WO2019080820A1 - 一种光刻方法、光刻产品和光刻材料 - Google Patents

一种光刻方法、光刻产品和光刻材料

Info

Publication number
WO2019080820A1
WO2019080820A1 PCT/CN2018/111325 CN2018111325W WO2019080820A1 WO 2019080820 A1 WO2019080820 A1 WO 2019080820A1 CN 2018111325 W CN2018111325 W CN 2018111325W WO 2019080820 A1 WO2019080820 A1 WO 2019080820A1
Authority
WO
WIPO (PCT)
Prior art keywords
molecule
light
group
molecular switch
effector molecule
Prior art date
Application number
PCT/CN2018/111325
Other languages
English (en)
French (fr)
Inventor
王丽江
王炜
朱松
Original Assignee
上海必修福企业管理有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 上海必修福企业管理有限公司 filed Critical 上海必修福企业管理有限公司
Priority to EP18871767.2A priority Critical patent/EP3702837A4/en
Priority to KR1020207013245A priority patent/KR20200078532A/ko
Priority to CA3078560A priority patent/CA3078560A1/en
Priority to US16/757,431 priority patent/US20200341373A1/en
Priority to JP2020520477A priority patent/JP2021500598A/ja
Publication of WO2019080820A1 publication Critical patent/WO2019080820A1/zh

Links

Images

Classifications

    • 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
    • G03F7/70—Microphotolithographic exposure; Apparatus therefor
    • G03F7/70216—Mask projection systems
    • G03F7/70283—Mask effects on the imaging process
    • G03F7/70291—Addressable masks, e.g. spatial light modulators [SLMs], digital micro-mirror devices [DMDs] or liquid crystal display [LCD] patterning devices
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
    • G02B27/10—Beam splitting or combining systems
    • G02B27/1006—Beam splitting or combining systems for splitting or combining different wavelengths
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B27/00—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00
    • G02B27/28—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 for polarising
    • G02B27/283—Optical systems or apparatus not provided for by any of the groups G02B1/00 - G02B26/00, G02B30/00 for polarising used for beam splitting or combining
    • 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
    • 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
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
    • G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
    • 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
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/22—Exposing sequentially with the same light pattern different positions of the same surface
    • 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
    • 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
    • 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
    • G03F7/70—Microphotolithographic exposure; Apparatus therefor
    • G03F7/70008—Production of exposure light, i.e. light sources
    • G03F7/7005—Production of exposure light, i.e. light sources by multiple sources, e.g. light-emitting diodes [LED] or light source arrays
    • 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
    • G03F7/70—Microphotolithographic exposure; Apparatus therefor
    • G03F7/70216—Mask projection systems
    • G03F7/70325—Resolution enhancement techniques not otherwise provided for, e.g. darkfield imaging, interfering beams, spatial frequency multiplication, nearfield lenses or solid immersion lenses
    • 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
    • G03F7/70—Microphotolithographic exposure; Apparatus therefor
    • G03F7/70425—Imaging strategies, e.g. for increasing throughput or resolution, printing product fields larger than the image field or compensating lithography- or non-lithography errors, e.g. proximity correction, mix-and-match, stitching or double patterning
    • G03F7/70466—Multiple exposures, e.g. combination of fine and coarse exposures, double patterning or multiple exposures for printing a single feature
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B6/00—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings
    • G02B6/10—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type
    • G02B6/105—Light guides; Structural details of arrangements comprising light guides and other optical elements, e.g. couplings of the optical waveguide type having optical polarisation effects

