2, and y is an integer from 1 to 3).
  • the metal-containing precursor may include at least one compound selected from the group consisting of an aminotin compound, an aminotitanium compound, an aminohafnium compound, an aminozirconium compound, and an aminoindium compound.
  • aminotin compounds may include n-butyltris(dimethylamino)tin, t-butyltris(dimethylamino)tin, bis(dimethylamino)dimethyltin, bis(dimethyl)dibutyltin, azidotrimethyltin, bis(dimethylamino)dibutyltin, and the like.
  • alkoxytin compounds may include bis(tert-butoxide)dimethyltin, bis(dimethoxy)dimethyltin.
  • the photosensitive group in the metal-containing precursor may include at least one group selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an i-propyl group, a t-butyl group, and a —CH x F y (wherein x is an integer of 0 to 2, and y is an integer of 1 to 3).
  • a first gas G1 is supplied into the processing chamber 102 via a gas nozzle 141. Then, in the processing chamber 102, the metal-containing precursor of the first gas G1 is adsorbed onto the surface of the undercoat film UF to form a metal-containing precursor film PF.
  • the metal-containing precursor film PF may contain, for example, Sn, Ti, Hf, Zr, In, etc.
  • the metal-containing precursor film PF may be a metal complex.
  • the metal complex may contain, for example, aminotin.
  • step ST212 the gas in the processing chamber 102 is exhausted from the exhaust port 131 by the exhaust mechanism 132.
  • an inert gas or the like may be supplied to the substrate W. This allows excess gas such as metal-containing precursors to be purged.
  • An example of the inert gas is a noble gas such as He, Ar, Ne, Kr, or Xe, or nitrogen gas.
  • a second gas G2 containing a polyfunctional compound is supplied to the surface of the substrate W, and the second gas G2 reacts with the metal-containing precursor film PF to form a metal-containing resist film from the metal-containing precursor film PF.
  • the second gas G2 is a gas that reacts with the metal-containing precursor adsorbed on the surface of the undercoat film UF. Water and hydrogen peroxide are not included in the polyfunctional compound.
  • a compound having two or more valences (having two or more functional groups) may be used as the polyfunctional compound.
  • the polyfunctional compound may be divalent or may be trivalent or more.
  • the polyfunctional compound may include at least one compound ( ⁇ ) selected from the group consisting of polyalcohol, polythiol, polycarboxylic acid, polyisocyanate, and polyisothiocyanate.
  • polyalcohol may include ethylene glycol, glycerin, and the like.
  • polythiol may include ethanedithiol, toluenedithiol, and the like.
  • polycarboxylic acids may include glutaric acid, adipic acid, terephthalic acid (solution), etc.
  • polyisocyanates may include toluene diisocyanate, etc.
  • a second gas G2 is supplied into the processing chamber 102 through a gas nozzle 141.
  • the second gas G2 may include at least one selected from the group consisting of H 2 O gas, H 2 O 2 , O 3 , and O 2.
  • at least one selected from the group consisting of H 2 O gas, H 2 O 2 , O 3 , and O 2 is supplied into the processing chamber 102 as a gas different from the second gas G2. Then, the second gas G2 reacts with the metal-containing precursor film PF in the processing chamber 102 to form a metal-containing resist film.
  • step ST214 the gas in the processing chamber 102 is exhausted from the exhaust port 131 by the exhaust mechanism 132. At this time, an inert gas or the like may be supplied to the substrate W. This allows excess gas such as the second gas G2 to be purged.
  • step ST215 it is determined whether a given condition for ending step ST21 is satisfied.
  • the given condition may be that a cycle of steps ST211 to ST214 has been performed a preset number of times. The number of times may be once, less than five times, five or more times, or ten or more times.
  • step ST215 if it is determined that the given condition is not satisfied, the process returns to step ST211, and if it is determined that the given condition is satisfied, step ST21 is terminated.
  • the given condition may be a condition regarding the dimensions of the metal-containing resist film after step ST214.
  • step ST214 it is determined whether the dimensions of the metal-containing resist film (resist film thickness) have reached a given value or range, and the cycle of steps ST211 to ST214 may be repeated until the given value or range is reached.
  • the dimensions of the metal-containing resist film may be measured by an optical measuring device. In this manner, a metal-containing resist film is formed on the undercoat film UF.
  • a mixed gas GM containing a metal-containing precursor and a polyfunctional compound is used to form a metal-containing resist film.
  • the metal-containing precursor may be a known metal-containing precursor (such as a silicon-containing compound in an example containing Si) that can be used in the CVD method, or may be a metal-containing precursor described in the ALD method.
  • the polyfunctional compound may be a polyfunctional compound described in the ALD method.
  • the mixed gas GM may contain at least one selected from the group consisting of H 2 O, H 2 O 2 , O 3 , and O 2.
  • the mixed gas GM is supplied into the processing chamber 102 through the gas nozzle 141. The mixed gas GM undergoes a chemical reaction on the substrate W, thereby forming a metal-containing resist film on the undercoat film UF.
  • the temperature and pressure of the substrate support part 121 may be set appropriately.
  • the temperature of the substrate support part 121 may be adjusted by controlling the output of one or more of the heaters.
  • the temperature of the substrate support part 121 may be, for example, 25 to 350°C, and in one example, 50 to 200°C.
  • the pressure inside the processing chamber 102 may be, for example, 500 Torr or less.
  • step ST2 may include a step of heating and baking the metal-containing resist film.
