WO2022121888A1 - 钛锆氧化物纳米粒子、光刻胶、光刻胶的图案化方法及生成印刷电路板的方法 - Google Patents

钛锆氧化物纳米粒子、光刻胶、光刻胶的图案化方法及生成印刷电路板的方法 Download PDF

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WO2022121888A1
WO2022121888A1 PCT/CN2021/136049 CN2021136049W WO2022121888A1 WO 2022121888 A1 WO2022121888 A1 WO 2022121888A1 CN 2021136049 W CN2021136049 W CN 2021136049W WO 2022121888 A1 WO2022121888 A1 WO 2022121888A1
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Prior art keywords
photoresist
zirconium oxide
oxide nanoparticles
titanium zirconium
titanium
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PCT/CN2021/136049
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English (en)
French (fr)
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徐宏
何向明
王晓琳
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清华大学
北京华睿新能动力科技发展有限公司
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Application filed by 清华大学, 北京华睿新能动力科技发展有限公司 filed Critical 清华大学
Priority to KR1020237023261A priority Critical patent/KR20230128484A/ko
Priority to US18/266,249 priority patent/US20240043281A1/en
Priority to JP2023558927A priority patent/JP2024500565A/ja
Publication of WO2022121888A1 publication Critical patent/WO2022121888A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C01G25/02—Oxides
    • 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
    • G03F7/004—Photosensitive materials
    • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
    • 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
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/68—Preparation processes not covered by groups G03F1/20 - G03F1/50
    • G03F1/76—Patterning of masks by imaging
    • 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
    • G03F7/0042—Photosensitive materials with inorganic or organometallic light-sensitive compounds not otherwise provided for, e.g. inorganic resists
    • G03F7/0043—Chalcogenides; Silicon, germanium, arsenic or derivatives thereof; Metals, oxides or alloys thereof
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • 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
    • 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
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • 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
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • 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
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • 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
    • G03F7/26—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
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/32—Liquid compositions therefor, e.g. developers
    • G03F7/325—Non-aqueous compositions

Definitions

  • the present application relates to the technical field of photoresist, and in particular, to a photoresist, a method for patterning a photoresist, and a method for generating a printed circuit board.
  • Photoresist is the most critical basic material of lithography technology.
  • Photoresist is a kind of mixed material sensitive to light or radiation, usually composed of photoresist host material, photosensitizer, solvent and some other additives.
  • Photoresist host materials mainly include film-forming resins, molecular glass compounds, and inorganic oxides.
  • the photoresist is irradiated or irradiated by exposure sources such as ultraviolet light, electron beam, ion beam, excimer laser beam, X-ray, etc., its solubility, adhesion and other properties change significantly, and can be developed in an appropriate solvent to form photolithography graphics.
  • exposure sources such as ultraviolet light, electron beam, ion beam, excimer laser beam, X-ray, etc.
  • a titanium zirconium oxide nanoparticle the general molecular formula is Ti x Zry O z L n , wherein x, y and z are independently selected from any integers from 1 to 6, and n is selected from 5 to 30. Any integer, L is an organic ligand, and the organic ligand has a radical-initiated polymerization group.
  • the general molecular formula of the titanium zirconium oxide nanoparticles is Ti 2 Zr 6 O 6 L 20 , Ti 2 Zr 4 O 4 L 16 , Ti 2 Zr 4 O 5 L 14 or Ti 2 Zr 4 O 6 L 12 .
  • the mass percentage of the titanium zirconium oxide nanoparticles in the photoresist is 1% to 50%.
  • the organic ligand is an organic ligand containing a carbon-carbon double bond.
  • the organic ligand is selected from any one or more of acrylic acid, methacrylic acid and 3,3-dimethacrylic acid.
  • a photoresist includes an organic solvent and the titanium zirconium oxide nanoparticles.
  • the photoresist further includes a photoacid generator, which can be decomposed under illumination to form a photoacid catalyst, and the photoacid catalyst can catalyze the titanium zirconium oxide agglomeration of nanoparticles; and/or, the photoresist further includes a photoinitiator capable of initiating agglomeration of the titanium zirconium oxide nanoparticles.
  • the organic solvent is selected from propylene glycol monomethyl ether acetate, propylene glycol ethyl ether, propylene glycol monoacetate, ethylene glycol methyl ether acetate, ethyl acetate, butyl acetate, chloroform and dichloromethane any one or more of them.
  • a photoresist comprising an organic solvent and titanium zirconium oxide nanoparticles
  • the general molecular formula of the titanium zirconium oxide nanoparticles is Ti 2 Zr 6 O 6 L 20 , Ti 2 Zr 4 O 4 L 16 , Ti 2 Zr 4 O 5 L 14 or Ti 2 Zr 4 O 6 L 12
  • L is an organic ligand
  • the organic ligand has a radical-initiated polymerization group.
  • the organic ligand is selected from any one or more of acrylic acid, methacrylic acid and 3,3-dimethacrylic acid.
  • a photoresist combination product includes the photoresist and a developer.
  • the developer is selected from the group consisting of toluene, ortho-xylene, meta-xylene, para-xylene, mesitylene, ethyl acetate, butyl acetate, 4-methyl-2-pentanol, 4 -Methyl-2-pentanone, methyl ethyl ketone, propylene glycol monomethyl ether acetate, propylene glycol ethyl ether, propylene glycol monoacetate, ethylene glycol methyl ether acetate, 2-butanone, 2-heptanone, ethanol, Any one or more of n-propanol, isopropanol, n-butanol, isobutanol, n-hexane and cyclohexane.
  • a method for patterning described photoresist comprising the following steps:
  • the light source is irradiated on the pre-film-forming layer of the substrate through the mask to perform an exposure operation, so that the exposed area of the pre-film-forming layer forms titanium zirconium oxide nanoparticle agglomerates;
  • the developer is applied on the exposed pre-film formation layer, so that the unexposed area on the pre-film formation layer that is blocked by the mask is dissolved in the developer, and the exposed area of the pre-film formation layer is formed due to the formation of titanium zirconium oxide nanoparticles. and remain on the base.
  • the light source used in the exposure operation is an ultraviolet, deep ultraviolet or extreme ultraviolet light source, and the exposure dose is 4mJ/cm 2 to 50mJ/cm 2 .
  • the light source used in the exposure operation is an electron beam source with a dose of 10 ⁇ C/cm 2 to 10 mC/cm 2 .
  • the substrate is selected from a silicon plate.
  • a method of generating a printed circuit board comprising the steps of:
  • the pre-patterned sheet is etched using dry or wet methods.
  • metal nanoparticles In traditional photoresists, although some metal nanoparticles have the property of agglomeration under light, the metal nanoparticles that are not irradiated by light will be unstable due to contact with water in the air, which may also occur. agglomerates, so there is little difference in solubility between exposed and unexposed areas.
  • the inventors found that the metal oxide nanoparticles formed by the composite of titanium and zirconium have more stable properties in the air, and basically no longer agglomerate under the influence of air humidity.
  • the titanium zirconium oxide nanoparticles in the exposed area agglomerate under light, so that the solubility in the developing solution is reduced, while the titanium zirconium oxide nanoparticles in the unexposed area do not agglomerate, so that they can be dissolved in the developing solution and be remove.
  • the combination of titanium and zirconium improves the stability of metal nanoparticles in the air, thereby improving the solubility difference between the non-exposed area and the exposed area, improving the resolution of lithography patterns, and reducing line edge roughness, especially for high precision requirements.
  • the lithography quality of the device has been greatly improved.
  • the titanium zirconium oxide nanoparticles in the examples of the present application have free-radically polymerizable organic ligands, which on the one hand improves the dispersibility of the titanium zirconium oxide nanoparticles in organic solvents, and on the other hand, the organic ligands themselves can be exposed to light. Polymerization occurs under the lower temperature, which is beneficial to improve the solubility difference between the exposed area and the non-exposed area of the photoresist, and is beneficial to improve the quality of patterning.
  • FIG. 1 is an optical microscope photograph of the patterned photoresist layer of Example 1 of the application.
  • FIG. 2 is a scanning electron microscope photograph of the patterned photoresist layer of Example 1 of the application.
  • Example 3 is a scanning electron microscope photograph of the patterned photoresist layer of Example 2 of the present application.
  • FIG. 5 is a scanning electron microscope photograph of the patterned photoresist layer of Comparative Example 2 of the present application.
  • FIG. 6 is a scanning electron microscope photograph of the patterned photoresist layer of Example 6 of the present application.
  • FIG. 7 is a scanning electron microscope photograph of the patterned photoresist layer of Example 7 of the present application.
  • light used in this application includes, but is not limited to, ultraviolet, deep ultraviolet, and extreme ultraviolet light, and also broadly covers electron beams, X-rays, and the like.
  • the lithography pattern has become more and more fine, and the thickness of the photoresist film has gradually decreased, which requires the photoresist not only to have good etching resistance but also to have the characteristics of large differences in solubility before and after exposure.
  • different metal oxide-containing photoresist materials have been developed.
  • the existing metal oxides easily react with water in the air, so that the solubility difference between the exposed area and the non-exposed area does not change much, resulting in low lithography pattern resolution and high line edge roughness.