Definitions

  • the present invention relates to the field of lithography, and more particularly to a lithography method and a lithographic material.
  • Lithography is an important technical link in current industrial precision machining. Especially in the field of micro-nano processing, such as integrated circuit chips, MEMS devices, optical integration technology, precision optics and other fields have a wide range of applications.
  • the current mainstream high-precision lithography manufacturing processes include optical projection microlithography, electron beam direct writing, ion beam processing, and laser interference lithography.
  • the improvement in resolution can be achieved by increasing the numerical aperture NA of the lithography objective lens and shortening the exposure wavelength ⁇ .
  • the method of adding numerical aperture to the lithography technology is to use immersion lithography, and the most mature technology for short-wavelength exposure is to use an ArF light source with a wavelength of 193 nm. Even with the method of immersing the NA, the minimum resolution cannot be achieved. Break through 45nm.
  • EUV Ultraviolet
  • NNL next-generation lithography
  • electron beam In maskless lithography, electron beam (EB) has the characteristics of short wavelength, high resolution, long focal depth, easy control and flexible modification, and is widely used in mask manufacturing of optical and non-optical exposure.
  • EBDW electron beam direct writing
  • SOC system integrated chips
  • EBDW electron beam direct writing
  • the existing exposure-based lithography technology uses the traditional optical principle to improve the resolution based on the Rayleigh formula, mainly using the immersion method to increase the numerical aperture and the light source with shorter wavelength, especially the latter for lifting resolution.
  • the rate is decisive, but excimer light sources, electron beams, and even extreme ultraviolet light sources are complex, difficult, and costly to manufacture, so direct super-resolution exposure lithography machines are expensive and the resolution is still limited by the source. Diffraction limit.
  • a first aspect of the present invention provides a photolithography method comprising the following steps:
  • the molecular switch controllable effector molecule generating molecule is in a closed state, the second light is used to cause the molecular switch controllable effector molecule to generate a molecule in an open state, the first light and the second light overlapping region
  • the molecular switch controllable effector molecule produces a molecule in a closed state; at least a portion of the open molecularly controlled molecule of the controllable effector molecule produces a molecularly produced effector molecule such that the physical and/or chemical properties of the lithographic material in the open region of the molecular switch occur Variety;
  • the first light is single hollow light or multiple hollow light.
  • the second light at least partially covers an unilluminated area surrounded by the first light illumination area.
  • the second light is solid light.
  • At least one of the first light and the second light is array light.
  • the illumination region of the second light does not exceed the outer edge of the illumination region of the first light.
  • At least one of the first light and the second light is a multi-beam.
  • the molecular switch produces a control molecule that produces an effector molecule selected from the group consisting of a delithographic material protecting group molecule or an activating photolithographic material polymerization controlling molecule.
  • the delithography material protecting group molecule is selected from the group consisting of an acidic molecule, a basic molecule, and singlet oxygen.
  • the activated lithographic material polymerization control molecule is selected from the group consisting of polymerization initiation molecules.
  • the molecular switch controllable effector molecule produces a molecular structure comprising a molecular switch group and an effector molecule generating group.
  • the molecular switch controllable effector molecule produces a molecule in which a molecular switch group and an effector molecule generating group are linked by a chemical bond.
  • the molecular switch controllable effector molecule in an open state generates a molecule to generate an effector molecule in a manner selected from: changing a molecular switch controlled by an effector molecule to be opened The lighting conditions.
  • a change in the physical or chemical properties of the lithographic material refers to a change in solubility in the developer.
  • the method of altering the physical or chemical properties of the lithographic material is selected from the group consisting of removing protective groups from the lithographic material or polymerizing the polymer monomers in the lithographic material.
  • a second aspect of the invention provides a lithographic material comprising a molecular switch controllable effector molecule generating molecule and a compound sensitive to an effector molecule.
  • the effector molecule is selected from the group consisting of a lithographic material protecting group molecule or an activating lithographic material polymerization controlling molecule;
  • the lithographic material protecting group molecule is selected from the group consisting of an acidic molecule, a basic molecule, Singlet oxygen.
  • the activated lithographic material polymerization control molecule is selected from the group consisting of polymerization initiation molecules.
  • the effector molecule-sensitive compound is selected from the group consisting of an effector-sensitive polymer, an effector-sensitive polymerizable monomer, or an oligomer.
  • the molecular switch controllable effector molecule production molecule comprises a molecular switch group and an effector molecule generating group.
  • the molecular switch controllable effector molecule produces a molecule in which a molecular switch group and an effector molecule generating group are linked by a chemical bond.
  • a compound of the third aspect of the invention which comprises a molecular switching group and an effector molecule generating group.
  • the effector molecule is selected from the group consisting of a delithographic material protecting group molecule or an activating lithographic material polymerization controlling molecule.
  • the delithography material protecting group molecule is selected from the group consisting of an acidic molecule, a basic molecule, and singlet oxygen.
  • the activated lithographic material polymerization control molecule is selected from the group consisting of polymerization initiation molecules.
  • the molecular switch controllable effector molecule produces a molecule in which a molecular switch group and an effector molecule generating group are linked by a chemical bond.
  • Figure 1 is a schematic diagram of the basic principle of the dual-beam technology to achieve super-resolution
  • FIG. 2 is a schematic diagram of a controllable polymerization deprotection mode of a molecular switch
  • 3A and 3B are diagrams showing a mode of polymerization of a controllable monomer of a molecular switch
  • 4A and 4B are reaction forms of a common molecular switch
  • Figure 5 is a de-group reaction mode of the molecular switch of the pericyclic reaction system
  • FIG. 6 is a schematic diagram of a molecular switch controllable polymerization deprotection positive dual beam lithography mode
  • FIG. 7 is a schematic diagram of a negative switching double beam lithography mode of a molecular switch controllable monomer
  • FIGS. 8A and 8B are diagrams showing a process flow of a molecular switch controllable polymerization deprotection positive double beam lithography process
  • FIG. 9A and FIG. 9B are process diagrams of a molecular switch-controllable monomer polymerization negative double-beam lithography process
  • 10A and 10B are schematic diagrams of a dual beam shaping technique
  • 11A and 11B are two schematic forms of a parallelized two-beam lithography system
  • Figure 12 shows the scanning mode adopted by the two-beam array, which includes two coordinate system systems: Cartesian coordinate system scanning and polar coordinate system scanning.
  • the inventors of the present application have discovered a new lithography method through extensive exploratory research, and further provided a lithography material corresponding to the lithography method, and the lithography method and the lithography material can effectively break through the diffraction of light.
  • the present invention has been completed on the basis of the limit, thereby further improving the precision of lithography.
  • the present application provides a photolithography method
  • the photolithography method may include: providing a first light and a second light to a photolithographic material, the first light and the second light may partially overlap, the photolithography material
  • the molecular switch controllable effector molecule produces a molecule, and at least part of the molecular switch controllable effector molecule in the open state generates a molecule to produce an effector molecule, so that the physical or chemical properties of the photolithographic material in the open region of the molecular switch are changed.
  • the second light may be used to enable the molecular switch controllable effector molecule to generate an open state, and those skilled in the art may generate a molecular species according to a molecular switch controllable effector molecule, and perform lithography.
  • the second light may be ultraviolet light, visible light or infrared light, etc., for example, the second light It may have a wavelength of not more than 5 nm, 5-10 nm, 10-20 nm, 20-40 nm, 40-60 nm, 60-80 nm, 80-100 nm, 100-150 nm, 150-200 nm, 200-250 nm, 250-300 nm, 300- 350 nm, 350-400 nm, 400-450 nm, 450-500 nm, 500-550 nm, 550-600 nm, 600-650 nm, 650-700 nm, 700-750 nm, 750-800 nm, 800-850 nm, 850-900 nm, 900-950 nm, 950-1000 nm, 1000-12
  • the first light may be used to cause the molecular switch controllable effector molecule to generate a molecule in a closed state
  • the first light and the second light overlapping region may generally cause the molecular switch
  • the controllable effector molecule produces a molecule in a closed state, such that the molecular switchable controllable effector molecule produces a molecule in a closed state, for example, by turning the molecular switch controllable effector molecule in an open state into a closed state and/or maintaining
  • the closed state molecular switch controllable effector molecule produces the molecule in a closed state
  • those skilled in the art can determine the controllable effect of the molecular switch according to the molecular switch type controllable effector molecule to generate the molecular species, the content in the lithographic material and the like.
  • the molecule generates a condition that the molecule is in a closed state.
  • the first light may be ultraviolet light, visible light or infrared light, etc., for example, the first light may be a wavelength of not more than 5 nm, 5-10 nm, 10-20 nm.
  • nm 20-40 nm, 40-60 nm, 60-80 nm, 80-100 nm, 100-150 nm, 150-200 nm, 200-250 nm, 250-300 nm, 300-350 nm, 350-400 nm 400-450 nm, 450-500 nm, 500-550 nm, 550-600 nm, 600-650 nm, 650-700 nm, 700-750 nm, 750-800 nm, 800-850 nm, 850-900 nm, 900-950 nm, 950-1000 nm, 1000- 1200 nm, 1200-1400 nm, 1400-1600 nm, 1600-1800 nm, 1800-2000 nm, 2000-2500 nm, 2500-3000 nm, 3000-3500 nm, 3500-4000 nm, 4000-4500 nm, 4500-5000 nm, 5000-6000 nm,
  • the conditions for the molecular switch controllable effect molecule to be in an open state and a closed state are different, and those skilled in the art can according to the molecular switch. Controlling the type of effector molecule, determining the conditions under which the molecular switchable controllable effector molecule can be in different states. For example, the molecule can be controlled to control the effector molecule to produce a condition in which the molecule is in an open state, and the molecule can be controlled to produce a controllable effector molecule.
  • the condition that the molecule is in a closed state can cause the molecular switch controllable effector molecule to generate a condition that the molecule is changed from the closed state to the open state, and the molecular switch can control the effector molecule to generate a condition that the molecule is converted from the open state to the closed state.
  • the molecular switch controllable effect molecule under the second light irradiation condition can be turned on, and, for example, the molecular switch controllable effect molecule under the condition that the first light and the second light are simultaneously irradiated can be turned off.
  • the molecular switch controllable effect molecule under the first light irradiation condition can be in a closed state, and for example, the illumination condition that the first light can provide and the illumination condition that the second light can provide can generally be different. .
  • the first light and the second light may partially overlap each other, and the first light and the second light may only partially overlap each other, or one of the light and the other light may overlap each other.
  • all of the first light and the second light overlap each other, and for example, all of the second light and the first light overlap each other.
  • the first light may be single hollow light or multiple hollow light
  • the second light may cover at least part or all of the unlighted area surrounded by the first light illumination area.
  • the hollow light generally refers to any light that can form an illumination region, and the illumination region encloses a non-illuminated region, which refers to a region that is significantly weaker, closer to, or equal to zero than the illumination region.
  • the unlighted area may be one or more.
  • the first light may be a single hollow light, when the first light When the formed illumination area is surrounded by a plurality of unlit areas, the first light may be multiple hollow light.
  • the shape of the unilluminated area surrounded by the illumination area formed by the first light may be various regular or irregular shapes, and the shapes may be nano-scaled in a certain dimension, for example, in a specific embodiment of the present application
  • the shape of the unilluminated area may be a circle, an ellipse, a polygon, an extended line, etc., the diameter of the circle, the long axis of the ellipse, the short axis of the ellipse, the diameter of the polygon, the width of the extended line, etc.
  • nm may be Not more than 5 nm, 5-10 nm, 10-15 nm, 15-20 nm, 20-25 nm, 25-30 nm, 30-35 nm, 35-40 nm, 40-45 nm, 45-50 nm, 50-55 nm, 55-60 nm, 60- 65 nm, 65-70 nm, 70-75 nm, 75-80 nm, 80-85 nm, 85-90 nm, 90-95 nm, 95-100 nm, 100-110 nm, 110-120 nm, 120-130 nm, 130-140 nm, 140-150 nm, Sizes of 150-160 nm, 160-180 nm, 180-200 nm or more.
  • the hollow light may be ring light, have a hollow surface light, or the like. Further, the plurality of unlit areas may form an array, and the first light itself may be a multi-beam or array light. In another embodiment of the present application, the hollow light may be an annular light array, a surface light having a hollow array, or the like, and the surface light having a hollow array means that the plurality of unlighted areas form an array in the illumination area.
  • the second light may be solid light, which generally refers to light that is formed by the illuminated area that does not surround any non-illuminated areas. In some embodiments of the present application, the solid light may be a single light beam, a surface light, or the like. Further, the second light may be a multi-beam or an array of light. In another embodiment of the present application, the second light may be an array of light formed by a plurality of single light beams.
  • the illumination area of the second light does not exceed the outer edge of the illumination area of the first light, and the illumination area of the second light does not exceed the outer edge of the illumination area of the first light.
  • the illumination region of the light does not involve a region other than the first light illumination region and the unilluminated region surrounded by the first light illumination region, and the illumination region formed by the first light and/or the second light may be such that the light is photolithographically The area of illumination formed on the material.
  • the molecular switch controllable effector molecule generating molecule generally means that under certain conditions, it can be changed from an open state to a closed state and/or from a closed state to an open state, and in an open state, under certain conditions.
  • the molecule structure of the controllable effector molecule can be different.
  • the molecular switch controllable effector molecule produces a molecule in an open state, generally refers to a molecular switch controllable effector molecule.
  • the molecule can produce an effector molecule under certain conditions, so that the molecular switch controllable effector molecule in an open state produces a molecularly produced effector molecule.
  • the condition may be a condition without light, or may include an illumination condition, specifically, an illumination condition such as ultraviolet light, visible light, or infrared light, and for example, may be at a wavelength of not more than 5 nm, 5-10 nm, 10-20 nm, 20 -40 nm, 40-60 nm, 60-80 nm, 80-100 nm, 100-150 nm, 150-200 nm, 200-250 nm, 250-300 nm, 300-350 nm, 350-400 nm, 400-450 nm, 450-500 nm, 500-550 nm 550-600nm, 600-650nm, 650-700nm, 700-750nm, 750-800nm, 800-850nm, 850-900nm, 900-950
  • the molecular switch controllable effector molecule in the closed state generally refers to a condition in which a molecularly controlled effector molecule produces an effector molecule with respect to an open state, and is in a closed state under the same or similar conditions.
  • Molecular switch controllable effector molecules produce molecules that are substantially incapable of producing effector molecules.
  • the molecular switch controllable effector molecule produces a molecular production effector molecule, which may be a chemical bond cleavage of a partial group of a molecule generated by a molecular switch controllable effector molecule to generate an effector molecule, a molecular switch controllable effector molecule-generating molecule The group changes and converts into effector molecules.
  • the molecular switch controllable effector molecule generating molecules in an open state can generate effector molecules, and those skilled in the art can select a suitable kind of compound sensitive to the effector molecule according to the kind of the effector molecule.
  • a lithographic material comprising a compound that is sensitive to the effector molecule such that the effector molecule can change the physical properties and/or chemistry of the lithographic material in the open region of the molecular switch.
  • the effector molecule produced by the molecular switch controllable effector molecule may be a delithography material protecting group molecule, and the lithographic material protecting group molecule may be, but not limited to, an acidic molecule or a basic molecule.
  • the compound sensitive to the effector molecule may be an effector molecule sensitive polymer
  • the effector molecule sensitive polymer may be an acrylic acid and an acrylate material including, but not limited to, a protective group, and an aliphatic group.
  • a suitable group as a protective group for a compound sensitive to an effector molecule can be Including, but not limited to, t-BOC, etc., more specifically, in the presence of a molecule for protecting a protecting group, the protecting group in the molecular structure of the compound sensitive to the effector molecule can be removed, thereby allowing
  • the physical properties and/or chemical properties of the lithographic material of the deprotecting group (relative to the lithographic material without the deprotecting group)
  • the physical and/or chemical properties of the lithographic material may generally be a change in the solubility of the lithographic material in the developer, for example, sensitive to the effector molecule in the presence of the lithographic material protecting group molecule.
  • the protecting group in the molecular structure of the compound can be removed, so that the solubility of the photoprotective material from which the protecting group is removed can be increased or decreased in the developing solution.