  • the baking may be performed in an air atmosphere or an inert atmosphere.
  • the baking may be performed by heating the substrate W to 50° C. or more and 350° C. or less, 50° C. or more and 200° C. or less, or 80° C. or more and 150° C. or less.
  • each heater of the heat treatment apparatus 100 may function as a heating unit that performs baking.
  • the baking may be performed using a heat treatment system other than the heat treatment apparatus 100.
  • the processing method may be performed by a dry process using a plasma processing system (see Figures 2 and 3).
  • a substrate W may be provided on a substrate support 11 in a processing chamber 10 of a plasma processing apparatus 1 (step ST1), and a processing gas may be supplied from a gas supply unit 20 into the processing chamber 10 to form a metal-containing resist film RM (step ST2).
  • step ST2 When a plasma processing system is used, the above-mentioned ALD method or CVD method may be used in step ST2.
  • the composition (type, flow rate, and flow rate ratio) of the processing gas (first gas G1, second gas G2, mixed gas GM, etc.) in step ST2 and the temperature of the substrate support part 11 may be the same as in the case of using a heat processing system.
  • the temperature of the substrate support part 11 may be adjusted by controlling the pressure of the heat transfer gas (e.g., He) between the temperature control module or the electrostatic chuck 1111 and the rear surface of the substrate W.
  • plasma may be generated from the processing gas, or plasma may not be generated.
  • step ST21 and/or step ST22 may include a step of heating the substrate W to perform a bake process.
  • the bake process may be performed, for example, using a heat processing system.
  • the present processing method may be performed by a wet process (wet film formation) using a liquid processing system (see FIG. 4). That is, a substrate W may be provided on a spin chuck 311 in a processing chamber 310 of a liquid processing apparatus 300 (step ST1), and a film formation solution (resist precursor liquid) may be applied onto the substrate W from a processing liquid supply nozzle 331 to form a metal-containing resist film RM (step ST2).
  • a wet process wet film formation
  • a liquid processing system see FIG. 4
  • step (b) when step ST2 is performed by wet film formation, for example:
  • the step (b) includes applying a solution containing a metal-containing precursor and a polyfunctional compound onto the undercoat film, and heating the applied solution;
  • the metal-containing precursor comprises a metal complex comprising at least one metal selected from the group consisting of Sn, Ti, Hf, Zr, and In;
  • the polyfunctional compound comprises at least one compound ( ⁇ ) selected from the group consisting of polyalcohols, polythiols, polycarboxylic acids, polyisocyanates, and polyisothiocyanates.
  • the film-forming solution may contain a metal-containing precursor.
  • the metal-containing precursor contains a compound ( ⁇ ) having an amine group.
  • the compound ( ⁇ ) may contain a compound ( ⁇ 1) containing at least one metal selected from the group consisting of Sn, Ti, Hf, Zr, and In.
  • the compound ( ⁇ 1) may contain Sn.
  • the photosensitive group in the metal-containing precursor may contain at least one group selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an i-propyl group, a t-butyl group, and -CH x F y (wherein x represents an integer of 0 to 2, and y represents an integer of 1 to 3).
  • the metal-containing precursor contains at least one compound selected from the group consisting of an aminotin compound, an aminotitanium compound, an aminohafnium compound, an aminozirconium compound, and an aminoindium compound.
  • amino tin compounds may include n-butyl tris(dimethylamino)tin, t-butyl tris(dimethylamino)tin, bis(dimethylamino)dimethyltin, bis(dimethyl)dibutyltin, azidotrimethyltin, bis(dimethylamino)dibutyltin, etc.
  • alkoxy tin compounds may include bis(tert-butoxide)dimethyltin, bis(dimethoxy)dimethyltin.
  • the film-forming solution may contain a polyfunctional compound.
  • the polyfunctional compound may contain at least one compound ( ⁇ ) selected from the group consisting of polyalcohol, polythiol, polycarboxylic acid, polyisocyanate, and polyisothiocyanate.
  • polyalcohols may include ethylene glycol, glycerin, and the like.
  • polythiols may include ethanedithiol, toluenedithiol, and the like.
  • polycarboxylic acids may include glutaric acid, adipic acid, terephthalic acid (solution), and the like.
  • polyisocyanates may include toluene diisocyanate, and the like.
  • polyisothiocyanates may include butane diisothiocyanate, phenylene bis(isothiocyanate), and the like.
  • the second gas G2 may include at least one selected from the group consisting of H 2 O, H 2 O 2 , O 3 , and O 2 .
  • step ST2 may include a step of heating and baking the substrate W after the solution has been applied to the substrate W.
  • the baking may be performed, for example, using a heat treatment system (see FIG. 1).
  • the baking may be performed in an air atmosphere or in an inert atmosphere.
  • the baking may be performed by heating the substrate W to 50° C. or more and 350° C. or less, 50° C. or more and 200° C. or less, or 80° C. or more and 150° C. or less.
  • the deposition of the metal-containing resist film RM (step ST2) in this processing method may be performed by both a dry process using a heat treatment system (see FIG. 1) or a plasma processing system (see FIG. 2 and FIG. 3), and a wet process using a liquid processing system (see FIG. 4).
  • the reaction between the metal-containing precursor and the polyfunctional compound in step ST2 results in the metal-containing precursors being bonded to each other via a structure derived from the polyfunctional compound, and the metal composition ratio and film density in the metal-containing resist film are reduced.