  • the embodiment of the present application provides a titanium zirconium oxide nanoparticle, the titanium zirconium oxide nanoparticle, and the general molecular formula of the titanium zirconium oxide nanoparticle is Ti x Zr y O z L n , wherein x, y , z are independently selected from any integer from 1 to 6, n is selected from any integer from 5 to 30, L is an organic ligand, and the organic ligand has a radical-initiated polymerization group.
  • Embodiments of the present application further provide a photoresist including the titanium zirconium oxide nanoparticles, and the photoresist further includes an organic solvent.
  • metal nanoparticles In traditional photoresists, although some metal nanoparticles have the property of agglomeration under light, the metal nanoparticles that are not irradiated by light will be unstable due to contact with water in the air, which may also occur. agglomerates, so there is little difference in solubility between exposed and unexposed areas.
  • the inventors found that the metal oxide nanoparticles formed by the composite of titanium and zirconium have more stable properties in the air, and basically no longer agglomerate under the influence of air humidity.
  • the titanium zirconium oxide nanoparticles in the exposed area agglomerate under light, so that the solubility in the developing solution is reduced, while the titanium zirconium oxide nanoparticles in the unexposed area do not agglomerate, so that they can be dissolved in the developing solution and be remove.
  • the combination of titanium and zirconium improves the stability of metal nanoparticles in the air, thereby improving the solubility difference between the non-exposed area and the exposed area, improving the resolution of lithography patterns, and reducing line edge roughness, especially for high precision requirements.
  • the lithography quality of the device has been greatly improved.
  • the titanium zirconium oxide nanoparticles in the examples of the present application have free-radically polymerizable organic ligands, which on the one hand improves the dispersibility of the titanium zirconium oxide nanoparticles in organic solvents, and on the other hand, the organic ligands themselves can be exposed to light. Polymerization occurs under the lower temperature, which is beneficial to improve the solubility difference between the exposed area and the non-exposed area of the photoresist, and is beneficial to improve the quality of patterning.
  • the organic ligand can be coated on the surface of the titanium zirconium oxide nanoparticles, or can be mixed with metal ions in the titanium zirconium oxide nanoparticles.
  • the general molecular formula of titanium zirconium oxide nanoparticles is Ti x Zry O z L n .
  • x can be selected from 1, 2, 3, 4, 5 or 6.
  • y can be selected from 1, 2, 3, 4, 5 or 6.
  • z can be selected from 1, 2, 3, 4, 5 or 6.
  • x, y, z can be the same or different, and x, y, z can be arbitrarily combined according to any of the above options.
  • the titanium zirconium oxide nanoparticles may be represented by one of the following chemical formulae: Ti 1 Zr 1 O 1 L n , Ti 1 Zr 1 O 2 L n ; Ti 1 Zr 2 O 1 L n , Ti 1 Zr 2 O 2 L n , Ti 1 Zr 2 O 3 L n ; Ti 1 Zr 3 O 2 L n , Ti 1 Zr 3 O 3 L n , Ti 1 Zr 3 O 4 L n ; Ti 1 Zr 4 O 2 L n , Ti 1 Zr 4 O 3 L n , Ti 1 Zr 4 O 4 L n , Ti 1 Zr 4 O 5 L n ; Ti 1 Zr 5 O 2 L n , Ti 1 Zr 5 O 3 L n , Ti 1 Zr 5 O 4 L n , Ti 1 Zr 5 O 5 L n ; Ti 1 Zr 5 O 2 L n , Ti 1 Zr 5 O 3 L n , Ti 1 Zr 5 O 4 L n , Ti 1 Z
  • the titanium zirconium oxide nanoparticles may be represented by one of the following formulae: Ti 2 Zr 1 O 1 L n , Ti 2 Zr 1 O 2 L n , Ti 2 Zr 1 O 3 L n ; Ti 2 Zr 2 O 2 L n , Ti 2 Zr 2 O 3 L n , Ti 2 Zr 2 O 4 L n ; Ti 2 Zr 3 O 2 L n , Ti 2 Zr 3 O 3 L n , Ti 2 Zr 3 O 4 L n , Ti 2 Zr 3 O 5 L n ; Ti 2 Zr 4 O 2 L n , Ti 2 Zr 4 O 3 L n , Ti 2 Zr 4 O 4 L n , Ti 2 Zr 4 O 5 L n , Ti 2 Zr 4 O 6 L n ; Ti 2 Zr 5 O 2 L n , Ti 2 Zr 5 O 3 L n , Ti 2 Zr 5 O 4 L n , Ti 2 Zr 4 O 6 L n ; Ti 2 Zr
  • the titanium zirconium oxide nanoparticles may be represented by one of the following formulae: Ti3Zr1O2Ln , Ti3Zr1O3Ln , Ti3Zr1O4 L n ; Ti 3 Zr 2 O 2 L n , Ti 3 Zr 2 O 3 L n , Ti 3 Zr 2 O 4 L n , Ti 3 Zr 2 O 5 L n ; Ti 3 Zr 3 O 3 L n , Ti 3 Zr 3 O 4 L n , Ti 3 Zr 3 O 5 L n , Ti 3 Zr 3 O 6 L n ; Ti 3 Zr 4 O 4 L n , Ti 3 Zr 4 O 5 L n , Ti 3 Zr 4 O 6 L n ; Ti 3 Zr 5 O 5 L n , Ti 3 Zr 4 O 6 L n ; Ti 3 Zr 5 O 5 L n , Ti 3 Zr 5 O 6 L n ; Ti 3 Zr 6 O 6 L n .
  • the titanium zirconium oxide nanoparticles may be represented by one of the following formulae: Ti 4 Zr 1 O 3 L n , Ti 4 Zr 1 O 4 L n , Ti 4 Zr 1 O 5 L n , Ti 4 Zr 1 O 6 L n ; Ti 4 Zr 2 O 3 L n , Ti 4 Zr 2 O 4 L n , Ti 4 Zr 2 O 5 L n , Ti 4 Zr 2 O 6 L n ; Ti 4 Zr 3 O 3 L n , Ti 4 Zr 3 O 4 L n , Ti 4 Zr 3 O 5 L n , Ti 4 Zr 3 O 6 L n ; Ti 4 Zr 4 O 4 L n , Ti 4 Zr 4 O 5 L n , Ti 4 Zr 4 O 6 L n ; Ti 4 Zr 5 O 5 L n , Ti 4 Zr 4 O 6 L n ; Ti 4 Zr 5 O 5 L n , Ti 4 Zr 5 O 6 L n ; Ti 4 Zr
  • the titanium zirconium oxide nanoparticles may be represented by one of the following formulae: Ti 5 Zr 1 O 3 L n , Ti 5 Zr 1 O 4 L n , Ti 5 Zr 1 O 5 L n , Ti 5 Zr 1 O 6 L n ; Ti 5 Zr 2 O 4 L n , Ti 5 Zr 2 O 5 L n , Ti 5 Zr 2 O 6 L n ; Ti 5 Zr 3 O 5 L n , Ti 5 Zr 3 O 6 L n ; Ti 5 Zr 4 O 5 L n , Ti 5 Zr 4 O 6 L n .
  • the titanium zirconium oxide nanoparticles may be represented by one of the following formulae: Ti 6 Zr 1 O 4 L n , Ti 6 Zr 1 O 5 L n , Ti 6 Zr 1 O 6 L n ; Ti 6 Zr 2 O 5 L n , Ti 6 Zr 2 O 6 L n ; Ti 6 Zr 3 O 5 L n , Ti 6 Zr 3 O 6 L n ; Ti 6 Zr 4 O 6 L n .
  • the chemical composition of the titanium zirconium oxide nanoparticles in the photoresist may be only one, or may contain multiple titanium zirconium oxide nanoparticles with different ratios of Ti, Zr, O, and L.
  • the general molecular formula of the titanium zirconium oxide nanoparticles may be Ti 2 Zr 6 O 6 L 20 , Ti 2 Zr 4 O 4 L 16 , Ti 2 Zr 4 O 5 L 14 or Ti 2 Zr 4 O 6 L 12 .
  • the titanium zirconium oxide nanoparticles represented by any one of the above general formulas may be included, or a plurality of titanium zirconium oxide nanoparticles respectively represented by a plurality of the above general formulae may be included.
  • the mass percentage of the titanium zirconium oxide nanoparticles in the photoresist is 1% to 50%.
  • the mass percentage of titanium zirconium oxide nanoparticles in the photoresist can be 1%-5%, 5%-10%, 10%-15%, 15%-20%, 20%-25%, 25% % ⁇ 30%, 30% ⁇ 35%, 35% ⁇ 40%, 40% ⁇ 45% or 45% ⁇ 50%.
  • the organic ligand is an organic ligand containing a carbon-carbon double bond.
  • the organic ligands containing carbon-carbon double bonds can undergo a radical addition reaction of carbon-carbon double bonds under light, so that titanium zirconium oxide nanoparticles can be polymerized.
  • a titanium zirconium oxide nanoparticle may contain one, two, three or more than three types of organic ligands.
  • the organic ligand may be selected from any one or more of acrylic acid (AA), methacrylic acid (MAA), and 3,3-dimethacrylic acid (DMAA).
  • the organic ligand L and the titanium zirconium oxide are linked by means of coordination bonds to form the titanium zirconium oxide nanoparticles.
  • the organic ligand L includes two adjacent Ti and/or Zr atoms connected to two adjacent Ti and/or Zr atoms in the general formula of the titanium zirconium oxide nanoparticle, respectively.