  • the effector molecule produced by the molecule switch controllable effector molecule may be a photolithography material dissolution inhibitor, and the photolithography material dissolution inhibitor may be a material including, but not limited to, a diazonaphthoquinone or the like.
  • the compound sensitive to the effector molecule may be an effector molecule-sensitive polymer, and the effector molecule-sensitive polymer may be a material including, but not limited to, a novolac resin, and the person skilled in the art may according to the type of the effector molecule, reaction conditions, and the like.
  • the parameter selects a suitable effector molecule sensitive polymer as a compound sensitive to the effector molecule
  • the effector molecule sensitive polymer may be a material including, but not limited to, phenolic formaldehyde, etc., more specifically, in the presence of a lithographic material dissolution inhibitor
  • the physical properties and/or chemical properties of the compound sensitive to the effector molecule may vary.
  • the physical and/or chemical properties of the lithographic material may generally be a change in the solubility of the lithographic material in the developer, for example, in the presence of a lithographic material dissolution inhibitor, the lithographic material in the developer The solubility can be increased or decreased.
  • the effector molecule produced by the molecular switch controllable effector molecule may be an activation lithography material polymerization control molecule, more specifically, a polymerization reaction initiation molecule, and the activation lithography material polymerization control molecule may be included but It is not limited to acidic molecules, basic molecules, singlet oxygen, various polymerization initiators, etc., and compounds sensitive to effector molecules may be effector-sensitive polymerizable monomers or oligomers, etc., and the activation lithography material polymerization control molecules The same may be the same as the effector molecule-sensitive polymerizable monomer or oligomer, which is usually a monomer and/or oligomer which can undergo polymerization, and more specifically, the effector molecule is sensitive.
  • the compound may be, but not limited to, an acrylate molecular monomer, a methacrylate molecular monomer, a vinyl molecular monomer, a vinyl ether molecular monomer, an epoxy molecular monomer, or the like.
  • the monomer or oligomer in the lithographic material may undergo a polymerization reaction in the presence of activating the photopolymerization control molecule to cause changes in the physical properties and/or chemical properties of the lithographic material.
  • the physical and/or chemical properties of the lithographic material may generally be a change in the solubility of the lithographic material in the developer, for example, as an effector molecule, in the presence of activating the photopolymerization control molecule.
  • the monomer or oligomer of the compound may undergo a polymerization reaction to increase or decrease the solubility of the photolithographic material in which the polymerization reaction occurs in the developer.
  • the molecular switch controllable effector molecule may comprise a molecular switch group and an effector molecule generating group in the molecular structure of the molecule.
  • the molecular switch group containing the molecular switch group can control the effector molecule to produce a molecule, which can usually undergo a configuration change under certain conditions, thereby enabling the molecular switch controllable effector molecule to generate a molecule from an open state to a closed state and/or Or changing from a closed state to an open state (a condition that the molecular switch controllable effector molecule produces a molecule in a closed state may include a condition of the first light illumination, and the condition that the molecular switch controllable effector molecule produces the molecule in an open state may be including
  • the condition of the dichroic light for example, the substance having the molecular switching group may be, but not limited to, a structure having proton transfer tautomerism, cis-trans isomerism, bond hetero-cleavage,
  • the substance may more specifically include, but is not limited to, a diarylethene compound, an azobenzene compound, a spiropyran compound, a spirooxazine compound, a fulgide compound, a salicylaldehyde aniline Schiff base. Class of compounds, etc.
  • the molecular switch controllable effector molecule containing the effector molecule generating group may be a group capable of releasing an effector molecule under certain conditions when the molecular switch controllable effector molecule is in an open state (the condition for releasing the effector molecule)
  • the light-emitting condition for producing an effector molecule as described above may be included, and the molecular switch capable of generating an effector molecule may control the effector molecule to generate a molecule, or may be when the molecular switch-controllable effector molecule produces the molecule in an open state, under certain conditions.
  • a conformational transition can occur (the conditions for conversion to an effector molecule can include the illumination conditions that produce the effector molecule as described above), thereby causing the molecularly switchable controllable effector molecule in the open state to transform itself into an effector molecule.
  • the substance having an effector molecule generating group may include, but is not limited to, a photoacid generating molecule, a photobase generating molecule, a photoactive molecule, a polymerization initiator generating molecule, etc., thereby releasing an acidic molecule, a basic molecule, and a singlet state, respectively. Oxygen, a polymer initiator or the like acts as an effector molecule.
  • the photoacid generating molecule may include an ionic type and a nonionic type, and the ionic type may specifically include, but not limited to, a diazonium hydrochloride compound, a diazosulfate compound, a diazosulfonate compound, and a diazo.
  • a fluorophosphate compound, an onium salt compound, or the like, and the onium salt compound may include, but not limited to, an iodonium salt compound, a selenium salt compound, a phosphonium salt compound, an arsenium salt compound, or the like.
  • the nonionic group may be, but not limited to, a polyhalogenated acetophenone compound, a triazine derivative compound, a sulfonyl chloride ester compound, or the like.
  • the photobase generating molecule may include, but is not limited to, a transition metal ion ammonia complex compound, a quaternary ammonium compound, an ester compound (including a ketoxime compound, a carbamate compound, a decyl carbamate).
  • the photosensitive molecule may be a porphyrin compound, a phthalocyanine molecular compound, and the polymerization initiator may be a benzoin ether compound or benzil.
  • a ketal compound an acetophenone compound, an acyl phosphine oxide compound, an ⁇ -chloroacetophenone compound, a sulfonyl acetophenone compound, a sulfonyloxyacetophenone compound, an azo compound, A peroxosulfide compound, a benzophenone compound, a thioxanthone compound, an anthraquinone compound, a diazonium salt compound, a phosphonium salt compound, or the like.
  • the molecular switch can control the effector molecule to generate a molecule, and the molecular switch group and the effector molecule generating group can be connected by a chemical bond, and the chemical bond can be, for example, an ionic bond, a covalent bond or the like.
  • the molecular switch controllable effector molecule generating molecule may be a p-toluenesulfonic acid compound, a trifluoromethanesulfonic acid compound, a methanesulfonic acid compound, a p-toluenesulfonic acid sulfonium salt. a compound, a sulfonium triflate compound, a sulfonium methanesulfonate compound, or the like.
  • the molecular switch-controllable effector molecule in the open state since the molecule-switchable controllable effect molecule in the open state can generate a molecule-generating effector molecule by including a condition of illumination, the molecular switch-controllable effector molecule in the open state generates an effector molecule.
  • the method may include changing the illumination condition of the molecular switch controllable effect molecule in the open state to generate a molecule, for example, may provide a third beam to the molecular switch controllable effect molecule generating molecule in an open state, or may change the second The parameters of the beam (eg, light intensity, wavelength, etc.) such that the molecularly switchable controllable molecules in the open state produce molecularly generated effector molecules.
  • the lithography method provided by the present application may further include: removing any one of a lithographic material that undergoes a change in physical or chemical properties or a lithographic material that has not changed.
  • a suitable method for removing a lithographic material that undergoes a change in physical or chemical properties or a lithographic material that has not changed depending on the type of lithographic material. For example, a portion of the lithographic material may be removed by dissolving a lithographic material having a higher solubility in a developing solution in a developing solution by a developing solution.
  • Another aspect of the present application provides a compound which is a molecular switch controllable effector molecule as described above which produces a molecule.
  • the effector molecule produced by the compound may be a lithographic material protecting group molecule, and the lithographic material protecting group molecule may be, but not limited to, an acidic molecule, a basic molecule, Singlet oxygen, etc.
  • the effector molecule produced by the molecule produced by the compound may be a lithographic material dissolution inhibitor, and the lithographic material dissolution inhibitor may be, but not limited to, diazonaphthoquinone or the like.
  • the effector molecule generated by the molecular switch controllable effector molecule may also be an activation lithography material polymerization control molecule, more specifically, a polymerization reaction initiation molecule, and the activation lithography material polymerization control molecule may be including but not limited to Acidic molecules, basic molecules, singlet oxygen, polymerization initiators, and the like.
  • Another aspect of the present application provides a lithographic material comprising a molecular switch controllable effector molecule generating molecule and a compound sensitive to an effector molecule.
  • the compound sensitive to the effector molecule may be an effector molecule-sensitive polymer, and the effector molecule-sensitive polymer may be acrylic acid and acrylate including, but not limited to, a protective group.
  • Materials such as materials, aliphatic cycloolefin materials, maleic anhydride materials, etc., those skilled in the art can select a suitable group as a protective group for a compound sensitive to an effector molecule according to the type of the effector molecule, reaction conditions and the like, and protect The group may be, but not limited to, t-BOC, etc., more specifically, the protecting group in the molecular structure of the compound sensitive to the effector molecule may be removed in the presence of the deprotecting molecule of the lithographic material.
  • the physical properties and/or chemical properties of the photoprotective material with respect to the deprotecting group can be varied.
  • the solubility of the compound which is not sensitive to the effector molecule and the compound which is deprotected by the effector molecule is usually changed in the developer, for example, the deprotection group is sensitive to the effector molecule.
  • the solubility of the compound in the developer is increased or decreased.
  • the compound sensitive to the effector molecule may be a material such as a novolac resin. More specifically, the compound sensitive to the effector molecule may be a material including, but not limited to, phenol formaldehyde.
  • the physical properties and/or chemical properties of the compound sensitive to the effector molecule may vary in the presence of a lithographic material dissolution inhibitor.
  • the physical and/or chemical properties of the lithographic material may generally be a change in the solubility of the lithographic material in the developer, for example, in the presence of a lithographic material dissolution inhibitor, the lithographic material in the developer The solubility can be increased or decreased.
  • the compound sensitive to the effector molecule may be an effector molecule-sensitive polymerizable monomer or oligomer, etc., and the compound sensitive to the effector molecule is usually a monomer and/or oligomer which can undergo polymerization, etc., more specifically
  • the compound sensitive to the effector molecule may be, but not limited to, an acrylate molecular monomer, a methacrylate molecular monomer, a vinyl molecular monomer, a vinyl ether molecular monomer, an epoxy molecule. Monomers, etc.
  • the monomer or oligomer in the lithographic material may undergo a polymerization reaction in the presence of activating the photopolymerization control molecule to cause changes in the physical properties and/or chemical properties of the lithographic material.
  • the solubility of the material obtained after the polymerization reaction and the photolithographic material which has not undergone polymerization changes in the developer for example, the solubility of the photolithographic material in which the polymerization reaction occurs in the developer is increased or decreased.
  • the lithographic material provided by the present application further includes components which may be included in other various lithographic materials, such as catalysts, initiators, auxiliaries, etc., which may be applicable in various fields. Defoamers, leveling agents, stabilizers, dispersants, etc. for lithographic materials.
  • the lithography method and lithography material provided by the present application are based on dual-beam super-resolution technology, the light source adopts a mature semiconductor laser, the cost is low, the resolution has no theoretical limit, and can reach below 10 nm process node, and the high-resolution lithography cost is greatly reduced.
  • the specific benefits are as follows:
  • the existing laser direct writing technology mainly uses semiconductor lasers, and its resolution cannot exceed 100 nm due to the limitation of laser wavelength. Therefore, nano-scale processing below 100 nm can not be realized by ordinary laser direct writing technology, and electron beam is still needed.
  • a higher resolution method, and the present application is based on the principle of dual beam technology, free from wavelength limitations, and can achieve resolutions below 100 nm.
  • the present application uses a low-cost solid-state semiconductor laser, which has high luminous efficiency, no high-voltage power supply, and low cost for a single light source to be easily expanded into multiple light sources.
  • the multi-beam method is easier to realize multiple beams than the electron beam, and it is more likely to realize large-scale, large-range, large-scale super-resolution nano multi-beam lithography, and the speed can be greatly improved compared with the electron beam.
  • the dual-beam principle adopted by the present application implements super-resolution lithography as far-field, but near-field.
  • Super-resolution implementation usually requires the imaging physical distance to be controlled within the near-field range, that is, within the wavelength length. This is extremely difficult to achieve in actual lithography, and super-RENS (Super Resolution Near-field Structure) is used.
  • the super-RENS layer needs to be realized first in the upper layer of the photoresist, and the process is more complicated and costly.
  • the far-field double-beam super-resolution realized in the present application is double in the far field range.
  • the beam-regulating PSPAG directly reacts on the photoresist, and there is no physical distance limitation problem of near-field imaging.
  • the imaging is simple and easy, and the photoresist process is completely consistent with the current mainstream process, and the process is mature and the connection is good.
  • the photoinduced acid production of conventional positive lithography PAG is uncontrollable.
  • the spatial resolution of chemical amplification etching after photo-induced acid production is controlled by the wavelength of the light source and the numerical aperture of the lens.
  • the PAG designed in the invention can realize the control of photoacid release under the control of the molecular switch, thereby effectively realizing the spatial resolution regulation of the photoacid release by using the light reversible regulation mode of the double beam, and getting rid of the wavelength and value of the light source. Aperture limitation.
  • the process as described in FIG. 1 is a basic principle process diagram for realizing super-resolution of the dual beam technology of the present invention.
  • the first step shown in the figure first opens the ring-shaped suppression light 1, that is, h ⁇ 1, which is an annular light formed by phase conversion, and its annular hollow can be adjusted in size, so that the resolution of the double beam can be adjusted by adjusting the size of the hollow portion.
  • the role of the beam 1 in the present invention is to turn off the molecular switch (even if the molecular switch controllable effector molecule produces the molecule in a closed state).
  • the second step shown is to concentrically superimpose the beam 2 on the basis of the ring light 1, ie h ⁇ 2, which is a beam of activated Gaussian beam.
  • the function of the beam 2 is to open the molecular switch (even if the molecular switch can be The effector molecule produces the molecule in an open state).
  • the third step of the double beam process of the present invention is to excite the photochemical reaction on the basis of the opening of the molecular switch.
  • the first method is that the ring suppression light 1 is not adjusted, and the 1 and 2 can be turned on or off. In this state, another wavelength is directly superimposed.
  • the second method is that the photochemical group and the molecular switch have the same wavelength, and the synchronization needs to be increased 1 And the intensity of 2 reaches the threshold at which the photochemical group reaction occurs.
  • FIG. 2 is a molecular switch controllable polymerization deprotection mode diagram.
  • the molecular characteristics and reaction modes of the final depolymerization groups of the polymer under molecular switch control are realized, and the final form is positive lithography.
  • 1 indicates a moiety having a molecular switching function (hereinafter referred to as molecular switch 1)
  • 2 indicates a moiety having a photoacid generating molecular function or a strong acid group (hereinafter referred to as an acid generating group 2)
  • 3 indicates a photobase generating agent function.
  • FIG. 3 A portion or a base molecular group (hereinafter referred to as a base group 3), and 4 indicates a portion having a function of a photosensitizer molecule (hereinafter referred to as a photosensitive molecule 4).
  • Figure A shows the molecular switch controllable photoacid generation molecule (PSPAG), in which the photoacid generation molecular characteristics include photoacid generator molecules and strong acid groups, and the molecular switch 1 can make the compound under the illumination of the activation beam h ⁇ 2.
  • PSPAG molecular switch controllable photoacid generation molecule
  • the inactive state OFF is converted to the active state ON, and the compound can be switched from the active state ON to the inactive state OFF under the illumination of the ring suppression beam h ⁇ 1, and the molecular switch 1 can be repeatedly switched under the alternating light of h ⁇ 1 and h ⁇ 2.
  • the acid-producing group 2 when the compound is OFF, the acid-producing group 2 cannot release the strong acid molecule or the strong acid molecule group cannot be dissociated from the compound, and when the compound is switched to ON, 2 releases the strong acid under the specific illumination of h ⁇ 3.
  • FIG B shows the molecular switch controllable photobase generating molecule (PSPBG), in which the photobase generating molecular characteristics include photobase generator molecules and strong base groups.
  • PSPBG molecular switch controllable photobase generating molecule
  • the PSPBG molecule shown in Figure B is when the compound is OFF.