  • the metal composition ratio and film density are reduced, in the subsequent development, the reaction tends to proceed sufficiently even when using not only highly reactive substances (e.g., highly corrosive substances such as hydrogen chloride, boron chloride, and hydrogen bromide), but also, for example, an organic acid described below, and a metal-containing resist film is formed.
  • the metal-containing precursors are bonded to each other via a structure derived from the polyfunctional compound, and a chemical structure with a relatively weak bond strength such as -Sn-X-A-X-Sn- (where X and A are the same as those in formula (1) above) is obtained compared to conventional bonds such as -Sn-O-Sn-, and the film density is reduced, and the reactivity tends to be improved in the subsequent development.
  • the type of polyfunctional compound used can be changed over time during the reaction between the metal-containing precursor and the polyfunctional compound in step ST2. As a specific example, in the early stage of the reaction (from the start of the reaction to the first elapsed time), a polyfunctional compound having a first carbon number is used.
  • a polyfunctional compound having a second carbon number greater than the first carbon number is used in the middle stage of the reaction. Furthermore, in the later stage of the reaction (from the second elapsed time to the end of the reaction), a polyfunctional compound having a third carbon number greater than the second carbon number is used.
  • a metal-containing resist film having a composition and/or density gradient in the film formation direction a metal-containing resist film in which the lower layer side is high density (high metal composition ratio) and the upper layer side is low density (low metal composition ratio) is obtained. From the same viewpoint, as another specific example, in the early stage of the reaction, a polyfunctional compound having a first functionality is used in the early stage of the reaction.
  • a polyfunctional compound having a second functionality less than the first functionality is used. Furthermore, in the later stage of the reaction, a polyfunctional compound having a third functionality less than the second functionality is used. Even in such an example, a metal-containing resist film having a density gradient in the film formation direction (a metal-containing resist film in which the lower layer side has a high density (high metal composition ratio) and the upper layer side has a low density (low metal composition ratio)) is obtained.
  • the processing method can further include, after steps (c) and (b), a step of exposing the substrate to light to form an exposed first region and an unexposed second region in the metal-containing resist film, and a step (d) of developing the substrate to selectively remove the second region from the metal-containing resist film.
  • the second region can be removed by a developing gas or a developing solution.
  • the developing gas or the developing solution can include an organic acid.
  • the organic acid can include at least one selected from the group consisting of alcohol, thiol, carboxylic acid, sulfonic acid, ⁇ -dicarbonyl compound, alkyl carbonate, and azole, and when these organic acids are employed, the contrast of development tends to be improved.
  • the alcohol can include nonafluoro-tert-butyl alcohol ((CF 3 ) 3 C—OH), trifluoroethanol, and the like.
  • Examples of the thiol can include methanethiol, allyl mercaptan, -trifluoroethanethiol, and the like.
  • Examples of carboxylic acids may include formic acid (HCOOH), acetic acid (CH 3 COOH), trichloroacetic acid (CCl 3 COOH), monofluoroacetic acid (CFH 2 COOH), difluoroacetic acid (CF 2 FCOOH), trifluoroacetic acid (CF 3 COOH) chloro-difluoroacetic acid (CCIF 2 COOH), sulfur-containing acetic acid, thioacetic acid (CH 3 COSH), thioglycolic acid (HSCH 2 COOH), trifluoroacetic anhydride ((CF 3 CO) 2 O), acetic anhydride ((CH 3 CO) 2 O), etc.
  • HCOOH formic acid
  • acetic acid CH 3 COOH
  • CCl 3 COOH trichloroacetic acid
  • Examples of sulfonic acids may include methanesulfonic acid, fluorosulfonic acid, 10-camphorsulfonic acid, etc.
  • Examples of ⁇ -dicarbonyl compounds may include acetylacetone (CH 3 C(O)CH 2 C(O)CH 3 ), trichloroacetylacetone (CCl 3 C(O)CH 2 C(O)CH 3 ), hexachloroacetylacetone (CCl 3 C(O)CH 2 C(O)CCl 3 ), trifluoroacetylacetone (CF 3 C(O)CH 2 C(O)CH 3 ), hexafluoroacetylacetone (HFAc, CF 3 C(O)CH 2 C(O)CF 3 ), and the like.
  • the developing gas or developing solution may include an inorganic acid.
  • the developing gas may include a halogen-containing gas.
  • the halogen-containing gas may be a gas containing a halogen-containing inorganic acid, and may be a gas containing Br or Cl.
  • the gas containing a halogen-containing inorganic acid is at least one selected from the group consisting of HBr gas, BCl 3 gas, HCl gas, HF gas, and HI gas.
  • the process gas is a mixed gas of a carboxylic acid and a hydrogen halide, or a mixed gas of acetic acid and formic acid.
  • the developer may be a liquid containing the above-mentioned halogen-containing inorganic acid.
  • the second region can be removed by a developing gas or developing solution containing a weak acid.
  • the weak acid can include an organic acid having an acid dissociation constant (pKa) of less than 16.
  • an organic acid having an acid dissociation constant (pKa) of less than 16 can be selected from the organic acids described above and used.
  • the weak acid can include an organic acid having an acid dissociation constant (pKa) of 0 or more and less than 16.
  • an organic acid having an acid dissociation constant (pKa) of 0 or more and less than 16 can be selected and used from the organic acids described above and used.
  • the present processing method can use a metal-containing resist-forming composition that includes a metal-containing precursor having a photosensitive group and a polyfunctional compound, the metal-containing precursor including a compound having a photosensitive group, an amine group, and/or an alkoxy group.