  • L is derived from an aliphatic compound or an aromatic compound.
  • the number of carbon atoms of L is, for example, 3 to 30, respectively, 3 to 20 may be selected, and 3 to 12 may be further selected.
  • the number of carbon-carbon double bonds of L may be 1-3, for example, 1.
  • L may include a straight chain group, a branched chain group or an alicyclic group, and may further include 1-4 aromatic rings, such as a benzene ring.
  • L is independently selected from any one of the following structures:
  • L may be selected from any one of acrylic ligands, methacrylic acid ligands, and 3,3-dimethacrylic acid ligands.
  • the photoresist includes a photoacid generator capable of decomposing under illumination to form a photoacid catalyst capable of catalyzing the titanium zirconium oxide nanoparticles reunion.
  • the photoresist includes a photoinitiator capable of initiating agglomeration of the titanium zirconium oxide nanoparticles.
  • any one or a combination of the photoacid generator and the photoinitiator is included in the photoresist.
  • the mass percentage of the photoacid generator and the photoinitiator in the photoresist may be 0-10% and not equal to 0, and may specifically be 0.01%-0.1%, 0.1%- 0.5%, 0.5% to 1%, 1% to 2%, 2% to 3%, 3% to 4% or 4% to 5%.
  • the photoacid generator may be selected from N-hydroxynaphthalimide trifluoromethanesulfonic acid, N-hydroxysuccinimide trifluoromethanesulfonic acid, and N-hydroxyphthalimide-p-toluene one or more of the sulfonic acids.
  • the photoinitiator may be selected from coumarins (eg, 7-diethylamino-3-(2'-benzimidazolyl)coumarin, etc.), benzoins (eg, benzoin dimethyl ether) etc.), one or more of alkyl phenones (such as ⁇ , ⁇ -diethoxyacetophenone, etc.).
  • coumarins eg, 7-diethylamino-3-(2'-benzimidazolyl)coumarin, etc.
  • benzoins eg, benzoin dimethyl ether
  • alkyl phenones such as ⁇ , ⁇ -diethoxyacetophenone, etc.
  • the photoresist may not contain a photoacid generator.
  • the organic solvent in the photoresist can be selected from a solvent with good solubility for the titanium zirconium oxide nanoparticles, so that the titanium zirconium oxide nanoparticles can be completely dissolved and fully dispersed in the organic solvent, so as to avoid the titanium zirconium in the photoresist.
  • the uneven dispersion of the oxide nanoparticles leads to different degrees of polymerization in different positions of the exposed area, so as to prevent the areas with insufficient polymerization degree in the exposed area from dissolving in the developer.
  • the organic solvent is selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol ethyl ether, propylene glycol monoacetate, ethylene glycol methyl ether acetate, ethyl acetate, butyl acetate, chloroform and dichloromethane any one or more.
  • the titanium zirconium oxide nanoparticles can be prepared by, but not limited to, the method of the following exemplary embodiments, the method comprising:
  • titanium ion source zirconium ion source and organic ligand source
  • the titanium ion source, the zirconium ion source and the organic ligand source are mixed in a solvent according to a stoichiometric ratio, and reacted at -25°C to 200°C to obtain the titanium zirconium oxide nanoparticles.
  • Ti in the titanium ion source can be +4 valence, for example, can be selected from +4 valent titanium carboxylate, hydrated carboxylate, organic sulfonate, hydrated organic sulfonate, alkoxide, halogen salt, nitrate, sulfuric acid one or more of the salts.
  • Zr in the zirconium ion source can be +4 valence, for example, it can be selected from the carboxylate of +4 valent zirconium, hydrated carboxylate, organic sulfonate, hydrated organic sulfonate, alkoxide, halogen salt, nitrate, sulfuric acid one or more of the salts.
  • the organic ligand source is the source of the organic ligand L, which can be an aliphatic compound or an aromatic compound.
  • the organic ligand source has a group capable of reacting with the titanium ion source and the zirconium ion source to generate a ligand, such as a carboxyl group or an acid anhydride group, and the organic ligand source also has a radical-initiated polymerization group, such as an alkenyl group.
  • the number of carbon atoms of the organic ligand source may be, for example, 3-30, optionally 3-20, and further optionally 3-12; the number of alkenyl groups may be, for example, 1-3, optionally 1.
  • the source of organic ligands may include linear, branched, or alicyclic groups.
  • the organic ligand source can include 1-4 aromatic rings, such as benzene rings.
  • the organic ligand source is selected from the group consisting of acrylic acid, methacrylic acid, 3-methylbut-2-enoic acid, 4-vinylbenzoic acid, 4-(prop-1-en-2-yl ) benzoic acid, 4-(2-methylprop-1-en-1-yl)benzoic acid, 2-(4-(2-methylprop-1-en-1-yl)phenyl)acetic acid, 2 One or more of -(4-vinylphenyl)acetic acid and 2-(4-(prop-1-en-2-yl)phenyl)acetic acid.
  • the solvent can be selected from one or more of organic solvents such as water, lipids, alcohols, ethers, cyclic ethers, benzenes, carboxylic acids and/or alkanes, including but not limited to tetrahydrofuran, 1 ,4-dioxane, benzene, toluene, p-xylene, o-xylene, m-xylene, dimethyl sulfoxide, N-methylpyrrolidone, N,N-dimethylacetamide, N,N-di Mixtures of one or more methylformamides.
  • organic solvents such as water, lipids, alcohols, ethers, cyclic ethers, benzenes, carboxylic acids and/or alkanes, including but not limited to tetrahydrofuran, 1 ,4-dioxane, benzene, toluene, p-xylene, o-xylene,
  • the reaction temperature of the titanium ion source, the zirconium ion source and the organic ligand source in the solvent may be 10°C to 100°C, such as 25°C.
  • the method further includes the steps of separating and purifying the titanium zirconium oxide nanoparticles, such as recrystallization, adding a poor solvent (such as water) for precipitation, extraction, One or more of the steps of washing, centrifugal separation, atmospheric distillation, vacuum distillation, rotary evaporation or vacuum drying.
  • a poor solvent such as water
  • Embodiments of the present application further provide a photoresist combination product, including the photoresist and developer according to any one of the above embodiments.
  • the photoresist combination product is used to form a patterned photoresist layer.
  • the developer and photoresist are matched to each other and are used to dissolve the unexposed photoresist.
  • the developer is selected from the group consisting of toluene, ortho-xylene, meta-xylene, para-xylene, mesitylene, ethyl acetate, butyl acetate, 4-methyl-2-pentanol, 4- Methyl-2-pentanone, methyl ethyl ketone, propylene glycol monomethyl ether acetate, propylene glycol ethyl ether, propylene glycol monoacetate, ethylene glycol methyl ether acetate, 2-butanone, 2-heptanone, ethanol, normal Any one or more of propanol, isopropanol, n-butanol, isobutanol, n-hexane and cyclohexane.
  • Embodiments of the present application also provide a method for patterning photoresist, comprising the following steps:
  • the developer is applied on the exposed pre-film formation layer, so that the unexposed area on the pre-film formation layer that is blocked by the mask is dissolved in the developer, and the exposed area of the pre-film formation layer is formed due to the formation of titanium zirconium oxide nanoparticles. and remain on the substrate, thereby forming a patterned photoresist layer.
  • the light source used in the exposure operation may be an ultraviolet, deep ultraviolet, extreme ultraviolet or electron beam light source.
  • the extreme ultraviolet light source refers to a light source with a wavelength of 10nm-14nm.
  • the wavelength of ultraviolet may be, for example, 254 nm or 365 nm.
  • the light source used in the exposure operation is an ultraviolet, deep ultraviolet or extreme ultraviolet light source, and the exposure dose is 4mJ/cm 2 -1000mJ/cm 2 , for example, 4mJ/cm 2 -50mJ/cm 2 .
  • the light source used in the exposure operation is an electron beam light source, and the exposure dose is 10 ⁇ C/cm 2 to 10 mC/cm 2 .
  • the exposure dose should be controlled in an appropriate range.
  • the exposure dose is too small, the energy will be too low, which is not conducive to the polymerization of titanium zirconium oxide nanoparticles in the exposed area, and is not conducive to the formation of the solubility difference between the exposed area and the non-exposed area, and the development effect is poor. If the exposure dose is too large, the reactive species that initiate the reaction may diffuse to the non-exposed area, causing the photoresist in the non-exposed area to react, thereby reducing the pattern accuracy.
  • the developer is primarily used to dissolve unpolymerized titanium zirconium oxide nanoparticles.
  • the organic ligands of the titanium zirconium oxide nanoparticles in the exposed area undergo radical polymerization of carbon-carbon double bonds to form aggregates, or the titanium zirconium oxides that have dropped the organic ligands are polymerized into aggregates under the initiation of free radicals.
  • the agglomerates in the exposed areas are insoluble in the developer, or the agglomerates in the exposed areas have low solubility in the developer, so even if they partially dissolve, the exposed areas are still covered by the agglomerates.
  • the developer and the organic solvent in the photoresist can be the same or different.
  • the solubility of the titanium zirconium oxide nanoparticles in the developer is lower than the solubility in the organic solvent of the photoresist, so as to prevent the titanium zirconium oxide nanoparticles from being dissolved in the developer due to insufficient degree of polymerization after exposure,
  • the exposure area is dissolved or partially dissolved, resulting in a decrease in the precision of the exposure pattern.