  • the base group 3 cannot release strong acid molecules or the strong acid molecule group cannot be dissociated from the compound.
  • the compound is converted from the inactive state OFF to the activated state ON under the illumination of the activation beam h ⁇ 2, and 3 releases the strong base molecule under the specific illumination of h ⁇ 3.
  • a strong base group dissociates from the compound.
  • the released strong base molecule reacts with a specific protecting group on the resin material to dissociate it, so that the resin molecule is deprotected.
  • Figure C shows a molecular switch controllable photoactive molecule (PSPSen) that activates the beam h ⁇ 2 to switch the compound from OFF to ON, whereby the photosensitizer molecule 4 is activated by photoactive activation, while the ring beam h ⁇ 1 causes the photoactive molecule 4 to turn off photoactive activation.
  • activation of photoactivated 4 activates oxygen molecules to singlet oxygen O3- at a specific wavelength h ⁇ 3.
  • Single - line oxygen has strong oxidizing properties and reacts with specific protecting groups of the resin material to dissociate them to achieve deprotection.
  • 3A, 3B is a molecular switch controllable monomer polymerization mode diagram.
  • 3A and 3B show the molecular characteristics and reaction modes of molecular polymerization of molecular switch controllable polymer monomers.
  • 3A, 3B denotes a moiety having a molecular switching function (hereinafter referred to as molecular switch 1)
  • 2 denotes a monomer molecule
  • 3 denotes a polymer molecule
  • 4 denotes a moiety having a photoinitiator molecule function
  • 5 denotes a photosensitizer molecule function.
  • photosensitizer molecule 5 indicates a moiety having a photoacid generating molecular function (hereinafter referred to as photoacid generating molecule 6), and 7 indicates a moiety having a photobase generating molecular function (hereinafter referred to as photobase generating molecule 7).
  • Figure 3A, 3B, Figure A shows the molecularly controlled polymerizable monomer molecule. The compound can be converted from the inactive state OFF to the active state ON under the illumination of the activation beam h ⁇ 2, and is activated by the ON state under the illumination of the ring suppression beam h ⁇ 1.
  • the compound For the inactive state OFF, the compound can be repeatedly switched under the alternating light of h ⁇ 1 and h ⁇ 2.
  • the molecule switch controllable monomer molecule described in A of FIG. 3A, 3B when the compound is OFF, the monomer molecule 2 cannot be polymerized, and when the compound is switched to ON by the activation beam h ⁇ 2, the monomer molecule 2 can be performed.
  • the polymerization reaction, after activation 2, is polymerized under the action of specific light and other components of h ⁇ 3 to form polymer 3.
  • Figure 3A, 3B, Figure B is a molecular switch controllable photoinitiator molecule, the PInit molecule 4 in the inactive state OFF can not initiate the polymerization reaction, and the molecular switch activates PInit after the activation of the beam, thereby acting on the h ⁇ 3 effect light and the monomer molecule.
  • the polymerization reaction is initiated.
  • Figure 3A, 3B shows a molecular switch controllable photoactive molecule (PSPSen), which activates the beam h ⁇ 2 to switch the compound from OFF to ON, whereby the photosensitizer molecule 5 is activated by photoactive activation, while the ring beam h ⁇ 1 causes the photoactive molecule 5 The photoactivation ability is turned off.
  • PSPSen molecular switch controllable photoactive molecule
  • FIG activated photoactive C 4 activated at a specific wavelength h ⁇ 3 activating oxygen to singlet oxygen O 3-, singlet oxygen initiator to achieve polymerization of the specific monomer molecules are polymerized molecules.
  • Figure 3A, 3B, Figure D shows the molecular switch controllable photoacid generation molecule (PSPAG), the photoacid generating group 6 can be repeatedly switched under the alternating light of h ⁇ 1 and h ⁇ 2, and the activated 6 is in h ⁇ 3 specific illumination. The strong acid molecules are released under the action of other components to polymerize the monomers.
  • Figure E shows the molecular switch controllable photobase generating molecule (PSPBG). After the photobase generating group 7 is activated by h ⁇ 2, the strong base molecule is released under the specific illumination of h ⁇ 3, and the monomer is polymerized under the action of other components. reaction.
  • Light-controlled molecular switches generally refer to molecules that can be reversibly converted to different molecular configurations under illumination of different wavelengths to present switching characteristics.
  • the reaction types of molecular switches can be classified into proton transfer tautomerism, cis-trans isomerization, bond hetero-cleavage, and pericyclic reaction systems.
  • Molecules having switching characteristics are mainly concentrated on compounds such as diarylethene compounds, azobenzene compounds, spiropyrans, spirooxazines, and fulgides.
  • the molecular switch in the present invention includes the reaction forms of the above several molecular switches, and as shown in FIGS.
  • A is a salicylaldehyde aniline Schiff base compound in the proton transfer tautomeric form, in UV/ Molecular switching can be realized under VIS.
  • B is a cis-trans isomer form, and azobenzene compounds are a class of molecules having excellent switching characteristics.
  • C and D belong to the spiropyrans and spirooxazines in the heterocrack reaction form of the bond, both of which achieve excellent molecular switching performance under two different illumination switches.
  • E is a reaction of a pericyclic reaction system, and its essential feature is that the hexatriene structure in the molecule is switched to a cyclohexadiene structure under illumination, and is reversibly converted under illumination.
  • Switching molecules that conform to such characteristics include fulgides, diarylethenes, and the like.
  • FIG. 5 is a de-group reaction of the molecular switch of the pericyclic reaction system.
  • Shown in Figure 5 is a molecular switch based on a molecular switch of a pericyclic reaction system to control the photoacids/photobase de-grouping.
  • the photoacid generator is mainly divided into an ionic type and a non-ionic type.
  • the ionic photoacid generator of the present invention mainly includes a diazonium salt compound such as a diazonium hydrochloride compound, a diazosulfate compound, and a diazobenzene.
  • the acid salt compound, the diazofluorophosphate compound, and the phosphonium salt compound such as an iodonium salt compound, a selenium salt compound, a phosphonium salt compound, an arsenic phosphonium salt compound, and the like.
  • the nonionic photoacid generator mainly includes an organic halogenated compound such as a polyhalogenated acetophenone compound, a triazine derivative compound, a sulfonyl chloride ester compound or the like. As shown in A in Fig. 5, based on the hexamethylene structure-based molecule, the dotted line represents various possible ring type, such as benzene ring compounds, cyclopentane compounds, cyclopentene compounds, and the like.
  • hexatriene structural molecules can reversibly interconvert with cyclohexadiene structure by intramolecular ring closure under the interaction of h ⁇ 1 and h ⁇ 2, while photoacid molecules at R1 position may be detached from cyclohexadiene structure by h ⁇ 3
  • the cyclohexadiene structure is irreversible to a benzene ring structure.
  • FIG. 5B based on the principle of FIG. A, a PSPAG based on a diarylene-based molecular structure, wherein R1 is a moiety having a function of producing a photoacid molecule, such as trifluoromethanesulfonic acid commonly used in photoacid generators.
  • the strong acid group has only closed-loop/open-loop reversible conversion in h ⁇ 1 and h ⁇ 2. Under the action of h ⁇ 3, the strong acid group is detached from the molecule, and diethylene-ethylene is controlled as a molecular switch to release the acid group.
  • FIG. 6 is a molecular switch controllable polymerization deprotection positive dual beam lithography pattern, that is, the polymerization of the photomolecular switch controllable effect molecule of the present invention in the photoresist under the action of the double beam
  • A is a ring suppression beam h ⁇ 1
  • 2 black solid circle
  • 3 wave curve
  • 4 black solid triangle
  • A is that when the annular suppression beam 1 is irradiated on the photoresist, the polymer chains in the photoresist are connected to the protective group, and the molecular switch control molecules in the photoresist are in the OFF state by default, so the ring beam 1 is Irradiation on top does not cause the molecules controlled by the molecular switch to chemically react with the photoresist.
  • B is a Gaussian active beam h ⁇ 2 concentrically superimposed on the annular suppression beam. When the beam passes through the center hole of the ring beam and acts on the photoresist, the originally inactive state 2 is activated as 6 in the figure ( The hollow triangle), ie the effector molecule controlled by the molecular switch, is activated.
  • C shown in Fig. 7 is an additional switching effect beam, that is, a h ⁇ 3 beam.
  • the activated molecule releases a free effect group, such as the strong acid, strong alkali, single line oxygen, etc.
  • the protective group 2 on the polymer dissociates from the polymer.
  • the dissociated photoresist polymer layer is decomposed after being exposed to the developer, and the protected polymer is not decomposed by the developer.
  • FIG. 7 Depicted in Figure 7 is a molecular switch controllable monomer polymerization negative two-beam lithography pattern.
  • 1 shown in A is a ring suppression beam h ⁇ 1
  • 2 (small wave line) represents a polymer monomer molecule of the photoresist
  • a of FIG. 3 represents a monomer molecule controlled by a molecular switch
  • 3 (a hollow square) ) indicates a molecular switch polymerization control molecule
  • 4 indicates a material to be treated.
  • FIG. A shows a Gaussian active beam h ⁇ 2 concentrically superimposed on the ring-shaped suppression beam.
  • 1 is a ring-shaped suppression light h ⁇ 1
  • 2 is a photoresist layer
  • 3 is a material to be processed, such as a silicon wafer.
  • the ring suppression beam is positioned on the photoresist-coated silicon wafer.
  • the activation beam 4 is superimposed on the position of the photoresist where the ring light is positioned, that is, h ⁇ 2 in FIGS. 8A and 8B, and the molecular switching effect molecules of the photoresist portion 5 irradiated by the activation beam 4 in FIGS. 8A and 8B are activated.
  • step three the effect light h ⁇ 3 acts on the activated region of the photoresist, and the molecular switch effect molecules in this region release the effect group to deprotect the protective group in the photoresist.
  • Steps 1 to 3 repeatedly perform step-scan exposure under program control, that is, connect to form a pattern to be etched.
  • step four after the developer is added, the photoresist portion of the deprotected group is dissolved by the developer, and the unexposed region is not dissolved by the developer.
  • step five the exposed silicon wafer region can be etched, processed, and processed.
  • step six the photoresist of this step is eluted to expose the surface of the silicon wafer including the etching pattern.
  • Step seven coating a new photoresist layer, ready to start the next lithography operation.
  • FIG. 9A, 9B Illustrated in Figures 9A, 9B is a process diagram of a molecular switch controllable monomer polymerization negative two-beam lithography process.
  • 1 is a ring-shaped suppression light h ⁇ 1
  • 2 is a photoresist layer
  • 3 is a material to be processed.
  • the annular suppression beam is positioned on the surface of the photoresist coated material.
  • Step 2 superimposing the activation beam 4 at the position of the photoresist where the ring light is positioned, that is, h ⁇ 2 in FIGS. 9A and 9B, and the molecular switch aggregation control molecules of the photoresist portion 5 irradiated by the activation beam 4 in FIG. 9A, 9B are activated.
  • the effect light h ⁇ 3 acts on the activated region of the photoresist, and the activated polymerization control molecule in this region acts on the monomer component in the photoresist to initiate the polymerization reaction.
  • Steps 1 to 3 repeatedly perform step-scan exposure under program control, that is, connect to form a pattern to be etched.
  • step four after the developer is added, the portion of the photoresist which is not exposed is dissolved by the developer, and the exposed region is protected by the polymer from being dissolved by the developer.
  • the exposed material area can be processed, etched, and processed.
  • the photoresist of this step is eluted to expose the surface of the material containing the treatment.
  • Step seven coating a new photoresist layer, ready to start the next lithography operation.
  • FIG. 10A and 10B A schematic diagram of a dual beam shaping technique is shown in Figs. 10A and 10B.
  • Gaussian beams and Gaussian ring beams are used, and the intensity distribution is nonlinearly distributed, so that the energy in the active region is not uniform and the scope cannot be precisely controlled.
  • the double-beam lithography system of the invention adopts a beam shaping method to modulate both the solid beam and the hollow beam into a flat-top beam shape, which can effectively improve the control precision of the processing edge.
  • the beam shaping method is used to shape the solid Gaussian beam and the vortex beam into corresponding solid flat top beams and flat top double beams, and the edges are steep and vertical, so that the energy distribution is more accurate.
  • FIGs. 10A and 10B A schematic diagram of a dual beam shaping technique is shown in Figs. 10A and 10B.
  • 10A, 10B shows that the solid Gaussian beam is shaped into a solid flat-top beam.
  • B shown in Figs. 10A and 10B is a vortex beam shaped into a hollow flat-top beam.
  • C shown in Figs. 10A, 10B indicates that the superimposed double beam can be directly shaped into a flat top double beam, or the shaped solid flat top beam and the hollow flat top beam are superimposed into a flat top double beam form.
  • D shown in Figs. 10A, 10B indicates that the size of the hollow size is adjusted by adjusting the energy of the hollow flat top beam.
  • E shown in Figures 10A, 10B represents the final write width of the solid flat-top beam under different adjustments of the hollow flat-top beam.
  • FIGS. 11A and 11B are two versions of a parallelized dual beam lithography system.
  • the dual beam adopts a method of directly generating a concentric beam and realizing parallelization.
  • h ⁇ 1 is an initial input beam of annular light
  • h ⁇ 2 and h ⁇ 3 are initial input beams of a solid Gaussian beam.
  • One device shown that h ⁇ 1 and h ⁇ 2 are merged by a beam splitter and then collected by the lens group 1 into the beam shaping device 2 to realize concentricity of h ⁇ 1 and h ⁇ 2.
  • the device 2 can usually be realized by a circularly-preserving fiber.
  • the concentric beams are converted by the beam shaping device 3 into a Gaussian beam of concentric beams into a flat top beam of average energy distribution.
  • the converted and expanded beam enters the microlens array group 4 and is converted into an array-type multi-beam through the microlens group.
  • the two-beam phase-conversion array group 5 corresponds to the microlens array group 4.
  • Each beam from the four beams enters a corresponding phase conversion unit, which realizes that h ⁇ 1 is converted from an initial beam to a ring beam, and h ⁇ 2 still maintains a solid beam, thereby realizing Array type double beam.
  • the array double beam enters the spatial light modulator 6 corresponding to the pixel unit, and the device can control the on and off of each pixel double beam by a computer program at a high speed, thereby modulating each double beam and controlling the writing of the pattern.
  • the two-beam array emerging from the spatial light modulator 6 is focused by the lens group 7, and then the image is reduced by the miniature image lens group 8, and finally high-speed parallel two-beam lithography is realized on the surface of the lithographic material 9.
  • the lithography material realizes displacement step control under the control of the precision displacement platform 10.
  • Scheme 2 in Figures 11A, 11B shows the manner in which annular light is generated to separate from the solid Gaussian beam.
  • h ⁇ 1 is an initial input beam of annular light
  • h ⁇ 2 and h ⁇ 3 are initial input beams of a solid Gaussian beam.
  • H ⁇ 1 first enters the polarizing device 2 after passing through the lens group 1, thereby generating a desired polarized light beam.
  • the solid Gaussian beam h ⁇ 2 is converted into a flat-top beam by the Gaussian beam shaper 4 through the lens group 3.
  • the ring beam converted by h ⁇ 1 is also converted into a hollow flat-top beam shape by the annular beam shaper 5.
  • the two beams are merged by the beam splitter 6 and passed through the phase-type diffraction grating array 7 to convert the polarized h ⁇ 1 into an array-type vortex light, that is, a ring-shaped light array, and the solid beam h ⁇ 2 is superimposed with the ring-shaped light array to pass through the spatial light.
  • Modulator 8 The phase type diffraction grating is coupled to the spatial light modulator and the pixel units are in one-to-one correspondence, thereby implementing individual switching control of each double beam cell, thereby controlling the writing of the pattern.
  • the two-beam array from the spatial light modulator 8 is focused by the lens group 9, and then the image is reduced by the miniature image lens group 10, and finally high-speed parallel two-beam lithography is realized on the surface of the lithography material 11.
  • the lithography material realizes displacement step control under the control of the precision displacement platform 12.
  • the two diagrams A and B shown in Fig. 12 show that the scanning mode adopted by the dual beam array shown in the present invention includes two coordinate system systems: Cartesian coordinate system scanning and polar coordinate system scanning. Two coordinate system modes can be switched depending on the characteristics of the desired pattern.
  • A is shown in Fig. 12 as an array scanning mode in a Cartesian coordinate system. After the lithographic pattern data is cut into a large number of rectangular blocks, the double beam is finally scanned from the corner vertices of the rectangular block to the vertices of the diagonal of the rectangular block in a serpentine manner.
  • B shows an array scanning mode in a polar coordinate system.
  • the lithographic patterns are symmetrically distributed in a circular center in a polar coordinate manner, and the array dots are patterned by circular scanning.
  • the two scanning system modes described in the present invention can be used separately in the lithography process, or can be mutually crossed, merged, and switched together, and the switching of the two coordinate systems is controlled by a computer program.
  • the positive lithography method operates as follows:
  • the annular suppression beam is positioned on the material coated with the photoresist
  • Steps 1 to 3 are repeatedly subjected to step-scan exposure under program control, that is, the formation of the connection is required. Etched pattern
  • the exposed areas can be etched, processed and processed;
  • the negative lithography method operates as follows:
  • the annular suppression beam is positioned on the surface of the material coated with the photoresist
  • Steps 1 to 3 are repeatedly subjected to step-scan exposure under the program control, that is, the connection is formed to be etched.
  • the exposed material area can be processed, etched and processed
  • the double-beam photoresist is mainly composed of a resin, a double-beam controllable molecular switch acid sensitizer (PSPAG), a solvent and an additive, etc., and the configuration method is as follows:
  • the double-beam photoresist is mainly composed of resin, double-beam controllable molecular switch sensitizer (PSPSen), photoacid generator, solvent and additives, etc., and the configuration method is as follows:
  • the double-beam photoresist is mainly composed of a resin, a double-beam controllable molecular switch photosensitive alkali generator (PSPBG), a solvent and an additive, etc., and the configuration method is as follows:
  • PSPAG photoacid generator molecule
  • the present invention effectively overcomes various shortcomings in the prior art and has high industrial utilization value.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)