  • the metal-containing precursor and the polyfunctional compound in the metal-containing resist-forming composition can be the same as those described in step ST2.
  • the metal-containing resist-forming composition can be a gas mixture of a gas containing a metal-containing precursor and a gas containing a polyfunctional compound.
  • the metal-containing resist-forming composition can be a liquid mixture of a liquid containing a metal-containing precursor and a liquid containing a polyfunctional compound.
  • the metal-containing resist film obtained by the present processing method may contain the following metal-containing resist: That is, in one embodiment, the metal-containing resist contains a compound having a repeating unit represented by the following formula (1) in the molecule. -(M-X-A-X)- (1)
  • M represents Sn, Ti, Hf, Zr, or In
  • X represents a divalent group derived from an end of a polyalcohol, a polythiol, a polycarboxylic acid, a polyisocyanate, or a polyisothiocyanate
  • A represents a divalent organic group having 2 to 10 carbon atoms.
  • the polyalcohol, polythiol, polycarboxylic acid, polyisocyanate, and polyisothiocyanate that can provide X in formula (1) may be the same as those described in step ST2.
  • the divalent group derived from the terminal of the polyalcohol contains an alkoxy bond.
  • the divalent group derived from the terminal of the polythiol contains a sulfide bond.
  • the divalent group derived from the terminal of the polycarboxylic acid contains an ester bond.
  • the divalent group derived from the terminal of the polyisocyanate contains a urethane bond.
  • the divalent group derived from the terminal of the polyisothiocyanate contains a thiourethane bond.
  • Examples of divalent organic groups that can provide A in formula (1) include optionally substituted hydrocarbon groups g2 having 2 to 10 carbon atoms.
  • Examples of optionally substituted hydrocarbon groups g2 include linear, branched, or cyclic divalent hydrocarbon groups.
  • Examples of linear, branched, or cyclic divalent hydrocarbon groups may include linear, branched, or cyclic alkylene groups and arylene groups. The linear, branched, or cyclic alkylene groups and arylene groups may each have at least one hydrogen atom in the molecule substituted with a halogen or the like.
  • ⁇ Configuration example of substrate processing system> 12 is a block diagram for explaining a configuration example of a substrate processing system SS according to an exemplary embodiment.
  • the substrate processing system SS includes a first carrier station CS1, a first processing station PS1, a first interface station IS1, an exposure apparatus EX, a second interface station IS2, a second processing station PS2, a second carrier station CS2, and a controller CT.
  • the first carrier station CS1 transports the first carrier C1 between the first carrier station CS1 and a system external to the substrate processing system SS.
  • the first carrier station CS1 has a mounting table including a plurality of first mounting plates ST1.
  • the first carrier C1 which may contain a plurality of substrates W or be empty, is mounted on each first mounting plate ST1.
  • the first carrier C1 has a housing capable of housing a plurality of substrates W therein.
  • the first carrier C1 is a FOUP (Front Opening Unified Pod).
  • the first carrier station CS1 also transports the substrate W between the first carrier C1 and the first processing station PS1.
  • the first carrier station CS1 further includes a first transport device HD1.
  • the first transport device HD1 is provided in the first carrier station CS1 so as to be located between the mounting table and the first processing station PS1.
  • the first transport device HD1 transports and transfers the substrate W between the first carrier C1 on each first mounting plate ST1 and the second transport device HD2 of the first processing station PS1.
  • the substrate processing system SS may further include a load lock module.
  • the load lock module may be provided between the first carrier station CS1 and the first processing station PS1.
  • the load lock module can switch its internal pressure to atmospheric pressure or vacuum. "Atmospheric pressure" may be the pressure inside the first transport device HD1.
  • “Vacuum” refers to a pressure lower than atmospheric pressure, and may be, for example, a medium vacuum of 0.1 Pa to 100 Pa.
  • the interior of the second transport device HD2 may be atmospheric pressure or a vacuum.
  • the load lock module may, for example, transport a substrate W from the first transport device HD1, which is at atmospheric pressure, to the second transport device HD2, which is at vacuum, and also transport a substrate W from the second transport device HD2, which is at vacuum, to the first transport device HD1, which is at atmospheric pressure.
  • the first processing station PS1 performs various processes on the substrate W.
  • the first processing station PS1 includes a pre-processing module PM1, a resist film forming module PM2, and a first heat treatment module PM3 (hereinafter collectively referred to as the "first substrate processing module PMa").
  • the first processing station PS1 also has a second transport device HD2 that transports the substrate W.
  • the second transport device HD2 transports and transfers the substrate W between two designated first substrate processing modules PMa, and between the first processing station PS1 and the first carrier station CS1 or the first interface station IS1.
  • the substrate W is subjected to pre-treatment.
  • the pre-treatment module PM1 includes a temperature adjustment unit that adjusts the temperature of the substrate W, a high-precision temperature adjustment unit that adjusts the temperature of the substrate W with high precision, and a base film formation unit that forms part or all of a base film on the substrate W.
  • the pre-treatment module PM1 includes a surface modification unit that performs a surface modification process on the substrate W.
  • Each processing unit of the pre-treatment module PM1 may include a heat treatment device 100 (see FIG. 1), a plasma treatment device 1 (see FIG. 2 and FIG. 3), and/or a liquid treatment device 300 (see FIG. 4).
  • the resist film forming module PM2 includes a dry coating unit.