  • the developer may be selected from the group consisting of toluene, ortho-xylene, meta-xylene, para-xylene, ethyl acetate, butyl acetate, ethanol, n-propanol, isopropanol, n-butanol, n-hexane and Any one or more of cyclohexane.
  • the developing temperature may be room temperature, for example, 20°C to 30°C.
  • the thickness of the pre-film formation layer after removing the organic solvent may be 10 nm ⁇ 500 nm.
  • the thickness of the pre-film formation layer can be 10nm ⁇ 50nm, 50nm ⁇ 100nm, 100nm ⁇ 150nm, 150nm ⁇ 200nm, 200nm ⁇ 250nm, 250nm ⁇ 300nm, 300nm ⁇ 350nm, 350nm ⁇ 400nm, 400nm ⁇ 450nm or 450nm ⁇ 500nm .
  • the substrate is selected from a silicon plate, which can be used for integrated circuit board fabrication.
  • Other substrates insoluble in developer can also be selected according to actual needs.
  • the deep ultraviolet and longer wavelength light sources are transmissive masks
  • the extreme ultraviolet is a reflective mask
  • the electron beam is exposed according to the pattern set by the software.
  • the embodiment of the present application also provides a method for generating a printed circuit board, comprising the following steps:
  • the regions of the silicon substrate with the photoresist layer are not etched, and the regions without the photoresist layer are etched.
  • Examples 1-5 and Comparative Examples 1-2 patterned photoresist layers were prepared through the following steps, and the entire process needed to be protected from light before the development was completed.
  • the exposure dose light intensity * time: when the exposure light source is ultraviolet, deep ultraviolet or extreme ultraviolet light source, the exposure dose can be 4mJ/cm 2 ⁇ 1000mJ/cm 2 ; When the exposure light source is an electron beam light source, the exposure dose is 10 ⁇ C/cm 2 to 10 mC/cm 2 .
  • the exposure operation is performed through a mask with a preset pattern.
  • the developer can be selected from any of toluene, ortho-xylene, meta-xylene, para-xylene, ethyl acetate, butyl acetate, ethanol, n-propanol, isopropanol, n-butanol, n-hexane or cyclohexane one or more.
  • This strong solubility polarity switch makes the unexposed areas dissolve while the exposed areas remain after development, and the mask pattern is successfully transferred to the surface of the silicon wafer.
  • the silicon wafer is blown dry by a nitrogen gun and is ready for use.
  • 0.5g metal oxide nanoparticles Ti 2 Zr 4 O 4 (OMc) 16 and 0.05g photoacid generator N-hydroxynaphthalimide trifluoromethanesulfonic acid were dissolved in 9.45g solvent propylene glycol monomethyl ether acetate, using Filter with a filter head with a pore size of 0.22 ⁇ m. Drop an appropriate amount of the filtered photoresist solution on the surface of the silicon wafer, and uniformly glue at a speed of 2000 r/min for 1 minute. Dry the solvent at 100°C for 1 minute.
  • Expose with a low-pressure mercury lamp with a wavelength of 254nm the exposure dose is 50mJ/cm 2 , develop with toluene, dry the surface of the silicon wafer with nitrogen, and observe the lithography pattern on the surface of the silicon wafer with an optical microscope and a scanning electron microscope, respectively, as shown in Figure 1 and shown in Figure 2.
  • Example 2 Basically the same as Example 1, the difference is only in the composition of the photoresist: 5g titanium zirconium oxide nanoparticles Ti 3 Zr 5 O 5 (DMAA) 22 , 0.05g photoacid generator N-hydroxynaphthalimide trifluoro Methanesulfonic acid, 4.45 g solvent dichloromethane.
  • the developer is selected from para-toluene, ortho-xylene and meta-xylene mixtures.
  • Example 2 Basically the same as Example 1, the difference is only in the composition of the photoresist: 1 g of titanium zirconium oxide nanoparticles Ti 4 Zr 3 O 4 (AA) 10 (MAA) 10 , 0.1 g of photoacid generator N-hydroxy o-phenylene Imide p-toluenesulfonic acid, 8.9 g solvent chloroform.
  • the developer is selected from para-xylene.