Abstract

一种光刻方法、光刻产品和光刻材料。光刻方法包括下列步骤：1)向光刻材料提供第一光（1）与第二光（2），至少部分的处于打开状态的分子开关可控效应分子产生分子产生效应分子，以使分子开关打开区域的光刻材料物理和/或化学性质发生变化；2)将发生物理或化学特性变化的光刻材料或者未发生变化的光刻材料之任一移除。该光刻方法可以有效突破光的衍射极限，从而进一步提升光刻的精度。

Description

一种光刻方法、光刻产品和光刻材料 技术领域
本发明涉及光刻领域，特别是涉及一种光刻方法和光刻材料。
背景技术
光刻技术是当前工业精密加工中重要的技术环节。特别是在微纳加工领域，如集成电路芯片、MEMS器件、光集成技术、精密光学等领域具有广泛应用。当前主流的高精密光刻制造工艺主要有，光学投影微缩光刻、电子束直写、离子束加工、激光干涉光刻等。
根据瑞利(Rayleigh)分辨率公式：R＝k1λ/NA可以知道，分辨率的提高可通过增大光刻物镜的数值孔径NA和缩短曝光波长λ来实现。目前光刻机技术增加数值孔径的办法是采用浸没式光刻技术，而短波长曝光目前最主流成熟的技术是采用波长193nm的ArF光源，即使采用浸没式提升NA的手段，最小分辨率也无法突破45nm。
当前认为极紫外线(EUV)、多波束无掩膜和纳米压印是下一代光刻(NGL)最有前景的候选技术。EUV技术最明显的特点是曝光波长可以缩短至13.5nm，从而极大的提升了分辨率。但在如此短波长的光源下，几乎所有物质都有很强的吸收性，所以不能使用传统的穿透式光学系统，而要改用反射式的光学系统，但是反射式光学系统难以设计成大的NA，造成分辨率无法提高。而且由于EUV掩模是采用反射式(通常都是穿透式)，所以制作十分困难。另外涉及到掩模的储存、运输及操作也非常困难。
在无掩膜光刻技术中，电子束(EB)具有波长短、分辨率高、焦深长、易于控制和修改灵活的特点，广泛应用于光学和非光学曝光的掩模制造。在系统集成芯片(SOC)的开发中，电子束直写(EBDW)比其它方法更具灵活性，它可直接接受图形数据成像，毋需复杂的掩模制作，因此具有广阔的前景。但其生产率很低，限制了使用。
现有的基于曝光式的光刻技术是采用传统光学原理基于瑞利公式在分辨率上的改进提升，主要是采用浸没法提高数值孔径以及采用更短波长的光源，特别是后者对提升分辨率起决定性作用，但准分子光源、电子束甚至极紫外光源制造复杂、难度大、而且成本极高，因此直接超分辨率曝光的光刻机成本十分昂贵，而且分辨率仍然受限于光源的衍射极限。
发明内容
鉴于以上所述现有技术的缺点，本发明的目的在于提供一种光刻方法和光刻材料，用于解决现有技术中的问题。
为实现上述目的及其他相关目的，本发明第一方面提供一种一种光刻方法，包括下列步骤：
1)向光刻材料提供第一光与第二光，所述第一光与第二光部分重叠，所述光刻材料中含有分子开关可控效应分子产生分子，所述第一光用于使所述分子开关可控效应分子产生分子处于关闭状态，所述第二光用于使所述分子开关可控效应分子产生分子处于打开状态，所述第一光与所述第二光重叠区域所述分子开关可控效应分子产生分子处于关闭状态；至少部分的处于打开状态的分子开关可控效应分子产生分子产生效应分子，以使分子开关打开区域的光刻材料物理和/或化学性质发生变化；
2)将发生物理或化学特性变化的光刻材料或者未发生变化的光刻材料之任一移除。
在本申请一些实施方式中，所述第一光为单空心光或多空心光。
在本申请一些实施方式中，所述第二光至少部分覆盖第一光光照区域所包围的无光照区域。
在本申请一些实施方式中，所述第二光为实心光。
在本申请一些实施方式中，所述第一光与第二光中至少有一个光为阵列光。
在本申请一些实施方式中，所述第二光的光照区域不超出第一光的光照区域的外缘。
在本申请一些实施方式中，所述第一光与第二光中至少有一个光为多光束。
在本申请一些实施方式中，所述分子开关可控效应分子产生分子所产生的效应分子选自去光刻材料保护基团分子或活化光刻材料聚合控制分子。
在本申请一些实施方式中，所述去光刻材料保护基团分子选自酸性分子、碱性分子、单线态氧。
在本申请一些实施方式中，所述活化光刻材料聚合控制分子选自聚合反应引发分子。
在本申请一些实施方式中，所述分子开关可控效应分子产生分子的分子结构中包括分子开关基团和效应分子产生基团。
在本申请一些实施方式中，所述分子开关可控效应分子产生分子中，分子开关基团与效应分子产生基团之间通过化学键连接。
在本申请一些实施方式中，所述步骤1)中，处于打开状态的分子开关可控效应分子产生分子产生效应分子的方式选自：改变处于打开状态的分子开关可控效应分子产生分子所经受的光照条件。
在本申请一些实施方式中，所述光刻材料物理或化学特性发生变化是指在显影液中的溶解性变化。
在本申请一些实施方式中，使所述光刻材料物理或化学特性发生变化的方法选自将光刻材料中的保护基团脱去或者使光刻材料中聚合物单体发生聚合。
本发明第二方面提供一种光刻材料，所述光刻材料包括分子开关可控效应分子产生分子以及对效应分子敏感的化合物。
在本申请一些实施方式中，所述效应分子选自去光刻材料保护基团分子或活化光刻材料聚合控制分子；所述去光刻材料保护基团分子选自酸性分子、碱性分子、单线态氧。
在本申请一些实施方式中，所述活化光刻材料聚合控制分子选自聚合反应引发分子。
在本申请一些实施方式中，所述效应分子敏感化合物选自效应分子敏感聚合物、效应分子敏感聚合单体或低聚物。
在本申请一些实施方式中，所述分子开关可控效应分子产生分子中包括分子开关基团和效应分子产生基团。
在本申请一些实施方式中，所述分子开关可控效应分子产生分子中，分子开关基团与效应分子产生基团之间通过化学键连接。
本发明第三方面一种化合物，所述化合物包括分子开关基团和效应分子产生基团。
在本申请一些实施方式中，所述效应分子选自去光刻材料保护基团分子或活化光刻材料聚合控制分子。
在本申请一些实施方式中，所述去光刻材料保护基团分子选自酸性分子、碱性分子、单线态氧。
在本申请一些实施方式中，所述活化光刻材料聚合控制分子选自聚合反应引发分子。
在本申请一些实施方式中，所述分子开关可控效应分子产生分子中，分子开关基团与效应分子产生基团之间通过化学键连接。
附图说明
图1为双光束技术实现超分辨的基本原理过程图；
图2为分子开关可控聚合脱保护模式图；
图3A、图3B为分子开关可控单体聚合模式图；
图4A、图4B为常用分子开关的反应形式；
图5为周环反应体系分子开关的一种脱基团反应方式；
图6为分子开关可控聚合脱保护正性双光束光刻模式图；
图7为分子开关可控单体聚合负性双光束光刻模式图；
图8A、图8B为分子开关可控聚合脱保护正性双光束光刻工艺过程图；
图9A、图9B为分子开关可控单体聚合负性双光束光刻工艺过程图；
图10A、图10B为双光束整形技术模式图；
图11A、图11B为并行化双光束光刻系统的两种方案形式；
图12为双光束阵列所采用的扫描方式包括直角坐标系扫描与极坐标系扫描两种坐标系体系方式。
具体实施方式
本申请发明人经过大量探索性研究，发现了一种新的光刻方法，并进一步提供了与光刻方法所对应的光刻材料，所述光刻方法和光刻材料可以有效突破光的衍射极限，从而进一步提升光刻的精度，在此基础上完成了本发明。
光刻方法
本申请一方面提供一种光刻方法，所述光刻方法可以包括：向光刻材料提供第一光与第二光，所述第一光与第二光可以部分重叠，所述光刻材料中含有分子开关可控效应分子产生分子，至少部分的处于打开状态的分子开关可控效应分子产生分子产生效应分子，以使分子开关打开区域的光刻材料物理或化学特性发生变化。
所述光刻方法中，所述第二光可以用于使所述分子开关可控效应分子产生分子处于打开状态，本领域技术人员可以根据分子开关可控效应分子产生分子的种类、在光刻材料中的含量等参数，确定可以使分子开关可控效应分子产生分子处于打开状态的条件，例如，所述第二光可以是紫外光、可见光或红外光等，再例如，所述第二光可以是波长为不大于5nm、5-10nm、10-20nm、20-40nm、40-60nm、60-80nm、80-100nm、100-150nm、150-200nm、200-250nm、250-300nm、300-350nm、350-400nm、400-450nm、450-500nm、500-550nm、550-600nm、600-650nm、650-700nm、700-750nm、750-800nm、800-850nm、850-900nm、900-950nm、950-1000nm、1000-1200nm、1200-1400nm、1400-1600nm、1600-1800nm、1800-2000nm、2000-2500nm、2500-3000nm、3000-3500nm、3500-4000nm、4000-4500nm、4500-5000nm、5000-6000nm、6000-7000nm、7000-8000nm、8000-9000nm、8000-9000nm、8000-9000nm、8000-9000nm、8000-9000nm、8000-9000nm、9000-10000nm、10000-12000nm、12000-14000nm、14000-16000nm、16000-18000nm、18000-20000nm或不低于20000nm的光。
所述光刻方法中，所述第一光可以用于使所述分子开关可控效应分子产生分子处于关闭状态，所述第一光与所述第二光重叠区域通常可以使所述分子开关可控效应分子产生分子处 于关闭状态，使所述分子开关可控效应分子产生分子处于关闭状态可以是例如：使处于打开状态的分子开关可控效应分子产生分子转变为关闭状态和/或维持处于关闭状态的分子开关可控效应分子产生分子处于关闭状态，本领域技术人员可以根据分子开关可控效应分子产生分子的种类、在光刻材料中的含量等参数，确定可以使分子开关可控效应分子产生分子处于关闭状态的条件，例如，所述第一光可以是紫外光、可见光或红外光等，再例如，所述第一光可以是波长为不大于5nm、5-10nm、10-20nm、20-40nm、40-60nm、60-80nm、80-100nm、100-150nm、150-200nm、200-250nm、250-300nm、300-350nm、350-400nm、400-450nm、450-500nm、500-550nm、550-600nm、600-650nm、650-700nm、700-750nm、750-800nm、800-850nm、850-900nm、900-950nm、950-1000nm、1000-1200nm、1200-1400nm、1400-1600nm、1600-1800nm、1800-2000nm、2000-2500nm、2500-3000nm、3000-3500nm、3500-4000nm、4000-4500nm、4500-5000nm、5000-6000nm、6000-7000nm、7000-8000nm、8000-9000nm、8000-9000nm、8000-9000nm、8000-9000nm、8000-9000nm、8000-9000nm、9000-10000nm、10000-12000nm、12000-14000nm、14000-16000nm、16000-18000nm、18000-20000nm或不低于20000nm的光的条件下。
所述光刻方法中，通常来说，对于同一种分子开关可控效应分子，使所述分子开关可控效应分子处于打开、关闭状态的条件是不同的，本领域技术人员可根据分子开关可控效应分子的种类，确定可以使分子开关可控效应分子产生分子处于不同状态的条件，例如，可以使分子开关可控效应分子产生分子处于打开状态的条件、可以使分子开关可控效应分子产生分子处于关闭状态的条件、可以使分子开关可控效应分子产生分子由关闭状态转化为打开状态的条件、可以使分子开关可控效应分子产生分子由打开状态转化为关闭状态的条件等。例如，可以使处于第二光照射条件下的分子开关可控效应分子处于打开状态，再例如，可以使处于第一光和第二光同时照射条件下的分子开关可控效应分子处于关闭状态，再例如，可以使处于第一光照射条件下的分子开关可控效应分子处于关闭状态，再例如，第一光所能够提供的光照条件与第二光所能够提供的光照条件通常可以是不同的。
所述光刻方法中，所述第一光与第二光部分重叠可以是第一光与第二光均只有部分相互重叠，也可以是其中一光的全部与另一光的部分相互重叠，例如，第一光的全部与第二光的部分相互重叠，再例如，第二光的全部与第一光的部分相互重叠。
所述光刻方法中，所述第一光可以为单空心光或多空心光，所述第二光可以至少部分或全部覆盖第一光光照区域所包围的无光照区域。所述空心光通常指任何可以形成光照区域、且光照区域包围有无光照区域的光，所述无光照区域是指相比光照区域光照明显弱化、趋近 于或等于零的区域。所述无光照区域可以为一个或多个，当所述第一光所形成的光照区域所包围的无光照区域为一个时，所述第一光可以是单空心光，当所述第一光所形成的光照区域所包围的无光照区域为多个时，所述第一光可以是多空心光。第一光所形成的光照区域所包围的无光照区域的形状可以是各种规则或者不规则的形状，这些形状在某一维度上可以是纳米级别的尺寸，例如，在本申请一具体实施方式中，无光照区域的形状可以是圆形、椭圆形、多边形、延伸的线条等，圆形的直径、椭圆形的长轴、椭圆形的短轴、多边形的直径、延伸线条的宽度等可以是不大于5nm、5-10nm、10-15nm、15-20nm、20-25nm、25-30nm、30-35nm、35-40nm、40-45nm、45-50nm、50-55nm、55-60nm、60-65nm、65-70nm、70-75nm、75-80nm、80-85nm、85-90nm、90-95nm、95-100nm、100-110nm、110-120nm、120-130nm、130-140nm、140-150nm、150-160nm、160-180nm、180-200nm或更大的尺寸。在本申请一具体实施方式中，所述空心光可以是环形光、具有空心的面光等。进一步的，所述多个无光照区域可以形成阵列，所述第一光本身可以为多光束或阵列光。在本申请另一具体实施方式中，所述空心光可以是环形光阵列、具有空心阵列的面光等，所述具有空心阵列的面光是指光照区域中，多个无光照区域形成阵列。所述第二光可以为实心光，所述实心光通常指所形成的光照区域并不包围任何非光照区域的光。在本申请一些实施方式中，所述实心光可以是单光光束、面光等。进一步的，所述第二光可以为多光束或阵列光。在本申请另一具体实施方式中，所述第二光可以是由多个单光光束所形成的阵列光。
所述光刻方法中，所述第二光的光照区域不超出第一光的光照区域的外缘，所述第二光的光照区域不超出第一光的光照区域的外缘通常指第二光的光照区域不涉及除第一光光照区域、第一光光照区域所包围的无光照区域以外的区域，所述第一光和/或第二光形成的光照区域可以是这些光在光刻材料上所形成的光照区域。
所述光刻方法中，分子开关可控效应分子产生分子通常指在一定条件下可以由打开状态转变为关闭状态和/或由关闭状态转变为打开状态、且在打开状态下可以在一定条件下产生效应分子的一类化合物，处于打开状态的分子开关可控效应分子产生分子和处于关闭状态的分子开关可控效应分子产生分子的分子结构式可以是不同的。所述分子开关可控效应分子产生分子处于打开状态通常指分子开关可控效应分子产生分子可以在一定的条件下产生效应分子，使处于打开状态的分子开关可控效应分子产生分子产生效应分子的条件可以是无光照的条件，也可以包括光照条件，具体可以是例如紫外光、可见光或红外光等的光照条件，再例如，可以是在波长不大于5nm、5-10nm、10-20nm、20-40nm、40-60nm、60-80nm、80-100nm、100-150nm、150-200nm、200-250nm、250-300nm、300-350nm、350-400nm、400-450nm、450-500nm、 500-550nm、550-600nm、600-650nm、650-700nm、700-750nm、750-800nm、800-850nm、850-900nm、900-950nm、950-1000nm、1000-1200nm、1200-1400nm、1400-1600nm、1600-1800nm、1800-2000nm、2000-2500nm、2500-3000nm、3000-3500nm、3500-4000nm、4000-4500nm、4500-5000nm、5000-6000nm、6000-7000nm、7000-8000nm、8000-9000nm、8000-9000nm、8000-9000nm、8000-9000nm、8000-9000nm、8000-9000nm、9000-10000nm、10000-12000nm、12000-14000nm、14000-16000nm、16000-18000nm、18000-20000nm或不低于20000nm的光的光照条件。所述处于关闭状态的分子开关可控效应分子产生分子通常指：相对于处于打开状态的分子开关可控效应分子产生分子能够产生效应分子的条件，在相同或相近的条件下，处于关闭状态的分子开关可控效应分子产生分子基本上不能够产生效应分子。在本申请一些实施方式中，分子开关可控效应分子产生分子产生效应分子可以是通过分子开关可控效应分子产生分子的部分基团的化学键断裂从而生成效应分子、分子开关可控效应分子产生分子上的基团发生变化从而转化成效应分子等方式。