  • the dry coating unit forms a resist film on the substrate W using a dry process such as a vapor phase deposition method.
  • the dry coating unit includes a CVD apparatus or an ALD apparatus that performs chemical vapor deposition of a resist film on the substrate W arranged in a chamber, or a PVD apparatus that performs physical vapor deposition of a resist film.
  • the dry coating unit may be a heat treatment apparatus 100 (see FIG. 1) or a plasma treatment apparatus 1 (see FIG. 2 and FIG. 3).
  • the resist film forming module PM2 includes a wet coating unit.
  • the wet coating unit forms a resist film on the substrate W using a wet process such as liquid phase deposition.
  • the wet coating unit may be a liquid processing device 300 (see FIG. 4).
  • an example of the resist film forming module PM2 includes both a wet coating unit and a dry coating unit.
  • the substrate W is subjected to heat treatment in the first heat treatment module PM3.
  • the first heat treatment module PM3 includes one or more of a pre-bake (Post Apply Bake: PAB) unit that performs heat treatment on the substrate W on which a resist film has been formed, a temperature adjustment unit that adjusts the temperature of the substrate W, and a high-precision temperature adjustment unit that adjusts the temperature of the substrate W with high precision.
  • a pre-bake (Post Apply Bake: PAB) unit that performs heat treatment on the substrate W on which a resist film has been formed
  • a temperature adjustment unit that adjusts the temperature of the substrate W
  • a high-precision temperature adjustment unit that adjusts the temperature of the substrate W with high precision.
  • Each of these units may have one or more heat treatment devices.
  • the multiple heat treatment devices may be stacked.
  • the heat treatment device may be, for example, heat treatment device 100 (see FIG. 1).
  • Each heat treatment may be performed at a predetermined temperature using a predetermined gas.
  • the first interface station IS1 has a third transport device HD3.
  • the third transport device HD3 transports and transfers the substrate W between the first processing station PS1 and the exposure device EX.
  • the third transport device HD3 has a housing that houses the substrate W, and may be configured so that the temperature, humidity, pressure, etc. within the housing can be controlled.
  • the exposure apparatus EX exposes the resist film on the substrate W using an exposure mask (reticle).
  • the exposure apparatus EX may be, for example, an EUV exposure apparatus having a light source that generates EUV light.
  • the second interface station IS2 has a fourth transport device HD4.
  • the fourth transport device HD4 transports and transfers substrates W between the exposure device EX and the second processing station PS2.
  • the fourth transport device HD4 has a housing that houses the substrates W, and may be configured so that the temperature, humidity, pressure, etc. within the housing can be controlled.
  • the second processing station PS2 performs various processes on the substrate W.
  • the second processing station PS2 includes a second heat treatment module PM4, a measurement module PM5, a development module PM6, and a third heat treatment module PM7 (hereinafter collectively referred to as the "second substrate processing module PMb").
  • the second processing station PS2 also has a fifth transport device HD5 that transports the substrate W.
  • the fifth transport device HD5 transports and transfers the substrate W between two designated second substrate processing modules PMb, and between the second processing station PS2 and the second carrier station CS2 or the second interface station IS2.
  • the substrate W is subjected to a thermal treatment in the second thermal treatment module PM4.
  • the thermal treatment module PM4 includes one or more of a post-exposure bake (PEB) unit that heat-treats the substrate W after exposure, a temperature adjustment unit that adjusts the temperature of the substrate W, and a high-precision temperature adjustment unit that adjusts the temperature of the substrate W with high precision.
  • PEB post-exposure bake
  • Each of these units may have one or more thermal treatment devices.
  • the multiple thermal treatment devices may be stacked.
  • the thermal treatment device may be, for example, the thermal treatment device 100 (see FIG. 1).
  • Each thermal treatment may be performed at a predetermined temperature using a predetermined gas.
  • the measurement module PM5 includes an imaging unit including a mounting stage for mounting the substrate W, an imaging device, a lighting device, and various sensors (temperature sensor, reflectance measurement sensor, etc.).
  • the imaging device may be, for example, a CCD camera that captures an image of the exterior of the substrate W.
  • the imaging device may be a hyperspectral camera that captures images by dispersing light into wavelengths. The hyperspectral camera may measure one or more of the pattern shape, dimensions, film thickness, composition, and film density of the resist film.
  • the substrate W is subjected to a developing process.
  • the developing module PM6 includes a dry developing unit that performs dry developing on the substrate W.
  • the dry developing unit may be, for example, the thermal processing apparatus 100 (see FIG. 1) or the plasma processing apparatus 1 (see FIG. 2 and FIG. 3).
  • the developing module PM6 includes a wet developing unit that performs wet developing on the substrate W.
  • the wet developing unit may be, for example, the liquid processing apparatus 300 (FIG. 4).
  • the developing module PM6 includes both a dry developing unit and a wet developing unit.
  • the substrate W is subjected to heat treatment in the third heat treatment module PM7.
  • the third heat treatment module PM7 includes one or more of a post bake (PB) unit that heat treats the substrate W after development, a temperature adjustment unit that adjusts the temperature of the substrate W, and a high-precision temperature adjustment unit that adjusts the temperature of the substrate W with high precision.
  • PB post bake
  • Each of these units may have one or more heat treatment devices.
  • the multiple heat treatment devices may be stacked.
  • the heat treatment device may be, for example, heat treatment device 100 (see FIG. 1). Each heat treatment may be performed at a predetermined temperature using a predetermined gas.