  • Example 2 Basically the same as Example 1, the difference is only in the composition of the photoresist: 2.5g titanium zirconium oxide nanoparticles Ti 2 Zr 6 O 6 (AA) 10 (DMAA) 10 , 0.08g photoacid generator N-hydroxynaphthalene Imide trifluoromethanesulfonic acid, 7.42 g solvent dichloromethane.
  • the developer is selected from para-xylene.
  • Electron beam lithography 0.5g metal oxide nanoparticles Ti 2 Zr 4 O 4 (OMc) 16 and 0.05g photoacid generator N-hydroxynaphthalimide trifluoromethanesulfonic acid dissolved in 9.45g solvent propylene glycol monomethyl ether acetate, filtered through a filter with a pore size of 0.22 ⁇ m. Drop an appropriate amount of the filtered photoresist solution on the surface of the silicon wafer, and uniformly glue at a speed of 2000 r/min for 1 minute. Dry the solvent at 80°C for 1 minute.
  • EUV lithography 0.5g metal oxide nanoparticles Ti 2 Zr 4 O 4 (OMc) 16 and 0.05g photoacid generator N-hydroxynaphthalimide trifluoromethanesulfonic acid dissolved in 9.45g solvent propylene glycol monomethyl ether acetate, filtered through a filter with a pore size of 0.22 ⁇ m. Drop an appropriate amount of the filtered photoresist solution on the surface of the silicon wafer, and uniformly glue at a speed of 2000 r/min for 1 minute. Dry the solvent at 80°C for 1 minute.
  • Exposure by EUV interference lithography with a dose of 77mJ/cm 2 develop with propylene glycol monomethyl ether acetate, dry the surface of the silicon wafer with nitrogen, and observe the lithography pattern on the surface of the silicon wafer with a scanning electron microscope, as shown in Figure 7 .
  • 0.5 g of metal oxide nanoparticles TiOC and 0.05 g of photoacid generator N-hydroxynaphthalimide trifluoromethanesulfonic acid were dissolved in 9.45 g of solvent propylene glycol monomethyl ether acetate, and filtered with a filter head with a pore size of 0.22 ⁇ m. Drop an appropriate amount of the filtered photoresist solution on the surface of the silicon wafer, and uniformly glue at a speed of 2000 r/min for 1 minute. Dry the solvent at 100°C for 1 minute.

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Abstract

一种光刻胶、光刻胶组合产品、光刻胶的图案化方法、生成印刷电路板的方法。其中光刻胶包括有机溶剂和钛锆氧化物纳米粒子，钛锆氧化物纳米粒子的分子通式为Ti xZr yO zL n,其中，x、y、z分别独立地选自1～6中的任意整数，n选自5～30中的任意整数，L为有机物配体，有机物配体具有可自由基引发聚合的基团。

Description

钛锆氧化物纳米粒子、光刻胶、光刻胶的图案化方法及生成印刷电路板的方法
相关申请
本申请要求2020年12月9日申请的，申请号为202011428100.6，名称为“光刻胶、光刻胶的图案化方法及生成印刷电路板的方法”的中国专利申请的优先权，在此将其全文引入作为参考。
技术领域
本申请涉及光刻胶技术领域，特别是涉及一种光刻胶、光刻胶的图案化方法及生成印刷电路板的方法。
背景技术
随着大规模集成电路集成度的不断提高，其特征尺寸越来越小，加工尺寸已经进入纳米级。集成电路的发展需要光刻技术的支持，光刻胶(或称光致抗蚀剂)是光刻技术最关键的基础材料。光刻胶是一类对光或者射线敏感的混合材料，通常由光刻胶主体材料、光敏剂、溶剂和其他一些添加剂等组成。光刻胶主体材料主要有成膜树脂、分子玻璃化合物、无机氧化物等几类。光刻胶经紫外光、电子束、离子束、准分子激光束、X射线等曝光源的照射或辐射，其溶解性、黏附性等性质发生明显变化，可以在适当的溶剂中显影形成光刻图形。
发明内容
基于此，有必要提供一种钛锆氧化物纳米粒子、光刻胶、光刻胶的图案化方法及生成印刷电路板的方法。
一种钛锆氧化物纳米粒子，分子通式为Ti xZr yO zL n,其中，x、y、z分别独立地选自1～6中的任意整数，n选自5～30中的任意整数，L为有机物配体，所述有机物配体具有可自由基引发聚合的基团。
在其中一个实施例中，所述钛锆氧化物纳米粒子的分子通式为Ti 2Zr 6O 6L 20、Ti 2Zr 4O 4L 16、Ti 2Zr 4O 5L 14或Ti 2Zr 4O 6L 12。
在其中一个实施例中，所述钛锆氧化物纳米粒子在所述光刻胶中的质量百分数为1％～50％。
在其中一个实施例中，所述有机物配体为含有碳碳双键的有机物配体。
在其中一个实施例中，所述有机物配体选自丙烯酸、甲基丙烯酸和3,3-二甲基丙烯酸中的任意一种或多种。
一种光刻胶，包括有机溶剂和所述钛锆氧化物纳米粒子。
在其中一个实施例中，所述光刻胶还包括光致产酸剂，所述光致产酸剂能够在光照下分解形成光酸催化剂，所述光酸催化剂能够催化所述钛锆氧化物纳米粒子的团聚；和/或，所述光刻胶还包括光引发剂，所述光引发剂能够引发所述钛锆氧化物纳米粒子的团聚。
在其中一个实施例中，所述有机溶剂选自丙二醇单甲醚醋酸酯、丙二醇乙醚、丙二醇单醋酸酯、乙二醇甲醚醋酸酯、乙酸乙酯、乙酸丁酯、氯仿及二氯甲烷中的任意一种或多种。
一种光刻胶，包括有机溶剂和钛锆氧化物纳米粒子，所述钛锆氧化物纳米粒子的分子通式为Ti 2Zr 6O 6L 20、Ti 2Zr 4O 4L 16、Ti 2Zr 4O 5L 14或Ti 2Zr 4O 6L 12，L为有机物配体，所述有机物配体具有可自由基引发聚合的基团。
在其中一个实施例中，所述有机物配体选自丙烯酸、甲基丙烯酸和3,3-二甲基丙烯酸中的任意一种或多种。
一种光刻胶组合产品，包括所述的光刻胶以及显影剂。
在其中一个实施例中，所述显影剂选自甲苯、邻二甲苯、间二甲苯、对二甲苯、均三甲苯、乙酸乙酯、乙酸丁酯、4-甲基-2-戊醇、4-甲基-2-戊酮、甲基乙基酮、丙二醇单甲醚醋酸酯、丙二醇乙醚、丙二醇单醋酸酯、乙二醇甲醚醋酸酯、2-丁酮、2-庚酮、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、正己烷及环己烷中的任意一种或多种。
一种所述的光刻胶的图案化方法，包括以下步骤：
将所述光刻胶涂布在基底表面，除去所述光刻胶中的有机溶剂，在所述基底表面上形成预成膜层；
将光源透过掩膜照射在所述基底的预成膜层上进行曝光操作，使得预成膜层的曝光区域形成钛锆氧化物纳米粒子团聚体；
将显影剂施加在曝光后的预成膜层上，使得预成膜层上被掩膜遮挡的未曝光区域溶解于显影剂中，而预成膜层的曝光区域由于形成钛锆氧化物纳米粒子而保留在基底上。
在其中一个实施例中，所述曝光操作所用的光源为紫外、深紫外或极紫外光源，曝光剂量为4mJ/cm 2～50mJ/cm 2。
在其中一个实施例中，所述曝光操作所用的光源为电子束源，剂量为10μC/cm 2～10mC/cm 2。
在其中一个实施例中，所述基底选自硅板。
一种生成印刷电路板的方法，包括如下步骤：
按照所述的光刻胶的图案化方法制备硅板基底上具有图案化光刻胶层的预图案化板材；
利用干法或湿法刻蚀所述预图案化板材。