所述光刻方法中，至少部分或全部的处于打开状态的分子开关可控效应分子产生分子可以产生效应分子，本领域技术人员可根据效应分子的种类，选择合适种类的对效应分子敏感的化合物，构成包括对效应分子敏感的化合物的光刻材料，从而效应分子可以使分子开关打开区域的光刻材料物理性质和/或化学性质发生变化。例如，所述分子开关可控效应分子产生分子所产生的效应分子可以是去光刻材料保护基团分子，所述去光刻材料保护基团分子可以是包括但不限于酸性分子、碱性分子、单线态氧等，所述对效应分子敏感的化合物可以是效应分子敏感聚合物，所述效应分子敏感聚合物可以是包括但不限于带有保护基团的丙烯酸及丙烯酸酯类材料、脂肪族环烯烃类材料、马来酸酐类材料等材料，本领域技术人员可根据效应分子的种类、反应条件等参数选择合适的基团作为对效应分子敏感的化合物的保护基团，保护基团可以是包括但不限于t-BOC等，更具体的，在去光刻材料保护基团分子存在的条件下，对效应分子敏感的化合物的分子结构中的保护基团可以被脱去，从而可以使脱去保护基团的光刻材料(相对于未脱去保护基团的光刻材料)的物理性质和/或化学性质发生变化。所述光刻材料的物理性质和/或化学性质通常可以是光刻材料在显影液中的溶解性发生变化，例如，在去光刻材料保护基团分子存在的条件下，对效应分子敏感的化合物的分子结构中的保护基团可以被脱去，从而使脱去保护基团的光刻材料在显影液中的溶解性可以升高或者降低。再例如，所述分子开关可控效应分子产生分子所产生的效应分子可以是光刻材料溶解抑制剂，所述光刻材料溶解抑制剂可以是包括但不限于重氮萘醌类等材料等，所述对效应分子敏感的化合物可以是效应分子敏感聚合物，所述效应分子敏感聚合物可以是包括但不限于线性酚醛 树脂类等材料，本领域技术人员可根据效应分子的种类、反应条件等参数选择合适的效应分子敏感聚合物作为对效应分子敏感的化合物，效应分子敏感聚合物可以是包括但不限于酚醛甲醛类等材料等，更具体的，在光刻材料溶解抑制剂存在的条件下，对效应分子敏感的化合物的的物理性质和/或化学性质可以发生变化。所述光刻材料的物理性质和/或化学性质通常可以是光刻材料在显影液中的溶解性发生变化，例如，在光刻材料溶解抑制剂存在的条件下，光刻材料在显影液中的溶解性可以升高或者降低。再例如，所述分子开关可控效应分子产生分子所产生的效应分子可以是活化光刻材料聚合控制分子，更具体可以是聚合反应引发分子，所述活化光刻材料聚合控制分子可以是包括但不限于酸性分子、碱性分子、单线态氧、各种聚合反应引发剂等，对效应分子敏感的化合物可以是效应分子敏感聚合单体或低聚物等，所述活化光刻材料聚合控制分子可以与效应分子敏感聚合单体或低聚物相同，所述对效应分子敏感的化合物通常是可发生聚合反应的单体和/或低聚物等，更具体的，所述对效应分子敏感的化合物可以是包括但不限于丙烯酸酯类分子单体、甲基丙烯酸酯类分子单体、乙烯基类分子单体、乙烯基醚类分子单体、环氧类分子单体等。在活化光刻材料聚合控制分子存在的条件下，光刻材料中的单体或低聚体可以发生聚合反应，从而使光刻材料的物理性质和/或化学性质发生变化。所述光刻材料的物理性质和/或化学性质通常可以是光刻材料在显影液中的溶解性发生变化，例如，在活化光刻材料聚合控制分子存在的条件下，作为对效应分子敏感的化合物的单体或低聚体可以发生聚合反应，从而使发生聚合反应的光刻材料在显影液中的溶解性升高或者降低。
所述光刻方法中，分子开关可控效应分子产生分子的分子结构中可以包括分子开关基团和效应分子产生基团。所述含有分子开关基团的分子开关可控效应分子产生分子通常可以在一定的条件下发生构型上的变化，从而可以使分子开关可控效应分子产生分子由打开状态转变为关闭状态和/或由关闭状态转变为打开状态(使分子开关可控效应分子产生分子处于关闭状态的条件可以包括第一光光照的条件，使分子开关可控效应分子产生分子处于打开状态的条件可以是包括第二光光照的条件)，例如，具有所述分子开关基团的物质可以是包括但不限于具有质子转移互变异构、顺-反异构、键的异裂、周环反应体系等结构的物质，更具体可以是包括但不限于二芳基乙烯类化合物、偶氮苯类化合物、螺吡喃类化合物、螺噁嗪类化合物、俘精酸酐类化合物、水杨醛缩苯胺类席夫碱类化合物等。所述含有效应分子产生基团的分子开关可控效应分子产生分子可以是当分子开关可控效应分子产生分子处于打开状态时、在一定条件下能够释放效应分子的基团(释放效应分子的条件可以包括如上所述的产生效应分子的光照条件)，所述能够产生效应分子的分子开关可控效应分子产生分子还可以是当分子开关 可控效应分子产生分子处于打开状态时、在一定条件下能够发生构型上的转变(转变为效应分子的条件可以包括如上所述的产生效应分子的光照条件)，从而使处于打开状态的分子开关可控效应分子产生分子自身转变为效应分子。所述具有效应分子产生基团的物质可以是包括但不限于光酸产生分子、光碱产生分子、光敏分子、聚合反应引发剂产生分子等，从而可以分别释放酸性分子、碱性分子、单线态氧、聚合物引发剂等作为效应分子。所述光酸产生分子可以包括离子型和非离子型，所述离子型具体可以是包括但不限于重氮盐酸盐类化合物、重氮硫酸盐类化合物、重氮磺酸盐类化合物、重氮氟磷酸盐类化合物和鎓盐类化合物等，所述鎓盐类化合物可以是包括但不限于碘鎓盐类化合物、硒鎓盐类化合物、磷鎓盐类化合物、砷鎓盐类化合物等，所述非离子型基团可以是包括但不限于多卤代苯乙酮类化合物、三嗪衍生物类化合物、磺酰氯酯化物类化合物等。所述光碱产生分子可以包括但不限于过渡金属离子氨络合物类化合物、季铵盐类化合物、酯类类化合物(包括酮肟酯类化合物、氨基甲酸酯类化合物、氨基甲酸肟基酯类化合物)、甲酰胺类化合物、三芳基甲醇类化合物等，所述光敏分子可以是卟啉化合物类化合物、酞菁分子类化合物，聚合反应引发剂产生分子可以是安息香醚类化合物、苯偶酰缩酮类化合物、苯乙酮类化合物、酰类氧化膦类化合物、α-氯代苯乙酮类化合物、磺酰基苯乙酮类化合物、磺酰基氧苯乙酮类化合物、偶氮类化合物、过氧(硫)化物类化合物、二苯甲酮类化合物、硫杂蒽酮类化合物、醌类化合物、重氮盐类化合物、鎓盐类化合物等。所述分子开关可控效应分子产生分子中，分子开关基团与效应分子产生基团之间可以通过化学键连接，所述化学键可以是例如离子键、共价键等。在本申请的具体实施例中，所述分子开关可控效应分子产生分子可以是对甲苯磺酸类化合物、三氟甲磺酸类化合物、甲磺酸类化合物、对甲苯磺酸硫鎓盐类化合物、三氟甲磺酸硫鎓盐类化合物、甲磺酸硫鎓盐类化合物等。
所述光刻方法中，由于可以通过包括光照的条件使处于打开状态的分子开关可控效应分子产生分子产生效应分子，所述使所述处于打开状态的分子开关可控效应分子产生效应分子的方式可以包括改变处于打开状态的分子开关可控效应分子产生分子所经受的光照条件，例如，可以是向处于打开状态的分子开关可控效应分子产生分子提供第三光束，也可以是改变第二光束的参数(例如，光照强度、波长等)，从而使处于打开状态的分子开关可控效应分子产生分子产生效应分子。
本申请所提供的光刻方法，还可以包括：将发生物理或化学特性变化的光刻材料或者未发生变化的光刻材料之任一移除。本领域技术人员可根据光刻材料的种类，选择合适的将发生物理或化学特性变化的光刻材料或者未发生变化的光刻材料移除的方法。例如，可以通过 显影液，将在显影液中溶解性较高的光刻材料溶解于显影液中，从而移除该部分光刻材料。
化合物
本申请另一方面提供一种化合物，所述化合物即如上所述的分子开关可控效应分子产生分子。
本申请所提供的化合物中，所述化合物所产生的效应分子可以是去光刻材料保护基团分子，所述去光刻材料保护基团分子可以是包括但不限于酸性分子、碱性分子、单线态氧等。所述化合物所产生分子所产生的效应分子可以是光刻材料溶解抑制剂，所述光刻材料溶解抑制剂可以是包括但不限于重氮萘醌等。所述分子开关可控效应分子产生分子所产生的效应分子也可以是活化光刻材料聚合控制分子，更具体可以是聚合反应引发分子，所述活化光刻材料聚合控制分子可以是包括但不限于酸性分子、碱性分子、单线态氧、聚合反应引发剂等。
光刻材料
本申请另一方面提供一种光刻材料，所述光刻材料包括分子开关可控效应分子产生分子以及对效应分子敏感的化合物。
本申请所提供的光刻材料中，所述对效应分子敏感的化合物可以是效应分子敏感聚合物，所述效应分子敏感聚合物可以是包括但不限于带有保护基团的丙烯酸及丙烯酸酯类材料、脂肪族环烯烃类材料、马来酸酐类材料等材料，本领域技术人员可根据效应分子的种类、反应条件等参数选择合适的基团作为对效应分子敏感的化合物的保护基团，保护基团可以是包括但不限于t-BOC等，更具体的，在去光刻材料保护基团分子存在的条件下，对效应分子敏感的化合物的分子结构中的保护基团可以被脱去，从而可以使脱去保护基团的光刻材料(相对于未脱去保护基团的光刻材料)的物理性质和/或化学性质发生变化。未脱去保护基团的对效应分子敏感的化合物和脱去保护基团的对效应分子敏感的化合物在显影液中的溶解性通常发生变化，例如，脱去保护基团的对效应分子敏感的化合物在显影液中的溶解性升高或者降低。所述对效应分子敏感的化合物可以是线性酚醛树脂类等材料，更具体的，所述对效应分子敏感的化合物可以是包括但不限于酚醛甲醛类等材料等。在光刻材料溶解抑制剂存在的条件下，对效应分子敏感的化合物的物理性质和/或化学性质可以发生变化。所述光刻材料的物理性质和/或化学性质通常可以是光刻材料在显影液中的溶解性发生变化，例如，在光刻材料溶解抑制剂存在的条件下，光刻材料在显影液中的溶解性可以升高或者降低。所述对效应分子敏感的化合物可以是效应分子敏感聚合单体或低聚物等，所述对效应分子敏感的化合物通常是可发生聚合反应的单体和/或低聚物等，更具体的，所述对效应分子敏感的化合物可以是包括但 不限于丙烯酸酯类分子单体、甲基丙烯酸酯类分子单体、乙烯基类分子单体、乙烯基醚类分子单体、环氧类分子单体等。在活化光刻材料聚合控制分子存在的条件下，光刻材料中的单体或低聚体可以发生聚合反应，从而使光刻材料的物理性质和/或化学性质发生变化。聚合反应后所得的材料和未发生聚合反应的光刻材料在显影液中的溶解性发生变化，例如，发生聚合反应的光刻材料在显影液中的溶解性升高或者降低。
本申请所提供的光刻材料中，还包括可以包括其他各种光刻材料中可以包括的组分，例如可以是催化剂、引发剂、助剂等，所述助剂可以是本领域各种适用于光刻材料的消泡剂、流平剂、稳定剂、分散剂等。
本申请所提供的光刻方法和光刻材料基于双光束超分辨技术，光源采用技术成熟的半导体激光器，成本低廉，分辨率没有理论极限，可以达到10nm工艺节点以下，高分辨光刻成本大大降低，具体有益效果如下：
1、现有的激光直写技术主要采用半导体激光器，其分辨率由于激光器波长的限制大多无法突破100nm以下，因此100nm以下的纳米级加工目前普通的激光直写技术无法实现，仍需借助电子束等更高分辨率的方法，而本申请基于双光束技术原理，摆脱了波长限制，能够实现100nm以下的分辨率。
2、与电子束直写等基于无掩膜超分辨光刻工艺的技术相比，本申请采用低成本的固态半导体激光器，发光效率高、无需高压电源、单个光源成本低廉便于扩展为多光源，同时采用多光束方式相比电子束实现多光束更容易，更有可能实现大尺度、大范围、大幅面的超分辨纳米多光束光刻，速度较电子束可大幅度提升。
3、与基于近场超分辨(Near-field super resolution)原理的光刻技术相比，本申请所采用的双光束原理所实现的超分辨光刻为远场(Far-field)，但近场超分辨的实现通常需要成像物理距离控制在近场范围以内，也就是波长长度以内，这在实际光刻中实现难度极大，而采用super-RENS(Super Resolution Near-field Structure)，即近场超分辨结构工艺的光刻的话，则需要在光刻胶上层先实现super-RENS层，工艺更复杂，成本很高，本申请所实现的远场双光束超分辨是在远场范围内通过双光束调控PSPAG直接在光刻胶上化学反应，没有近场成像的物理距离限制问题，成像简单易行，光刻胶工艺与目前的主流工艺完全一致，工艺成熟、衔接性好。
传统的正性光刻PAG发生光致产酸本身是无法受控的，发生光致产酸后化学放大蚀刻的空间分辨率是由光源波长及镜头数值孔径所调控的。本发明中所设计的PAG可以在分子开关的控制下实现光酸释放的受控，从而利用双光束的光可逆调控方式有效的实现了光酸释放的 空间分辨率调控，摆脱了光源波长及数值孔径的限制。
以下通过特定的具体实例说明本发明的实施方式，本领域技术人员可由本说明书所揭露的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加以实施或应用，本说明书中的各项细节也可以基于不同观点与应用，在没有背离本发明的精神下进行各种修饰或改变。
如图1所描述的过程为本发明所述双光束技术实现超分辨的基本原理过程图。图中所示第一步先打开环形抑制光1，即hν1，为通过相位转换所形成的环形光，其环形中空可调节大小，因此可以通过调节1中空部分的尺寸调整双光束的分辨率，本发明中光束1的作用是关闭分子开关(即使分子开关可控效应分子产生分子处于关闭状态)。所示第二步为在环形光1的基础上同心叠加光束2，即hν2，光束2为一束起激活作用的高斯光束，在本发明中光束2的作用是打开分子开关(即使分子开关可控效应分子产生分子处于打开状态)。本发明所述双光束过程第三步是在分子开关打开基础上激发光化学反应，方式一是不通过调节环形抑制光1，打开或者关闭1、2均可，在此状态下直接叠加另一波长的hν3，在第三种波长直接作用于分子开关所控制的光化学基团后，仅打开的分子开关部分发生光化学作用；方式二是光化学基团与分子开关作用波长一致，此时需同步提高1和2的强度达到光化学基团反应发生的阈值。
如图2中所描述的是分子开关可控聚合脱保护模式图。如图2所示为分子开关控制下几种最终实现聚合物脱保护基团的分子特征及反应模式，最终所实现形式即为正性光刻。图中1表示具有分子开关功能的部分(以下简称分子开关1)，2表示具有光酸产生分子功能的部分或强酸基团(以下简称产酸基团2)，3表示具有光碱产生剂功能的部分或碱分子基团(以下简称产碱基团3)，4表示具有光敏剂分子功能的部分(以下简称光敏分子4)。图A所示为分子开关可控光酸产生分子(PSPAG)，其中光酸产生分子特征包括光酸产生剂分子以及强酸基团两种形式，分子开关1可以在激活光束hν2光照下使化合物由失活态OFF转换为激活态ON，也可以在环形抑制光束hν1光照下使化合物由激活态ON转换为失活态OFF，而且分子开关1在hν1和hν2两种光交替下可以实现反复开关。图中A所述的PSPAG分子在化合物OFF时，产酸基团2无法释放强酸分子或者强酸分子基团无法从化合物中解离，而当化合物切换至ON时，2在hν3特定光照下释放强酸分子或者强酸基团从化合物中解离，释放的强酸分子与树脂材料上的特定保护基团反应将其解离，使得树脂分子实现脱保护。图B所示为分子开关可控光碱产生分子(PSPBG)，其中光碱产生分子特征包括光碱产生剂分子以及强碱基团两种形式，图B所示的PSPBG分子在化合物处于OFF时，产碱基团3无法释放强酸分子或者强酸分子 基团无法从化合物中解离，在激活光束hν2光照下化合物由失活态OFF转换为激活态ON，3在hν3特定光照下释放强碱分子或者强碱基团从化合物中解离。释放的强碱分子与树脂材料上的特定保护基团反应将其解离，使得树脂分子实现脱保护。图C所示为分子开关可控光敏分子(PSPSen)，激活光束hν2使化合物从OFF转换至ON，从而光敏剂分子4被激活光敏活化能力，而环形光束hν1使光敏分子4关闭光敏活化能力。图C中激活光敏活化的4在特定波长hν3下将氧分子活化为单线态氧O 3-，单线氧具有强氧化性，与树脂材料特定保护基团反应将其解离，实现脱保护。