  • the second carrier station CS2 transports the second carrier C2 between the second carrier station CS2 and a system external to the substrate processing system SS.
  • the configuration and functions of the second carrier station CS2 may be similar to those of the first carrier station CS1 described above.
  • the control unit CT controls each component of the substrate processing system SS to perform a given process on the substrate W.
  • the control unit CT stores a recipe in which the process procedure, process conditions, transport conditions, etc. are set, and controls each component of the substrate processing system SS to perform a given process on the substrate W according to the recipe.
  • the control unit CT may perform some or all of the functions of each control unit (control unit 200, control unit 2, and control unit 400 shown in Figures 1 to 4).
  • FIG. 13 is a flowchart showing a substrate processing method (hereinafter also referred to as "method MT") according to an exemplary embodiment.
  • the method MT includes a process ST100 of performing a pre-treatment on a substrate, a process ST200 of forming a resist film on the substrate, a process ST300 of performing a heat treatment (pre-bake: PAB) on the substrate on which the resist film has been formed, a process ST400 of performing EUV exposure on the substrate, a process ST500 of performing a heat treatment (post-exposure bake: PEB) on the substrate after exposure, a process ST600 of measuring the substrate, a process ST700 of developing the resist film on the substrate, a process ST800 of performing a heat treatment (post-bake: PB) on the substrate after development, and a process ST900 of etching the substrate.
  • the method MT may not include one or more of the above steps.
  • the method MT may not include the process
  • the method MT may be performed using a substrate processing system SS shown in FIG. 12.
  • a control unit CT of the substrate processing system SS controls each part of the substrate processing system SS to perform the method MT on a substrate W.
  • Step ST100 Pretreatment
  • a first carrier C1 accommodating a plurality of substrates W is loaded into a first carrier station CS1 of a substrate processing system SS.
  • the first carrier C1 is placed on a first placement plate ST1.
  • the first transport device HD1 sequentially takes out each substrate W from the first carrier C1 and transfers it to a second transport device HD2 of a first processing station PS1.
  • the substrate W is transported to a pre-processing module PM1 by the second transport device HD2.
  • the pre-processing module PM1 performs pre-processing on the substrate W.
  • the pre-processing may include, for example, one or more of temperature adjustment of the substrate W, formation of a part or all of an undercoat film on the substrate W, heating treatment of the substrate W, and high-precision temperature adjustment of the substrate W.
  • the pre-processing may include a surface modification treatment of the substrate W.
  • Step ST200 Forming a resist film
  • the substrate W is transported to the resist film forming module PM2 by the second transport device HD2.
  • a resist film is formed on the substrate W by the resist film forming module PM2.
  • the resist film is formed by a wet process such as a liquid phase deposition method.
  • a resist film is formed by spin-coating a resist film on the substrate W using a wet coating unit of the resist film forming module PM2.
  • the resist film is formed on the substrate W by a dry process such as a vapor phase deposition method.
  • a resist film is formed by vapor-depositing a resist film on the substrate W using a dry coating unit of the resist film forming module PM2.
  • the resist film in the process ST200 may be formed by using the present processing method (see FIG. 5). That is, a metal-containing resist film RM may be formed on the substrate W.
  • the formation of a resist film on the substrate W may be performed using both a dry process and a wet process.
  • a second resist film may be formed on the first resist film by a wet process.
  • the film thickness, material and/or composition of the first resist film and the second resist film may be the same or different.
  • Step ST300 Next, the substrate W is transported by the second transport device HD2 to the first thermal treatment module PM3.
  • the substrate W is subjected to a heat treatment (pre-baking: PAB) by the first thermal treatment module PM3.
  • the pre-baking may be performed in an air atmosphere or an inert atmosphere.
  • the pre-baking may be performed by heating the substrate W to 50° C. or more or 80° C. or more.
  • the heating temperature of the substrate W may be 250° C. or less, 200° C. or less, or 150° C. or less. In one example, the heating temperature of the substrate may be 50° C. or more and 250° C. or less.
  • the pre-baking may be performed continuously in the dry coating unit that performed the process ST200.
  • a process Edge Bead Removal: EBR
  • EBR Error Bead Removal
  • Step ST400 EUV exposure
  • the substrate W is transferred by the second transport device HD2 to the third transport device HD3 of the first interface station IS1.
  • the substrate W is then transported by the third transport device HD3 to the exposure device EX.
  • the substrate W is EUV exposed through an exposure mask (reticle) in the exposure device EX.
  • EUV has a wavelength in the range of 10 to 20 nm, for example.
  • EUV may have a wavelength in the range of 11 to 14 nm, and in one example has a wavelength of 13.5 nm.
  • a first region that is EUV exposed and a second region that is not EUV exposed are formed on the substrate W in accordance with the pattern of the exposure mask (reticle).
  • the film thickness of the first region may be smaller than the film thickness of the second region 2.
  • the substrate W is transferred from the fourth transport device HD4 of the second interface station IS2 to the fifth transport device HD5 of the second processing station PS2.
  • the substrate W is then transported by the fifth transport device HD5 to the second thermal treatment module PM4.
  • the substrate W is then subjected to a heating process (post-exposure bake: PEB) in the second thermal treatment module PM4.
  • the post-exposure bake may be performed in an air atmosphere.
  • the post-exposure bake may be performed by heating the substrate W to a temperature of 180° C. or higher and 250° C. or lower.