在传统的光刻胶中，虽然一些金属纳米粒子具有在光照下团聚的性能，但未被光照射的金属纳米粒子，由于会与空气中的水接触，造成金属纳米粒子不稳定，也会发生团聚，因此曝光区域和未曝光区域的溶解度差异不大。发明人发现，将钛锆复合形成的金属氧化物纳米粒子在空气中的性质更稳定，基本不会再受到空气湿度影响而团聚。因此，本申请中，曝光区域的钛锆氧化物纳米粒子在光照下团聚，从而在显影液中溶解度降低，而未曝光区域钛锆氧化物纳米粒子不团聚，从而能够在显影液中溶解而被去除。钛和锆的配合提高了金属纳米粒子在空气中的稳定性，从而提高了非曝光区域和曝光区域的溶解度差异，提高光刻图形分辨率、降低线边缘粗糙度，尤其对于精密度要求较高的器件的光刻质量具有很大提升。
另外，本申请实施例的钛锆氧化物纳米粒子具有可自由基聚合的有机物配体，一方面提高钛锆氧化物纳米粒子在有机溶剂中的分散性，另一方面有机物配体本身可在光照下发生聚合，从而有利于提高光刻胶曝光区和非曝光区的溶解度差异，有利于提高图案化的质量。
附图说明
为了更清楚地说明本公开实施例中的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本公开的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本申请实施例1的图案化光刻胶层的光学显微镜照片。
图2为本申请实施例1的图案化光刻胶层的扫描电子显微镜照片。
图3为本申请实施例2的图案化光刻胶层的扫描电子显微镜照片。
图4为本申请对比例1的图案化光刻胶层的扫描电子显微镜照片。
图5为本申请对比例2的图案化光刻胶层的扫描电子显微镜照片。
图6为本申请实施例6的图案化光刻胶层的扫描电子显微镜照片。
图7为本申请实施例7的图案化光刻胶层的扫描电子显微镜照片。
具体实施方式
为了便于理解本申请，下面将参照相关附图对本申请进行更全面的描述。附图中给出 了本申请的较佳实施例。但是，本申请可以以许多不同的形式来实现，并不限于本文所描述的实施例。相反地，提供这些实施例的目的是使对本申请的公开内容的理解更加透彻全面。
除非另有定义，本文所使用的所有的技术和科学术语与属于本申请的技术领域的技术人员通常理解的含义相同。本文中在本申请的说明书中所使用的术语只是为了描述具体的实施例的目的，不是旨在于限制本申请。本文所使用的术语“和/或”包括一个或多个相关的所列项目的任意的和所有的组合。
本申请使用的“光”一词的范围包括但不限于紫外、深紫外和极紫外光，还广义的涵盖电子束、X射线等。
近年来，光刻图形越来越精细，光刻胶膜的厚度也逐渐减小，这就要求光刻胶不仅要具有好的抗刻蚀性质而且具有曝光前后溶解性差异大的特点。为了增强光刻胶的抗刻蚀性，已经开发了不同的含金属氧化物的光刻胶材料。然而，现有的金属氧化物容易与空气中的水反应，使得曝光区和非曝光区溶解性差异变化不大，造成光刻图形分辨率不高、线边缘粗糙度程度高。因此，有必要针对传统光刻胶的光刻图形分辨率不高、线边缘粗糙度程度高的问题，提供一种光刻胶、光刻胶的图案化方法及生成印刷电路板的方法。本申请实施例提供一种钛锆氧化物纳米粒子，所述钛锆氧化物纳米粒子，所述钛锆氧化物纳米粒子的分子通式为Ti xZr yO zL n,其中，x、y、z分别独立地选自1～6中的任意整数，n选自5～30中的任意整数，L为有机物配体，所述有机物配体具有可自由基引发聚合的基团。本申请实施例还提供一种包括所述钛锆氧化物纳米粒子的光刻胶，所述光刻胶还包括有机溶剂。
在传统的光刻胶中，虽然一些金属纳米粒子具有在光照下团聚的性能，但未被光照射的金属纳米粒子，由于会与空气中的水接触，造成金属纳米粒子不稳定，也会发生团聚，因此曝光区域和未曝光区域的溶解度差异不大。发明人发现，将钛锆复合形成的金属氧化物纳米粒子在空气中的性质更稳定，基本不会再受到空气湿度影响而团聚。因此，本申请中，曝光区域的钛锆氧化物纳米粒子在光照下团聚，从而在显影液中溶解度降低，而未曝光区域钛锆氧化物纳米粒子不团聚，从而能够在显影液中溶解而被去除。钛和锆的配合提高了金属纳米粒子在空气中的稳定性，从而提高了非曝光区域和曝光区域的溶解度差异，提高光刻图形分辨率、降低线边缘粗糙度，尤其对于精密度要求较高的器件的光刻质量具有很大提升。
另外，本申请实施例的钛锆氧化物纳米粒子具有可自由基聚合的有机物配体，一方面提高钛锆氧化物纳米粒子在有机溶剂中的分散性，另一方面有机物配体本身可在光照下发 生聚合，从而有利于提高光刻胶曝光区和非曝光区的溶解度差异，有利于提高图案化的质量。
钛锆氧化物纳米粒子中，有机物配体可以是包被在钛锆氧化物纳米粒子的表面，也可以是与金属离子共混在钛锆氧化物纳米粒子中。
钛锆氧化物纳米粒子的分子通式为Ti xZr yO zL n。x可选自1、2、3、4、5或6。y可选自1、2、3、4、5或6。z可选自1、2、3、4、5或6。x、y、z可以相同或不同，x、y、z可按照以上任意选择进行随意组合。
在一些实施例中，x＝1，钛锆氧化物纳米粒子可以由以下化学式中的一个所表示：Ti 1Zr 1O 1L n、Ti 1Zr 1O 2L n；Ti 1Zr 2O 1L n、Ti 1Zr 2O 2L n、Ti 1Zr 2O 3L n；Ti 1Zr 3O 2L n、Ti 1Zr 3O 3L n、Ti 1Zr 3O 4L n；Ti 1Zr 4O 2L n、Ti 1Zr 4O 3L n、Ti 1Zr 4O 4L n、Ti 1Zr 4O 5L n；Ti 1Zr 5O 2L n、Ti 1Zr 5O 3L n、Ti 1Zr 5O 4L n、Ti 1Zr 5O 5L n、Ti 1Zr 5O 6L n；Ti 1Zr 6O 2L n、Ti 1Zr 6O 3L n、Ti 1Zr 6O 4L n、Ti 1Zr 6O 5L n、Ti 1Zr 6O 6L n。
在一些实施例中，x＝2，钛锆氧化物纳米粒子可以由以下化学式中的一个所表示：Ti 2Zr 1O 1L n、Ti 2Zr 1O 2L n、Ti 2Zr 1O 3L n；Ti 2Zr 2O 2L n、Ti 2Zr 2O 3L n、Ti 2Zr 2O 4L n；Ti 2Zr 3O 2L n、Ti 2Zr 3O 3L n、Ti 2Zr 3O 4L n、Ti 2Zr 3O 5L n；Ti 2Zr 4O 2L n、Ti 2Zr 4O 3L n、Ti 2Zr 4O 4L n、Ti 2Zr 4O 5L n、Ti 2Zr 4O 6L n；Ti 2Zr 5O 2L n、Ti 2Zr 5O 3L n、Ti 2Zr 5O 4L n、Ti 2Zr 5O 5L n、Ti 2Zr 5O 6L n；Ti 2Zr 6O 2L n、Ti 2Zr 6O 3L n、Ti 2Zr 6O 4L n、Ti 2Zr 6O 5L n、Ti 2Zr 6O 6L n。
在一些实施例中，x＝3，钛锆氧化物纳米粒子可以由以下化学式中的一个所表示：Ti 3Zr 1O 2L n、Ti 3Zr 1O 3L n、Ti 3Zr 1O 4L n；Ti 3Zr 2O 2L n、Ti 3Zr 2O 3L n、Ti 3Zr 2O 4L n、Ti 3Zr 2O 5L n；Ti 3Zr 3O 3L n、Ti 3Zr 3O 4L n、Ti 3Zr 3O 5L n、Ti 3Zr 3O 6L n；Ti 3Zr 4O 4L n、Ti 3Zr 4O 5L n、Ti 3Zr 4O 6L n；Ti 3Zr 5O 5L n、Ti 3Zr 5O 6L n；Ti 3Zr 6O 6L n。
在一些实施例中，x＝4，钛锆氧化物纳米粒子可以由以下化学式中的一个所表示：Ti 4Zr 1O 3L n、Ti 4Zr 1O 4L n、Ti 4Zr 1O 5L n、Ti 4Zr 1O 6L n；Ti 4Zr 2O 3L n、Ti 4Zr 2O 4L n、Ti 4Zr 2O 5L n、Ti 4Zr 2O 6L n；Ti 4Zr 3O 3L n、Ti 4Zr 3O 4L n、Ti 4Zr 3O 5L n、Ti 4Zr 3O 6L n；Ti 4Zr 4O 4L n、Ti 4Zr 4O 5L n、Ti 4Zr 4O 6L n；Ti 4Zr 5O 5L n、Ti 4Zr 5O 6L n；Ti 4Zr 6O 6L n。
在一些实施例中，x＝5，钛锆氧化物纳米粒子可以由以下化学式中的一个所表示：Ti 5Zr 1O 3L n、Ti 5Zr 1O 4L n、Ti 5Zr 1O 5L n、Ti 5Zr 1O 6L n；Ti 5Zr 2O 4L n、Ti 5Zr 2O 5L n、Ti 5Zr 2O 6L n；Ti 5Zr 3O 5L n、Ti 5Zr 3O 6L n；Ti 5Zr 4O 5L n、Ti 5Zr 4O 6L n。
在一些实施例中，x＝6，钛锆氧化物纳米粒子可以由以下化学式中的一个所表示：Ti 6Zr 1O 4L n、Ti 6Zr 1O 5L n、Ti 6Zr 1O 6L n；Ti 6Zr 2O 5L n、Ti 6Zr 2O 6L n；Ti 6Zr 3O 5L n、Ti 6Zr 3O 6L n； Ti 6Zr 4O 6L n。
上述各化学式中n为5～30中的任一整数。在一些实施例中，n＝6、8、10、12、16、18、20、22、24、26或28。在一些进一步的实施例中，n＝12、14、16或20。
在一些实施例中，光刻胶中的钛锆氧化物纳米粒子的化学组成可以仅为一种，也可含有多种不同Ti、Zr、O、L比例的钛锆氧化物纳米粒子。
在一些实施例中，所述钛锆氧化物纳米粒子的分子通式可以为Ti 2Zr 6O 6L 20、Ti 2Zr 4O 4L 16、Ti 2Zr 4O 5L 14或Ti 2Zr 4O 6L 12。在光刻胶中，可仅包括由任一种上述通式表示的钛锆氧化物纳米粒子，或者包括由上述通式中的多种分别表示的多种钛锆氧化物纳米粒子。
在一些实施例中，所述钛锆氧化物纳米粒子在所述光刻胶中的质量百分数为1％～50％。具体的，钛锆氧化物纳米粒子在光刻胶中的质量百分数可以为1％～5％、5％～10％、10％～15％、15％～20％、20％～25％、25％～30％、30％～35％、35％～40％、40％～45％或45％～50％。