如图3A、3B中所描述的是分子开关可控单体聚合模式图。图3A、3B所示为分子开关可控聚合物单体分子聚合反应的分子特征及反应模式。图3A、3B中1表示具有分子开关功能的部分(以下简称分子开关1)，2表示单体分子，3表示聚合分子，4表示具有光引发剂分子功能的部分，5表示具有光敏剂分子功能的部分(以下简称光敏剂分子5)，6表示具有光酸产生分子功能的部分(以下简称光酸产生分子6)，7表示具有光碱产生分子功能的部分(以下简称光碱产生分子7)。图3A、3B中图A所示为分子开关可控聚合单体分子，化合物可以在激活光束hν2光照下由失活态OFF转换为激活态ON，在环形抑制光束hν1光照下由激活态ON转换为失活态OFF，化合物在hν1和hν2两种光交替下可以实现反复开关。图3A、3B中A所述的分子开关可控聚合单体分子在化合物处于OFF时，单体分子2无法发生聚合反应，而当化合物通过激活光束hν2切换至ON时，单体分子2可以进行聚合反应，激活后2在hν3特定光照及其他成分共同作用下发生聚合反应，生成聚合物3。图3A、3B中图B为分子开关可控光引发剂分子，处于未激活状态OFF的PInit分子4无法引发聚合反应，激活光束作用后分子开关激活PInit，从而在hν3效应光以及单体分子作用下引发聚合反应。图3A、3B中图C所示为分子开关可控光敏分子(PSPSen)，激活光束hν2使化合物从OFF转换至ON，从而光敏剂分子5被激活光敏活化能力，而环形光束hν1使光敏分子5关闭光敏活化能力。图C中激活光敏活化的4在特定波长hν3下将氧分子活化为单线态氧O 3-，单线氧引发特定单体分子聚合反应实现分子聚合。图3A、3B中图D所示为分子开关可控光酸产生分子(PSPAG)，光酸产生基团6在hν1和hν2两种光交替下可以实现反复开关，激活后的6在hν3特定光照下释放强酸分子，并在其他成分共同作用下使单体发生聚合反应。图E所示为分子开关可控光碱产生分子(PSPBG)，光碱产生基团7经过hν2激活后，在hν3特定光照下释放强碱分子，并在其他成分共同作用下使单体发生聚合反应。
光控的分子开关通常是指分子可以在不同波长的光照下可逆转换为不同的分子构型，从而呈现开关特征。目前分子开关的反应类型可以分为质子转移互变异构、顺-反异构、键的异 裂、周环反应体系等几类。具有开关特性的分子主要集中在：二芳基乙烯类化合物、偶氮苯类化合物、螺吡喃类化合物、螺噁嗪类化合物、俘精酸酐类化合物等化合物上。本发明中所述分子开关包括以上几种分子开关的反应形式，如图4A、4B所示A为质子转移互变异构形式中的水杨醛缩苯胺类席夫碱类化合物，在UV/VIS下可实现分子开关转换。如图4A、4B所示B为顺-反异构形式，偶氮苯类化合物是一类具有优良开关特性的分子。如图4A、4B所示C与D属于键的异裂反应形式中的螺吡喃类化合物和螺噁嗪类化合物，其两者均可在两种不同光照切换下实现优良的分子开关性能。如图4A、4B所示E为周环反应体系反应，其基本特征是分子中的己三烯结构在光照下切换为环己二烯结构，并在光照下可逆转换。符合此类特征的开关分子包括俘精酸酐类化合物、二芳基乙烯类化合物等。
如图5中所描述的是周环反应体系分子开关的一种脱基团反应方式。图5中所示为一种基于周环反应体系分子开关的一种分子开关控制光酸\光碱脱基团的方式。光产酸剂主要分为离子型和非离子型，本发明中所述离子型光酸产生剂主要包括重氮盐类化合物如重氮盐酸盐类化合物、重氮硫酸盐类化合物、重氮磺酸盐类化合物、及重氮氟磷酸盐类化合物，和鎓盐类化合物如碘鎓盐类化合物、硒鎓盐类化合物、磷鎓盐类化合物、砷鎓盐类化合物等。所述非离子型光酸产生剂主要包括有机卤代化合物如多卤代苯乙酮类类化合物、三嗪衍生物类化合物、磺酰氯酯化物类化合物等。如图5中A所示，基于己三烯结构的分子，虚线代表可能的各种环形分子类型，如苯环类化合物、环戊烷类化合物、环戊杂环类化合物等各类可能的环形分子，己三烯结构分子在hν1与hν2相互作用下可以通过分子内闭环与环己二烯结构可逆互变，而在R1位的光酸分子则可能在hν3作用下与环己二烯结构脱离，从而使得环己二烯结构不可逆成为苯环结构。如图5中B所示，基于图A的原理一种基于二芳乙烯类分子结构的PSPAG，其中R1为具有产生光酸分子功能的部分，如光酸产生剂中常用的三氟甲磺酸等强酸基，在hν1与hν2仅发生闭环/开环可逆转换，在hν3作用下，强酸基团则从分子脱离，二芳乙烯作为分子开关对酸基团释放可控。
如图6中所描述的是分子开关可控聚合脱保护正性双光束光刻模式图，即本发明所述的光分子开关可控效应分子在双光束作用下光刻胶中所发生的聚合物脱保护光化学反应的过程原理。图中A中所示1为环形抑制光束hν1，2(黑色实心圆)表示光刻胶高分子所携保护基团，3(波浪曲线)表示光刻胶高分子主链，4(黑色实心三角)表示分子开关可控聚合物脱保护反应分子。图A所表示过程为，环形抑制光束1照射在光刻胶上时，光刻胶中高分子链均连接着保护基团，光刻胶中分子开关控制分子默认在OFF状态，因此在环形光束1照射在上面时不会使得分子开关所控分子对光刻胶发生化学反应。图中B所示5为同心叠加在环形 抑制光束上的高斯激活光束hν2，当光束通过环形光束中心孔作用到光刻胶上时，原本处于失活状态的2被激活为图中的6(空心三角)，即分子开关所控效应分子被激活。图中C所示7为另外切换的作用光束，即hν3光束，在光束7的作用下，被激活的分子释放出游离效应基团，如被发明所述强酸、强碱、单线氧等，作用于高分子上的保护基团2，将其从高分子上解离。解离后的光刻胶高分子层暴露在显影液后会被分解，而被保护的高分子则不会被显影液所分解。
图7中所描述的是分子开关可控单体聚合负性双光束光刻模式图。图中A中所示1为环形抑制光束hν1，2(小波浪线)表示光刻胶高分子单体分子，对于图三所述A则表示分子开关所控单体分子，3(空心斜方块)表示分子开关聚合控制分子，4表示待处理材料。图A所表示过程为，环形抑制光束1定位照射在光刻胶上时，光刻胶中单体分子均处于初始解聚分散状态，光刻胶中分子开关控制分子默认在OFF状态，因此在环形光束1照射在上面时不会使得分子开关所控分子对光刻胶发生化学反应。图中B所示5为同心叠加在环形抑制光束上的高斯激活光束hν2，当光束通过环形光束中心孔作用到光刻胶上时，原本处于失活状态的3或2(图三所述A)被激活，以图中所示6(黑色实心斜方块)，即分子开关所控聚合控制分子被激活。图中C所示7为在hν3效应光束的作用下，被激活的分子引发聚合反应，从而在曝光处发生固化反应。曝光后发生固化的图形在后续显影液处理下不会被洗脱下来，其他未曝光区域则被显影液所清洗而暴露出未曝光区域的材料表面。
图8A、8B所示步骤一中，1为环形抑制光hν1，2为光刻胶层，3为待加工材料，如硅片。以硅晶圆光刻为例，首先，环形抑制光束在涂布光刻胶的硅晶圆片上进行定位。步骤二，在环形光所定位的光刻胶的位置叠加激活光束4，即图8A、8B中hν2，图8A、8B中激活光束4所照射光刻胶部位5的分子开关效应分子被激活。步骤三，效应光hν3作用于光刻胶被激活的区域，此区域的分子开关效应分子释放效应基团，将光刻胶中的保护基团脱保护。步骤一至步骤三在程序控制下反复进行步进扫描曝光，即连接形成所要蚀刻的图形。步骤四，加入显影液后，已经脱保护基团的光刻胶部分被显影液溶解，而没有曝光的区域则不会被显影液溶解。步骤五，暴露出来的硅片区域可进行蚀刻、处理及加工操作。步骤六，洗脱掉这一步操作的光刻胶，暴露出包含此次蚀刻图形的硅片表面。步骤七，涂布新的光刻胶层，准备开始下一轮光刻操作。
图9A、9B中所描述的是分子开关可控单体聚合负性双光束光刻工艺过程图。图中步骤一中，1为环形抑制光hν1，2为光刻胶层，3为待加工材料。首先，环形抑制光束在涂布光刻胶的材料表面上进行定位。步骤二，在环形光所定位的光刻胶的位置叠加激活光束4，即 图9A、9B中hν2，图9A、9B中激活光束4所照射光刻胶部位5的分子开关聚合控制分子被激活。步骤三，效应光hν3作用于光刻胶被激活的区域，此区域的活化聚合控制分子与光刻胶中单体成分发生作用，引发聚合反应。步骤一至步骤三在程序控制下反复进行步进扫描曝光，即连接形成所要蚀刻的图形。步骤四，加入显影液后，没有曝光的光刻胶部分被显影液溶解，而曝光的区域由聚合物保护则不会被显影液溶解。步骤五，暴露出来的材料区域可进行处理、蚀刻及加工等操作。步骤六，洗脱掉这一步操作的光刻胶，暴露出包含此次处理的材料表面。步骤七，涂布新的光刻胶层，准备开始下一轮光刻操作。
图10A、10B中所示为双光束整形技术模式图。通常的双光束系统均采用高斯光束以及高斯环形光束，光强分布非线性分布，因此会造成作用区能量不均匀，无法精确控制作用域。本发明所述双光束光刻系统采用光束整形方法，将实心光束和空心光束均调制为平顶光束形态，可以有效提高加工边缘的控制精度。本发明中采用光束整形的方式将实心高斯光束以及涡旋光束均整形为相应的实心平顶光束以及平顶双光束，且边缘均陡峭垂直，这样能量作用分布更为精确。图10A、10B中所示A表示实心高斯光束经过整形后成为实心平顶光束。图10A、10B中所示B为涡旋光束经整形后成为中空平顶光束。图10A、10B中所示C表示已叠加的双光束可直接整形为平顶双光束，或将整形后的实心平顶光束与中空平顶光束叠加成为平顶双光束形式。图10A、10B中所示D表示通过调整中空平顶光束能量大小调整中空尺寸的大小。图10A、10B中所示E表示中空平顶光束不同调整下实心平顶光束最终写入宽度。
图11A、11B中所描述的是并行化双光束光刻系统的两种方案形式。如图11A、11B所示方案一，双光束采用直接产生同心光束后实现并行化的方式。如图11A、11B方案一中所示hν1为环形光初始输入光束，hν2、hν3为实心高斯光束初始输入光束。方案一种所示hν1和hν2通过分光镜汇合后经过透镜组1聚集进入光束整形装置2实现hν1与hν2同心，装置2通常可以采用保圆偏光纤实现。同心后的光束经过光束整形装置3将同心光束的高斯光束转换为能量分布平均的平顶光束。转换并扩束后的光束进入微透镜阵列组4，经过微透镜组转换为阵列型的多光束。双光束相位转换阵列组5与微透镜阵列组4相对应，每一束从4出来的光束进入对应的相位转换单位将实现hν1由初始光束转换为环形光束，而hν2仍然保持实心光束，从而实现阵列型双光束。阵列双光束进入像素单元对应的空间光调制器6，此装置可以通过计算机程序高速控制每个像素双光束的通断，从而可以调制每束双光束并控制图形的写入。从空间光调制器6出来的双光束阵列通过透镜组7聚焦，再通过微缩图像透镜组8实现图像的微缩，最终在光刻材料9表面实现高速并行双光束光刻。光刻材料在精密位移平台10控制下实现位移步进控制。
图11A、11B中方案二表示采用环形光产生与实心高斯光束分离的方式。如图11A、11B方案二中所示hν1为环形光初始输入光束，hν2、hν3为实心高斯光束初始输入光束。hν1首先通过透镜组1后进入偏振装置2，从而产生所需要的偏振光束。而实心高斯光束hν2通过透镜组3，经过高斯光束整形器4转换为平顶光束。hν1所转换的环形光束也通过环形光束整形器5转换为中空平顶光束形态。整形后的两束光经过分光镜6汇合后，经过相位型衍射光栅阵列7，将偏振的hν1转换为阵列型涡旋光，即环形光阵列，同时实心光束hν2与环形光阵列叠加共同通过空间光调制器8。相位型衍射光栅与空间光调制器相耦合并像素单元一一对应，从而实现每个双光束单元格的单独开关控制，从而控制图形的写入。与方案一相同，方案二从空间光调制器8出来的双光束阵列通过透镜组9聚焦，再通过微缩图像透镜组10实现图像的微缩，最终在光刻材料11表面实现高速并行双光束光刻。光刻材料在精密位移平台12控制下实现位移步进控制。
图12中所示A与B两图表示本发明中所示双光束阵列所采用的扫描方式包括直角坐标系扫描与极坐标系扫描两种坐标系体系方式。根据所需刻图案的特征不同可切换两种坐标系方式。图12中A所示为直角坐标系下的阵列扫描方式，光刻图案数据被切分成大量矩形块后，双光束从矩形块一个角顶点以蛇形方式最终扫描到矩形块对角线顶点。图12中B所示为极坐标系下的阵列扫描方式，光刻图案按照极坐标方式圆形中心对称分布，阵列点通过圆形扫描实现图案光刻。本发明所述的两种扫描体系方式可在光刻过程中单独使用，也可相互交叉、融合、切换共同采用，由计算机程序控制两种坐标系的切换。
实施例1
正性光刻方法按如下步骤进行操作：
1)环形抑制光束在涂布光刻胶的材料上进行定位；
2)在环形光所定位的光刻胶的位置叠加实心光束激活；
3)光刻胶被激活区域的分子开关控制效应分子释放效应基团，将光刻胶中的保护基团脱保护；步骤一至步骤三在程序控制下反复进行步进扫描曝光，即连接形成所要蚀刻的图形；
4)加入显影液将已经脱保护基团的光刻胶部分溶解，而没有曝光的区域则不会被显影液溶解；
5)暴露出来的区域可进行蚀刻、处理及加工操作；
6)洗脱掉这一轮操作的光刻胶，暴露出包含此次蚀刻图形的材料表面；
7)涂布新的光刻胶层，准备开始下一轮光刻操作。
实施例2
负性光刻方法按如下步骤进行操作：
1)环形抑制光束在涂布光刻胶的材料表面上进行定位；
2)在环形光所定位的光刻胶的位置叠加激活光束控制分子激活；
3)光刻胶被激活的区域的活化聚合控制分子与光刻胶中单体成分发生作用，引发聚合反应，步骤一至步骤三在程序控制下反复进行步进扫描曝光，即连接形成所要蚀刻的图形；
4)加入显影液将没有曝光的光刻胶部分被显影液溶解，而曝光的区域由聚合物保护则不会被显影液溶解；
5)暴露出来的材料区域可进行处理、蚀刻及加工等操作；
6)洗脱掉这一步操作的光刻胶，暴露出包含此次处理的材料表面；
7)涂布新的光刻胶层，准备开始下一轮光刻操作。
实施例3
双光束光刻胶主要由树脂、双光束可控分子开关感光产酸剂(PSPAG)、溶剂和添加剂等按一定比例配置而成，配置方法如下：
1)在避光条件下，将0.005～10份的双光束可控分子开关感光产酸剂(PSPAG)溶于20～90份的有机溶剂中；
2)待溶解完全后，向其中继续加入5～80份的酸降解型树脂和0～60份溶解抑制剂，搅拌均匀，即得到双光束正性光刻胶。
实施例4
双光束光刻胶主要由树脂、双光束可控分子开关感光敏化剂(PSPSen)、光产酸剂、溶剂和添加剂等按一定比例配置而成，配置方法如下：
1)在避光条件下，将0.0001～2份的双光束可控分子开关感光敏化剂(PSPSen)和0.005～10份的光生酸剂溶于20～90份的有机溶剂中；
2)待溶解完全后，向其中继续加入5～80份的酸降解型树脂和0～60份溶解抑制剂，搅拌均匀，即得到双光束正性光刻胶。
实施例5
双光束光刻胶主要由树脂、双光束可控分子开关感光产碱剂(PSPBG)、溶剂和添加剂等按一定比例配置而成，配置方法如下：
1)在避光条件下，将0.005～10份的双光束可控分子开关感光产碱剂(PSPBG)溶于20～90份的有机溶剂中；
2)待溶解完全后，向其中继续加入5～80份的碱降解型树脂和0～60份溶解抑制剂，搅拌均匀，即得到双光束正性光刻胶。
实施例6
一种双光束可控分子开关感光产酸剂分子(PSPAG)合成方法如下：
1)所述一种PSPAG分子合成路线如图13所示，化合物1与化合物1A在Pd(OAc) 2和Xantphos催化作用下反应生成化合物2，化合物2与化合物2A在Pd 2(dba )3、KOAc、PCy 3、1,4-dioxane在130℃催化下反应生成化合物3；
2)化合物4与Br 2、AcOH、CH 2Cl 2反应生成化合物5，化合物5与化合物5A在Pd(PPh 3) 4催化下，于dioxane:H 2O比例9：1溶剂中反应生成化合物6，并与NBS在THF下生成化合物7；
3)化合物7与先前反应生成的化合物3在Pd(PPh 3) 4、PPh 3、K 3PO 4、1,4-dioxane催化下生成化合物8，化合物8与CF 3SO 3Cl在NEt 3、CH 2Cl 2中反应生成最终目标分子；
4)最终经核磁谱(图14)与质谱(图15)鉴定为目标分子。
综上所述，本发明有效克服了现有技术中的种种缺点而具高度产业利用价值。
上述实施例仅例示性说明本发明的原理及其功效，而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下，对上述实施例进行修饰或改变。因此，举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利要求所涵盖。