  • Step ST600 Measurement
  • the substrate W is transported to the measurement module PM5 by the fifth transport device HD5.
  • the measurement module PM5 measures the substrate W.
  • the measurement may be an optical measurement or another measurement.
  • the measurement by the measurement module PM5 includes measurement of the appearance and/or dimensions of the substrate W using a CCD camera.
  • the measurement by the measurement module PM5 includes measurement of one or more of the pattern shape, dimensions, film thickness, composition, and film density of the resist film (hereinafter also referred to as "pattern shape, etc.”) using a hyperspectral camera.
  • the control unit CT determines whether or not there is an exposure abnormality in the substrate W based on the measured appearance and dimensions of the substrate W and/or the pattern shape, etc. In one embodiment, if the control unit CT determines that there is an exposure abnormality, the substrate W may be reworked or discarded without being developed by process ST700. Reworking of the substrate W may be performed by removing the resist on the substrate W and returning to process ST200 to form a resist film again. Reworking after development may cause damage to the substrate W, but by performing reworking before development, damage to the substrate W can be avoided or suppressed.
  • Step ST700 Development
  • the substrate W is transported to the developing module PM6 by the fifth transport device HD5.
  • the developing module PM6 the resist film of the substrate W is developed. Either the first region exposed to EUV or the second region not exposed to EUV is selectively removed by the development.
  • the development process may be performed by dry development or wet development.
  • the development process may be performed by combining dry development and wet development.
  • a desorption process may be performed one or more times.
  • the desorption process includes descumming or smoothing the surface of the resist film by using an inert gas such as helium or a plasma of the inert gas.
  • the development process may be performed by heating the substrate W to 100° C. or more and 350° C. or less.
  • the dry development process may be performed by setting the pressure to 10 Torr or less.
  • the development process may be performed for 0.5 minutes to 2 hours.
  • the present processing method can also be carried out as a part of a developing method. That is, in one embodiment, the developing method includes the steps of (a) providing a substrate having an undercoat film and a metal-containing resist on the undercoat film, (b) exposing the metal-containing resist through an exposure mask to form an exposed first region and an unexposed second region in the metal-containing resist, and (c) selectively removing one of the first region and the second region, and the metal-containing resist in the step (a) includes a compound having a repeating unit represented by the above formula (1) in its molecule.
  • the substrate W is transported by the fifth transport device HD5 to the third thermal treatment module PM7, where it is subjected to a heat treatment (post-bake).
  • the post-bake may be performed in an air atmosphere, or in a reduced pressure atmosphere containing N2 or O2 .
  • the post-bake may be performed by heating the substrate W to 150°C or more and 250°C or less.
  • the post-bake may be performed in the second thermal treatment module PM4 instead of the third thermal treatment module PM7.
  • the substrate W may be optically measured by the measurement module PM4PM5. Such a measurement may be performed in addition to or instead of the measurement in the process ST600.
  • the controller CT judges the presence or absence of anomalies such as defects, scratches, and foreign matter adhesion in the developed pattern of the substrate W based on the measured appearance, dimensions, and/or pattern shape of the substrate W.
  • the substrate W may be reworked or discarded without performing etching in step ST900.
  • the opening dimension of the resist film of the substrate W may be adjusted using a dry coating unit (such as a CVD apparatus or an ALD apparatus).
  • Step ST900 Etching
  • the substrate W is transferred to the sixth transport device HD6 of the second carrier station CS2 by the fifth transport device HD5, and is transported to the second carrier C2 of the second placement plate ST2 by the sixth transport device HD6.
  • the second carrier C2 is then transported to a plasma processing system (not shown).
  • the plasma processing system may be, for example, the plasma processing system shown in FIG. 2 and FIG. 3.
  • the undercoat film UF of the substrate W is etched using the developed resist film as a mask. This completes the method MT. Note that in the process ST700, when the resist film is developed using a plasma processing device, etching may be performed subsequently in a plasma processing chamber of the plasma processing device.
  • the present processing method may also be performed as a part of an etching method. That is, in one embodiment, the method includes the steps of: (a) providing a substrate having an undercoat film and a metal-containing resist on the undercoat film, wherein the metal-containing resist has at least one opening; and (b) etching the undercoat film through the opening, wherein the metal-containing resist contains a compound having a repeating unit represented by the above formula (1) in its molecule.
  • a method for processing a substrate comprising: (a) providing a substrate having an undercoat; (b) forming a metal-containing resist film on the undercoat film using a metal-containing precursor having a photosensitive group and a polyfunctional compound;
  • the substrate processing method comprises:
  • the compound ( ⁇ ) includes a compound ( ⁇ 1) containing at least one metal selected from the group consisting of Sn, Ti, Hf, Zr, and In.
  • the photosensitive group comprises at least one group selected from the group consisting of a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an i-propyl group, a t-butyl group, and -CH x F y (wherein x is an integer of 0 to 2, and y is an integer of 1 to 3).
  • Appendix 6 The substrate processing method according to any one of Appendix 1 to Appendix 5, wherein the polyfunctional compound includes at least one compound ( ⁇ ) selected from the group consisting of polyalcohols, polythiols, polycarboxylic acids, polyisocyanates, and polyisothiocyanates.
  • the polyfunctional compound includes at least one compound ( ⁇ ) selected from the group consisting of polyalcohols, polythiols, polycarboxylic acids, polyisocyanates, and polyisothiocyanates.