在一些实施例中，所述有机物配体为含有碳碳双键的有机物配体。含有碳碳双键的有机物配体可在光照下发生碳碳双键自由基加成反应，使得钛锆氧化物纳米粒子聚合。一种钛锆氧化物纳米粒子中可含有一种、两种、三种或多于三种类型的有机物配体。在一实施例中，一种钛锆氧化物纳米粒子中可含有两种有机物配体，钛锆氧化物纳米粒子的可以表示为Ti xZr yO zL1 n1L2 n2，n1和n2分别为大于或等于0的整数，且n1+n2＝n。在一实施例中，一种钛锆氧化物纳米粒子中可含有三种有机物配体，钛锆氧化物纳米粒子的可以表示为Ti xZr yO zL1 n1L2 n2L3 n3，n1、n2和n3分别为大于或等于0的整数，且n1+n2+n3＝n。L1、L2、L3分别表示不同种类的有机物配体。在一些实施例中，所述有机物配体可选自丙烯酸(AA)、甲基丙烯酸(MAA)及3,3-二甲基丙烯酸(DMAA)中的任意一种或多种。
在一些实施例中，有机物配体L与钛锆氧化物通过配位键的方式连接，以构成所述钛锆氧化物纳米粒子。有机物配体L包括分别与钛锆氧化物纳米粒子分子通式中两个相邻的Ti和/或Zr原子连接的
Figure PCTCN2021136049-appb-000001
且包括碳碳双键，例如L具有烯基。L源自脂肪族化合物或芳香族化合物。L的碳原子数例如分别为3-30个，可选为3-20个，进一步可选为3-12个。L的碳碳双键的数量可以为1-3个，例如为1个。L可以包括直链基、支链基或脂环基，并可以进一步包括1-4个芳环，如苯环。
在一些实施例中，L独立的选自如下结构中的任意一种：
Figure PCTCN2021136049-appb-000002
Figure PCTCN2021136049-appb-000003
在示例性的实施例中，L可以选自丙烯酸配位基、甲基丙烯酸配位基和3,3-二甲基丙烯酸配位基中的任意一种。
在一些实施例中，所述光刻胶包括光致产酸剂，所述光致产酸剂能够在光照下分解形成光酸催化剂，所述光酸催化剂能够催化所述钛锆氧化物纳米粒子的团聚。在一些实施例中，所述光刻胶包括光引发剂，所述光引发剂能够引发所述钛锆氧化物纳米粒子的团聚。在一些实施例中，光刻胶中包括所述光致产酸剂和所述光引发剂中的任意一种或两种的组合。在一些实施例中，光致产酸剂和所述光引发剂在所述光刻胶中的质量百分数可以为0～10％且不等于0，具体可以为0.01％～0.1％、0.1％～0.5％、0.5％～1％、1％～2％、2％～3％、3％～4％或4％～5％。在一些实施例中，光致产酸剂可选自N-羟基萘酰亚胺三氟甲磺酸、N-羟基琥珀酰亚胺三氟甲磺酸及N-羟基邻苯酰亚胺对甲苯磺酸中的一种或多种。在一些实施例中，光引发剂可选自香豆素类(例如7-二乙基氨基-3-(2′-苯并咪唑基)香豆素等)、安息香类(例如安息香双甲醚等)、烷基苯酮类(例如α，α-二乙氧基苯乙酮等)中的一种或多种。在电子束光刻或极紫外光刻中，所述光刻胶中可不含有光致产酸剂。
光刻胶中的有机溶剂可选自对钛锆氧化物纳米粒子具有较好溶解性的溶剂，使钛锆氧化物纳米粒子能够完全溶解、充分分散在有机溶剂中，避免光刻胶中钛锆氧化物纳米粒子分散不均而导致曝光区域不同位置的聚合度不同，从而避免曝光区域聚合度不够的区域溶解在显影剂中。在一些实施例中，所述有机溶剂选自丙二醇单甲醚醋酸酯、丙二醇乙醚、丙二醇单醋酸酯、乙二醇甲醚醋酸酯、乙酸乙酯、乙酸丁酯、氯仿及二氯甲烷中的任意一种或多种。
在一些实施例中，所述钛锆氧化物纳米粒子可以通过但不限于以下示例性实施例的方法制备，该方法包括：
提供钛离子源、锆离子源和有机配体源；
将所述钛离子源、锆离子源和有机配体源在溶剂中根据化学计量比混合，并在-25℃至200℃反应得到所述钛锆氧化物纳米粒子。
钛离子源中Ti可以为+4价，例如可以选自+4价钛的羧酸盐、水合羧酸盐、有机磺酸盐、水合有机磺酸盐、醇盐、卤素盐、硝酸盐、硫酸盐中的一种或多种。
锆离子源中Zr可以为+4价，例如可以选自+4价锆的羧酸盐、水合羧酸盐、有机磺酸盐、水合有机磺酸盐、醇盐、卤素盐、硝酸盐、硫酸盐中的一种或多种。
有机配体源为有机物配体L的来源，可以为脂肪族化合物或芳香族化合物。有机配体源具有能够与钛离子源和锆离子源反应生成配位基的基团，例如羧基或酸酐基团，并且有机配体源还具有可自由基引发聚合的基团，如烯基。
有机配体源的碳原子数例如可以为3-30个，可选为3-20个，进一步可选为3-12个；烯基数例如可以为1-3个，可选为1个。在一些实施例中，有机配体源可以包括直链基、支链基或脂环基。在一些实施例中，有机配体源可以包括1-4个芳环，如苯环。
在一些实施例中，所述有机物配体源选自丙烯酸、甲基丙烯酸、3-甲基丁-2-烯酸、4-乙烯基苯甲酸、4-(丙-1-烯-2-基)苯甲酸、4-(2-甲基丙-1-烯-1-基)苯甲酸、2-(4-(2-甲基丙-1-烯-1-基)苯基)乙酸、2-(4-乙烯基苯基)乙酸、2-(4-(丙-1-烯-2-基)苯基)乙酸中的一种或多种。
所述溶剂可以选自水、脂类、醇类、醚类、环醚类、苯类、羧酸类和/或烷烃类等有机溶剂中的一种或多种，包括但不限于四氢呋喃、1,4-二氧六环、苯、甲苯、对二甲苯、邻二甲苯、间二甲苯、二甲亚砜、N-甲基吡咯烷酮、N,N-二甲基乙酰胺、N,N-二甲基甲酰胺的一种或多种的混合。
所述钛离子源、锆离子源和有机配体源在溶剂中的反应温度可以为10℃至100℃，如25℃。
在一实施例中，得到所述钛锆氧化物纳米粒子后，所述方法还包括将钛锆氧化物纳米粒子分离提纯的步骤，例如进行重结晶、加入不良溶剂(例如水)沉淀、萃取、洗涤、离心分离、常压蒸馏、减压蒸馏、旋转蒸发或真空干燥等步骤中的一种或多种。
本申请实施例还提供一种光刻胶组合产品，包括上述任一实施例的光刻胶以及显影剂。光刻胶组合产品用于形成图案化的光刻胶层。
显影剂与光刻胶是相互匹配的，用于溶解未曝光的光刻胶。在一些实施例中，所述显影剂选自甲苯、邻二甲苯、间二甲苯、对二甲苯、均三甲苯、乙酸乙酯、乙酸丁酯、4-甲基-2-戊醇、4-甲基-2-戊酮、甲基乙基酮、丙二醇单甲醚醋酸酯、丙二醇乙醚、丙二醇单醋酸酯、乙二醇甲醚醋酸酯、2-丁酮、2-庚酮、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、正己烷及环己烷中的任意一种或多种。
本申请实施例还提供一种光刻胶的图案化方法，包括以下步骤：
将所述光刻胶涂布在基底表面，除去所述光刻胶中的有机溶剂，在所述基底表面上形成预成膜层；
将光源透过掩膜照射在所述基底的预成膜层上进行曝光操作，使得预成膜层的曝光区域形成钛锆氧化物纳米粒子团聚体；以及
将显影剂施加在曝光后的预成膜层上，使得预成膜层上被掩膜遮挡的未曝光区域溶解于显影剂中，而预成膜层的曝光区域由于形成钛锆氧化物纳米粒子而保留在基底上，从而形成图案化的光刻胶层。
所述曝光操作所用的光源可以为紫外、深紫外、极紫外或电子束光源。其中极紫外光源指波长为10nm-14nm的光源。紫外的波长例如可以为254nm或365nm。在一些实施例中，所述曝光操作所用的光源为紫外、深紫外或极紫外光源，曝光剂量为4mJ/cm 2～1000mJ/cm 2，例如4mJ/cm 2～50mJ/cm 2。在另一实施例中，所述曝光操作所用的光源为电子束光源，曝光剂量为10μC/cm 2～10mC/cm 2。曝光剂量应控制在合适的范围内，曝光剂量过小则能量过低不利于曝光区域钛锆氧化物纳米粒子的聚合，不利于形成曝光区域和非曝光区域溶解度的差异，显影效果差。曝光剂量过大则可能会使引发反应的活性物质扩散到非曝光区，使非曝光区的光刻胶发生反应，从而使图形精度降低。
在一些实施例中，显影剂主要用于溶解未聚合的钛锆氧化物纳米粒子。曝光区域钛锆氧化物纳米粒子的有机物配体发生碳碳双键自由基聚合而形成团聚体，或者脱落有机物配体的钛锆氧化物在自由基引发下聚合为团聚体。曝光区域的团聚体在显影剂中不溶解于显影剂中，或者曝光区域的团聚体在显影剂中的溶解度小，即使部分溶解也能够使得曝光区域仍然被团聚体覆盖。显影剂与光刻胶中的有机溶剂可以相同或不同。在一些实施例中，钛锆氧化物纳米粒子在显影剂中的溶解性小于在光刻胶有机溶剂中的溶解性，避免钛锆氧化物纳米粒子曝光后聚合度不够而溶解于显影液中，使得曝光区域溶解或部分溶解，造成曝光图案精度降低。在一些实施例中，显影剂可选自甲苯、邻二甲苯、间二甲苯、对二甲苯、乙酸乙酯、乙酸丁酯、乙醇、正丙醇、异丙醇、正丁醇、正己烷及环己烷中的任意一种或多种。在一些实施例中，显影的温度可以为室温，例如为20℃～30℃。
在一实施例中，去除有机溶剂后的预成膜层的厚度可以为10nm～500nm。具体的，预成膜层的厚度可以为10nm～50nm、50nm～100nm、100nm～150nm、150nm～200nm、200nm～250nm、250nm～300nm、300nm～350nm、350nm～400nm、400nm～450nm或450nm～500nm。
在一些实施例中，所述基底选自硅板，可用于集成电路板制备。还可根据实际需求选择其他不溶于显影剂的基底。
在一些实施例中，关于掩膜，深紫外及更长波长光源为透射掩膜，极紫外为反射掩膜，电子束根据软件所设图形曝光。
本申请实施例还提供一种生成印刷电路板的方法，包括如下步骤：
按照所述的光刻胶的图案化方法制备硅板基底上具有图案化光刻胶层的预图案化板材；以及
利用干法或湿法刻蚀所述预图案化板材，所述硅板基底的具有光刻胶层的区域未被刻蚀，而没有光刻胶层的区域被刻蚀。
实施例1～5和对比例1～2均通过下述步骤制备图案化的光刻胶层，且在显影完成前均需要全程避光。
1.称取适量的钛锆氧化物纳米粒子Ti xZr yO zL n和光致产酸剂和有机溶剂配置成光刻胶溶液，震荡溶解，滤胶后待用。