Claims (28)

  1. 一种光刻方法，包括下列步骤：
    1)向光刻材料提供第一光与第二光，所述第一光与第二光部分重叠，所述光刻材料中含有分子开关可控效应分子产生分子，所述第一光用于使所述分子开关可控效应分子产生分子处于关闭状态，所述第二光用于使所述分子开关可控效应分子产生分子处于打开状态，所述第一光与所述第二光重叠区域所述分子开关可控效应分子产生分子处于关闭状态；至少部分的处于打开状态的分子开关可控效应分子产生分子产生效应分子，以使分子开关打开区域的光刻材料物理和/或化学性质发生变化；
    2)将发生物理或化学特性变化的光刻材料或者未发生变化的光刻材料之任一移除。
  2. 如权利要求1所述的光刻方法，其特征在于，所述第一光和第二光之一为单空心光，所述第一光和第二光之二至少部分覆盖所述第一光和第二光之一光照区域所包围的无光照区域。
  3. 如权利要求1所述的光刻方法，其特征在于，所述第一光和第二光之一为多空心光，所述第一光和第二光之二至少部分覆盖第一光光照区域所包围的无光照区域。
  4. 如权利要求3所述的光刻方法，其特征在于，所述第一光与第二光中至少有一个光为阵列光。
  5. 如权利要求3～4任一所述的光刻方法，其特征在于，所述第一光与第二光中至少有一个光为多光束。
  6. 如权利要求2～5任一所述的光刻方法，其特征在于，所述第一光和第二光之二的光照区域不超出第一光和第二光之一的光照区域的外缘。
  7. 如权利要求1～6任一所述的光刻方法，其特征在于，所述分子开关可控效应分子产生分子所产生的效应分子选自去光刻材料保护基团分子。
  8. 如权利要求7所述的光刻方法，其特征在于，所述去光刻材料保护基团分子选自酸性分子、碱性分子、单线态氧。
  9. 如权利要求1～6任一所述的光刻方法，其特征在于，所述分子开关可控效应分子产生分子所产生的效应分子选自活化光刻材料聚合控制分子。
  10. 如权利要求9所述的光刻方法，其特征在于，所述活化光刻材料聚合控制分子选自聚合反应引发分子。
  11. 如权利要求7～10任一所述的光刻方法，其特征在于，所述分子开关可控效应分子产生分子的分子结构中包括分子开关基团和效应分子产生基团。
  12. 如权利要求11所述的光刻方法，其特征在于，分子开关基团与效应分子产生基团之 间通过化学键连接。
  13. 如权利要求1～12任一所述的光刻方法，其特征在于，所述步骤1)中，处于打开状态的分子开关可控效应分子产生分子产生效应分子的方式是指改变处于打开状态的分子开关可控效应分子产生分子所经受的光照条件。
  14. 如权利要求1～13任一所述的光刻方法，其特征在于，所述光刻材料物理或化学特性发生变化是指在显影液中的溶解性变化。
  15. 一种由如权利要求1～14任一所述的光刻方法，其特征在于，使所述光刻材料物理或化学特性发生变化的方法选自将光刻材料中的保护基团脱去或者使光刻材料中聚合物单体发生聚合。
  16. 一种由权利要求1～15任一所述的光刻方法产生的产品。
  17. 一种光刻材料，所述光刻材料包括分子开关可控效应分子产生分子以及对效应分子敏感的化合物。
  18. 如权利要求17所述的光刻材料，其特征在于，所述效应分子选自去光刻材料保护基团分子或活化光刻材料聚合控制分子。
  19. 如权利要求18所述的光刻材料，其特征在于，所述去光刻材料保护基团分子选自酸性分子、碱性分子、单线态氧。
  20. 如权利要求18所述的光刻材料，其特征在于，所述活化光刻材料聚合控制分子选自聚合反应引发分子。
  21. 如权利要求17～20任一所述的光刻材料，其特征在于，所述效应分子敏感化合物选自效应分子敏感聚合物、效应分子敏感聚合单体或低聚物。
  22. 如权利要求17～21任一所述的光刻材料，其特征在于，所述分子开关可控效应分子产生分子中包括分子开关基团和效应分子产生基团。
  23. 如权利要求22所述的光刻材料，其特征在于，所述分子开关可控效应分子产生分子中，分子开关基团与效应分子产生基团之间通过化学键连接。
  24. 一种化合物，所述化合物包括分子开关基团和效应分子产生基团。
  25. 如权利要求24所述的化合物，其特征在于，所述效应分子选自去光刻材料保护基团分子或活化光刻材料聚合控制分子。
  26. 如权利要求25所述的化合物，其特征在于，所述去光刻材料保护基团分子选自酸性分子、碱性分子、单线态氧。
  27. 如权利要求25所述的化合物，其特征在于，所述活化光刻材料聚合控制分子选自聚合 反应引发分子。
  28. 如权利要求24～27任一所述的化合物，其特征在于，所述分子开关可控效应分子产生分子中，分子开关基团与效应分子产生基团之间通过化学键连接。
PCT/CN2018/111325 2017-10-23 2018-10-23 一种光刻方法、光刻产品和光刻材料 WO2019080820A1 (zh)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP18871767.2A EP3702837A4 (en) 2017-10-23 2018-10-23 PHOTOLITHOGRAPHY PROCESS, PHOTOLITHOGRAPHY PRODUCT AND PHOTOLITHOGRAPHY MATERIAL
KR1020207013245A KR20200078532A (ko) 2017-10-23 2018-10-23 리소그래피 방법, 리소그래피 제품과 리소그래피 재료
CA3078560A CA3078560A1 (en) 2017-10-23 2018-10-23 Lithographic method, lithographic product and lithographic material
US16/757,431 US20200341373A1 (en) 2017-10-23 2018-10-23 Lithographic Method, Lithographic Product and Lithographic Material
JP2020520477A JP2021500598A (ja) 2017-10-23 2018-10-23 リソグラフィ方法、リソグラフィ製品及びリソグラフィ材料

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201710995525.7 2017-10-23
CN201710995525 2017-10-23

Publications (1)

Publication Number Publication Date
WO2019080820A1 true WO2019080820A1 (zh) 2019-05-02

Family

ID=66246790

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2018/111325 WO2019080820A1 (zh) 2017-10-23 2018-10-23 一种光刻方法、光刻产品和光刻材料

Country Status (6)

Country Link
US (1) US20200341373A1 (zh)
EP (1) EP3702837A4 (zh)
JP (1) JP2021500598A (zh)
KR (1) KR20200078532A (zh)
CA (1) CA3078560A1 (zh)
WO (1) WO2019080820A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113939872A (zh) * 2019-05-21 2022-01-14 上海必修福企业管理有限公司 一种光学系统及光学方法
JP2022535843A (ja) * 2019-06-06 2022-08-10 クソロ ゲーエムベーハー 二色光重合によって出発材料を局所的に重合するプロセスおよび装置ならびに成形体の体積印刷方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102768466A (zh) * 2011-05-05 2012-11-07 中国科学院理化技术研究所 化学增幅型正性光刻胶、制备方法及其在双光子精细加工中的应用
CN106932914A (zh) * 2017-04-17 2017-07-07 鲁东大学 一种三维阵列空心光斑的产生方法及装置
CN107272180A (zh) * 2017-07-17 2017-10-20 鲁东大学 一种纳米尺度的均匀光学隧道产生方法和装置

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102011081247A1 (de) * 2011-08-19 2013-02-21 Carl Zeiss Smt Gmbh Belichtungsanlage und Verfahren zur strukturierten Belichtung einer lichtempfindlichen Schicht
US9063434B2 (en) * 2013-01-11 2015-06-23 University Of Utah Research Foundation Sub-diffraction-limited patterning and imaging via multi-step photoswitching

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102768466A (zh) * 2011-05-05 2012-11-07 中国科学院理化技术研究所 化学增幅型正性光刻胶、制备方法及其在双光子精细加工中的应用
CN106932914A (zh) * 2017-04-17 2017-07-07 鲁东大学 一种三维阵列空心光斑的产生方法及装置
CN107272180A (zh) * 2017-07-17 2017-10-20 鲁东大学 一种纳米尺度的均匀光学隧道产生方法和装置

Non-Patent Citations (5)

* Cited by examiner, † Cited by third party
Title
GAN, FUXI ET AL.: "Breaking Through the Optical Diffraction Limits, Developing the Nano-Optics and Photonics", ACTA OPTICA SINICA, vol. 31, no. 9, 30 September 2011 (2011-09-30), pages 0900104 - 1 -0900104-9, XP055686119 *
HAN, ANYUN: "Wavefront ENgineering and Optical Super Resolution", SEMICONDUCTOR INFORMATION, vol. 35, no. 3, 30 June 1998 (1998-06-30), pages 1 - 17, XP055686112 *
LI, RUIJI ET AL.: "A Self-Contained Photoacid Generator for Super Acid Based on Photochromic Terarylene", CHEMICAL COMMUNICATIONS, vol. 53, no. 31, 24 March 2017 (2017-03-24) - 21 April 2017 (2017-04-21), pages 4339 - 4341, XP055593965, ISSN: 1359-7345, DOI: 10.1039/C7CC01635B *
LI, SHUAI ET AL.: "A Review on Concept and Development of Stimulated Emission Depletion Microscopy (STED)", ACTA LASER BIOLOGY SINICA, vol. 22, no. 2, 30 April 2013 (2013-04-30), pages 103 - 113, XP055686116 *
See also references of EP3702837A4 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113939872A (zh) * 2019-05-21 2022-01-14 上海必修福企业管理有限公司 一种光学系统及光学方法
CN113939872B (zh) * 2019-05-21 2024-01-30 上海必修福企业管理有限公司 一种光学系统及光学方法
JP2022535843A (ja) * 2019-06-06 2022-08-10 クソロ ゲーエムベーハー 二色光重合によって出発材料を局所的に重合するプロセスおよび装置ならびに成形体の体積印刷方法

Also Published As

Publication number Publication date
CA3078560A1 (en) 2019-05-02
EP3702837A1 (en) 2020-09-02
KR20200078532A (ko) 2020-07-01
US20200341373A1 (en) 2020-10-29
JP2021500598A (ja) 2021-01-07
EP3702837A4 (en) 2021-08-04

Similar Documents

Publication Publication Date Title
EP0500321B1 (en) High speed aqueous solvent developable photopolymer compositions
KR101741276B1 (ko) 레지스트 조성물 및 패턴 형성법
US7714988B2 (en) System and method for absorbance modulation lithography
US10522428B2 (en) Critical dimension control by use of a photo agent
US20070122734A1 (en) Molecular photoresist
WO2016025210A1 (en) Critical dimension control in photo-sensitized chemically-amplified resist
WO2019080820A1 (zh) 一种光刻方法、光刻产品和光刻材料
US8551689B2 (en) Methods of manufacturing semiconductor devices using photolithography
JP5486141B2 (ja) 光開始反応
Spangenberg et al. Recent advances in two-photon stereolithography
JP3992550B2 (ja) 感活性エネルギー線樹脂組成物、感活性エネルギー線樹脂フィルム及び該フィルムを用いるパターン形成方法
CN111880383A (zh) 一种高密度光刻图案处理方法
Zhang et al. Advanced lithography materials: From fundamentals to applications
CN113156773B (zh) 一种合作吸收双光束超分辨光刻系统及方法
TW202013078A (zh) 半導體裝置的製造方法
US6669995B1 (en) Method of treating an anti-reflective coating on a substrate
KR19980024040A (ko) 고해상도 레지스트용 고감도 광활성 중합체 및 현상제
TWI307451B (en) Photoresist composition
JP2023502600A (ja) リソグラフィ装置、パターニングシステム、及び積層構造体をパターニングする方法
KR100252217B1 (ko) 반도체장치의 제조를 위한 원자외선 노광용 포토레지스트 조성용 구조제 수지와 그 제조방법 및 그 구조제 수지를 포함하는 원자외선 노광용 포토레지스트 조성물
KR100253084B1 (ko) 반도체장치의제조를위한원자외선노광용포토레지스트조성용구조제수지와그제조방법및그구조제수지를포함하는원자외선노광용포토레지스트조성물
KR100252218B1 (ko) 반도체장치의 제조를 위한 원자외선 노광용 포토레지스트 조성용 구조제 수지와 그 제조방법 및 그 구조제 수지를 포함하는 원자외선 노광용 포토레지스트 조성물
CN112034691A (zh) 一种阴阳文互补光强掩膜版双光束投影光刻装置及方法
CN115356895A (zh) 利用正负可调光刻胶特性一步制备微纳结构的系统及方法
JP2023051836A (ja) フォトレジスト組成物及びパターン形成方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18871767

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 3078560

Country of ref document: CA

ENP Entry into the national phase

Ref document number: 2020520477

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20207013245

Country of ref document: KR

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2018871767

Country of ref document: EP

Effective date: 20200525