  • step (Appendix 10) 10. The substrate processing method according to claim 1, wherein the step (b) includes forming the metal-containing resist film by using a mixed gas containing the metal-containing precursor and the polyfunctional compound.
  • the metal-containing precursor comprises a metal complex containing at least one metal selected from the group consisting of Sn, Ti, Hf, Zr, and In.
  • polyfunctional compound includes at least one compound ( ⁇ ) selected from the group consisting of polyalcohols, polythiols, polycarboxylic acids, polyisocyanates, and polyisothiocyanates.
  • the organic acid includes at least one selected from the group consisting of an alcohol, a thiol, a carboxylic acid, a sulfonic acid, a ⁇ -dicarbonyl compound, an alkyl carbonate, and an azole.
  • a metal-containing resist comprising a compound having a repeating unit represented by the following formula (1) in the molecule: -(M-X-A-X)- (1)
  • M represents Sn, Ti, Hf, Zr or In
  • X represents a divalent group derived from a terminal functional group of a polyalcohol, a polythiol, a polycarboxylic acid, a polyisocyanate or a polyisothiocyanate
  • A represents a divalent organic group having 2 to 10 carbon atoms.
  • a substrate processing system having one or more substrate processing apparatuses and a control unit, The control unit, for the one or more substrate processing apparatuses, (a) providing a substrate having an undercoat film; (b) forming a metal-containing resist film on the undercoat film using a metal-containing precursor having a photosensitive group and a polyfunctional compound; A substrate processing system configured to perform the steps of:
  • a device manufacturing method comprising the steps of: (a) providing a substrate having an undercoat; (b) forming a metal-containing resist film on the undercoat film using a metal-containing precursor having a photosensitive group and a polyfunctional compound; A device manufacturing method comprising the steps of:
  • Appendix 22 A computer of a substrate processing system having one or more substrate processing apparatuses and a control unit, (a) providing a substrate having an undercoat film; (b) forming a metal-containing resist film on the undercoat film using a metal-containing precursor having a photosensitive group and a polyfunctional compound; A program that executes the following.
  • (Appendix 24) (a) providing a substrate having an undercoat and a metal-containing resist on the undercoat; (b) exposing the metal-containing resist through an exposure mask to form a first exposed area and a second unexposed area in the metal-containing resist; (c) selectively removing one of the first region and the second region; Including, The developing method according to the above (a), wherein the metal-containing resist contains a compound having a repeating unit represented by the following formula (1) in the molecule: -(M-X-A-X)- (1) (In the above formula (1), M represents Sn, Ti, Hf, Zr or In, X represents a divalent group derived from a terminal functional group of a polyalcohol, a polythiol, a polycarboxylic acid, a polyisocyanate or a polyisothiocyanate, and A represents a divalent organic group having 2 to 10 carbon atoms.)
  • (Appendix 25) (a) providing a substrate having an undercoat and a metal-containing resist on the undercoat, wherein the metal-containing resist has at least one opening; (b) etching the undercoat film through the opening; Including, The etching method, wherein the metal-containing resist contains a compound having a repeating unit represented by the following formula (1) in the molecule: -(M-X-A-X)- (1)
  • M represents Sn, Ti, Hf, Zr or In
  • X represents a divalent group derived from a terminal functional group of a polyalcohol, a polythiol, a polycarboxylic acid, a polyisocyanate or a polyisothiocyanate
  • A represents a divalent organic group having 2 to 10 carbon atoms.
  • Plasma processing device 2: Control unit, 10: Plasma processing chamber, 1: Substrate support unit, 20: Gas supply unit, 30: Power supply, 100: Heat processing device, 102: Processing chamber, 120: Stage heater, 121: Substrate support unit, 141: Gas nozzle, 200: Control unit, 300: Liquid processing device, 311: Spin chuck, 321: Cup, 331: Processing liquid supply nozzle, 351: Cleaning liquid supply nozzle, 400: Control unit, RM: Metal-containing resist film, UF: Base film, W: Substrate

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PCT/JP2023/038633 2022-11-08 2023-10-26 基板処理方法、金属含有レジスト形成用組成物、金属含有レジスト及び基板処理システム Ceased WO2024101166A1 (ja)

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EP23888514.9A EP4617777A1 (en) 2022-11-08 2023-10-26 Substrate processing method, composition for forming metal-containing resist, metal-containing resist, and substrate processing system
KR1020257018129A KR20250107207A (ko) 2022-11-08 2023-10-26 기판 처리 방법, 금속 함유 레지스트 형성용 조성물, 금속 함유 레지스트 및 기판 처리 시스템
CN202380076750.4A CN120153326A (zh) 2022-11-08 2023-10-26 基板处理方法、含金属抗蚀剂形成用组合物、含金属抗蚀剂和基板处理系统
US19/199,672 US20250264805A1 (en) 2022-11-08 2025-05-06 Substrate processing method, composition for forming metal-containing resist, metal-containing resist, and substrate processing system

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WO2022016123A1 (en) * 2020-07-17 2022-01-20 Lam Research Corporation Dry deposited photoresists with organic co-reactants
JP2022539721A (ja) * 2019-06-27 2022-09-13 ラム リサーチ コーポレーション フォトレジスト乾式蒸着のための装置

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JP2022539721A (ja) * 2019-06-27 2022-09-13 ラム リサーチ コーポレーション フォトレジスト乾式蒸着のための装置
WO2022016123A1 (en) * 2020-07-17 2022-01-20 Lam Research Corporation Dry deposited photoresists with organic co-reactants

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