2.设置匀胶机的转速、时间(与涂布胶膜厚度相关)，取少量光刻胶溶液旋涂于硅片表面，除溶剂制得预成膜层。
3.将预成膜层置于曝光光源下，设置曝光剂量＝光强*时间：当曝光光源为紫外、深紫外或极紫外光源时，曝光剂量可以为4mJ/cm 2～1000mJ/cm 2；当曝光光源为电子束光源时，曝光剂量为10μC/cm 2～10mC/cm 2。透过具有预设图案的掩膜进行曝光操作。
4.曝光完成后，取出硅片，室温下采用显影剂显影。显影剂可选自甲苯、邻二甲苯、间二甲苯、对二甲苯、乙酸乙酯、乙酸丁酯、乙醇、正丙醇、异丙醇、正丁醇、正己烷或环己烷中的任意一种或多种。这种强溶解性极性转换使得显影后，未曝光区域溶解而曝光区域保留，将掩膜图形成功转移到硅片表面。
5.显影完成后，氮气枪吹干硅片，待用。
6.光学显微镜或扫描电镜下观察成像图形。
实施例1
Ti 2Zr 4O 4(OMc) 16晶体合成：
1.901g钛酸四丁酯，2.681g 80％正丁醇锆的正丁醇溶液和4.095g甲基丙烯酸混合，室温密闭存放，一定时间后得晶体Ti 4Zr 4O 6(OBu) 4(OMc) 16。0.5g Ti 4Zr 4O 6(OBu) 4(OMc) 16溶于二氯甲烷，加入0.088g乙酰丙酮，搅拌30分钟，除去易挥发物，粗产物为Ti 2Zr 4O 4(OMc) 16和Ti(OBu) 2(acac) 2的混合物，粗产物溶于二氯甲烷，结晶分离得Ti 2Zr 4O 4(OMc) 16。其中，Mc＝methacrylate。
图案化的光刻胶层的制备：
0.5g金属氧化物纳米粒子Ti 2Zr 4O 4(OMc) 16和0.05g光致产酸剂N-羟基萘酰亚胺三氟甲磺酸溶于9.45g溶剂丙二醇单甲醚醋酸酯，用孔径0.22μm的滤头过滤。将适量过滤后的光刻胶溶液滴在硅片表面，以2000r/min的转速匀胶，时间1分钟。在100℃烘干溶剂， 时间1分钟。用波长为254nm的低压汞灯曝光，曝光剂量为50mJ/cm 2，用甲苯显影，硅片表面用氮气吹干，分别用光学显微镜和扫描电子显微镜观察硅片表面的光刻图形，如图1和图2所示。
实施例2
以与实施例1相同的方法合成Ti 2Zr 4O 4(OMc) 16，区别仅在不对粗产物进行提纯，直接将0.5g金属氧化物纳米粒子Ti 2Zr 4O 4(OMc) 16与Ti(OBu) 2(acac) 2的混合物和0.05g光致产酸剂N-羟基萘酰亚胺三氟甲磺酸溶于9.45g溶剂丙二醇单甲醚醋酸酯，用孔径0.22μm的滤头过滤。将适量过滤后的光刻胶溶液滴在硅片表面，以2000r/min的转速匀胶，时间1分钟。在100℃烘干溶剂，时间1分钟。用波长为254nm的低压汞灯曝光，曝光剂量为20mJ/cm 2，用甲苯显影，硅片表面用氮气吹干，用扫描电子显微镜观察硅片表面的光刻图形，如图3所示。
实施例3
与实施例1基本相同，区别仅在光刻胶的组成：5g钛锆氧化物纳米粒子Ti 3Zr 5O 5(DMAA) 22，0.05g光致产酸剂N-羟基萘酰亚胺三氟甲磺酸，4.45g溶剂二氯甲烷。显影剂选自对甲苯、邻二甲苯和间二甲苯混合物。
实施例4
与实施例1基本相同，区别仅在光刻胶的组成：1g钛锆氧化物纳米粒子Ti 4Zr 3O 4(AA) 10(MAA) 10，0.1g光致产酸剂N-羟基邻苯酰亚胺对甲苯磺酸，8.9g溶剂氯仿。显影剂选自对二甲苯。
实施例5
与实施例1基本相同，区别仅在光刻胶的组成：2.5g钛锆氧化物纳米粒子Ti 2Zr 6O 6(AA) 10(DMAA) 10，0.08g光致产酸剂N-羟基萘酰亚胺三氟甲磺酸，7.42g溶剂二氯甲烷。显影剂选自对二甲苯。
实施例6
Ti 2Zr 4O 4(OMc) 16晶体合成与实施例1相同。
图案化的光刻胶层的制备：
电子束光刻：0.5g金属氧化物纳米粒子Ti 2Zr 4O 4(OMc) 16和0.05g光致产酸剂N-羟基萘酰亚胺三氟甲磺酸溶于9.45g溶剂丙二醇单甲醚醋酸酯，用孔径0.22μm的滤头过滤。将适量过滤后的光刻胶溶液滴在硅片表面，以2000r/min的转速匀胶，时间1分钟。在80℃烘干溶剂，时间1分钟。在电子束光刻机中曝光，剂量为1.8mC/cm 2，用丙二醇单甲醚醋 酸酯显影，硅片表面用氮气吹干，用扫描电子显微镜观察硅片表面的光刻图形，如图6所示。
实施例7
Ti 2Zr 4O 4(OMc) 16晶体合成与实施例1相同。
图案化的光刻胶层的制备：
极紫外光刻：0.5g金属氧化物纳米粒子Ti 2Zr 4O 4(OMc) 16和0.05g光致产酸剂N-羟基萘酰亚胺三氟甲磺酸溶于9.45g溶剂丙二醇单甲醚醋酸酯，用孔径0.22μm的滤头过滤。将适量过滤后的光刻胶溶液滴在硅片表面，以2000r/min的转速匀胶，时间1分钟。在80℃烘干溶剂，时间1分钟。利用极紫外干涉光刻曝光，剂量为77mJ/cm 2，用丙二醇单甲醚醋酸酯显影，硅片表面用氮气吹干，用扫描电子显微镜观察硅片表面的光刻图形，如图7所示。
对比例1
1g钛酸异丙酯与2.37g甲基丙烯酸混合，搅拌5分钟，加入2mL正丙醇，搅拌10分钟，加入1.23g水和2mL正丙醇，搅拌30分钟，除去溶剂后得到含Ti的纳米粒子TiOC。
0.5g金属氧化物纳米粒子TiOC和0.05g光致产酸剂N-羟基萘酰亚胺三氟甲磺酸溶于9.45g溶剂丙二醇单甲醚醋酸酯，用孔径0.22μm的滤头过滤。将适量过滤后的光刻胶溶液滴在硅片表面，以2000r/min的转速匀胶，时间1分钟。在100℃烘干溶剂，时间1分钟。用波长为254nm的低压汞灯曝光，曝光剂量为50mJ/cm 2，用甲苯显影，硅片表面用氮气吹干，用扫描电子显微镜观察硅片表面的光刻图形，如图4所示。
对比例2
与对比例1基本相同，区别仅在于曝光剂量为120mJ/cm 2。用扫描电子显微镜观察硅片表面的光刻图形，如图5所示。
从图1～图2和图6～图7可以看到实施例1中Ti 2Zr 4O 4(OMc) 16晶体配制的光刻胶分别通过合适剂量的254nm汞灯、电子束、极紫外光源曝光后，均可以得到高对比度，低线条边缘粗糙度和低线宽粗糙度的线条图形。其中通过电子束或极紫外光刻可以得到线宽在几十纳米的线条图形。从图3可以看到实施例2中Ti 2Zr 4O 4(OMc) 12与Ti(OBu) 2(acac) 2的混合物配制的光刻胶仍可得到分辨良好的线条图形，且具有更高的灵敏度。而从图4和图5可以看到对比例中的含Ti纳米粒子TiOC配制的光刻胶，通过紫外曝光后得到的线条图形对比度差(图4)，且存在线条图形薄膜溶胀导致的线条变形缺陷(线条上的白条)，剂量增大后无明显溶胀现象，但存在线条边缘粗糙的问题(图5)。
以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上所述实施例仅表达了本申请的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对申请专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本申请构思的前提下，还可以做出若干变形和改进，这些都属于本申请的保护范围。因此，本申请专利的保护范围应以所附权利要求为准。

Claims (18)

  1. 一种钛锆氧化物纳米粒子，其特征在于，所述钛锆氧化物纳米粒子的分子通式为Ti xZr yO zL n,其中，x、y、z分别独立地选自1～6中的任意整数，n选自5～30中的任意整数，L为有机物配体，所述有机物配体具有可自由基引发聚合的基团。
  2. 根据权利要求1所述的钛锆氧化物纳米粒子，其特征在于，所述钛锆氧化物纳米粒子的分子通式为Ti 2Zr 6O 6L 20、Ti 2Zr 4O 4L 16、Ti 2Zr 4O 5L 14或Ti 2Zr 4O 6L 12。
  3. 根据权利要求1或2所述的钛锆氧化物纳米粒子，其特征在于，所述钛锆氧化物纳米粒子在所述光刻胶中的质量百分数为1％～50％。
  4. 根据权利要求1～3任一项所述的钛锆氧化物纳米粒子，其特征在于，所述有机物配体为含有碳碳双键的有机物配体。
  5. 根据权利要求1～4任一项所述的钛锆氧化物纳米粒子，其特征在于，所述有机物配体选自丙烯酸、甲基丙烯酸和3,3-二甲基丙烯酸中的任意一种或多种。
  6. 一种光刻胶，包括根据权利要求1～5任一项所述的钛锆氧化物纳米粒子及有机溶剂。
  7. 根据权利要求6所述的光刻胶，其特征在于，还包括光致产酸剂，所述光致产酸剂能够在光照下分解形成光酸催化剂，所述光酸催化剂能够催化所述钛锆氧化物纳米粒子的团聚。
  8. 根据权利要求6或7所述的光刻胶，其特征在于，还包括光引发剂，所述光引发剂能够引发所述钛锆氧化物纳米粒子的团聚。
  9. 根据权利要求6～8任一项所述的光刻胶，其特征在于，所述有机溶剂选自丙二醇单甲醚醋酸酯、丙二醇乙醚、丙二醇单醋酸酯、乙二醇甲醚醋酸酯、乙酸乙酯、乙酸丁酯、氯仿及二氯甲烷中的任意一种或多种。
  10. 一种光刻胶，其特征在于，包括有机溶剂和钛锆氧化物纳米粒子，所述钛锆氧化物纳米粒子的分子通式为Ti 2Zr 6O 6L 20、Ti 2Zr 4O 4L 16、Ti 2Zr 4O 5L 14或Ti 2Zr 4O 6L 12，L为有机物配体，所述有机物配体具有可自由基引发聚合的基团。
  11. 根据权利要求10所述的光刻胶，其特征在于，所述有机物配体选自丙烯酸、甲基丙烯酸和3,3-二甲基丙烯酸中的任意一种或多种。
  12. 一种光刻胶组合产品，其特征在于，包括权利要求6～11任一项所述的光刻胶以及显影剂。
  13. 根据权利要求10所述的光刻胶组合产品，其特征在于，所述显影剂选自甲苯、邻二甲苯、间二甲苯、对二甲苯、均三甲苯、乙酸乙酯、乙酸丁酯、4-甲基-2-戊醇、4-甲基 -2-戊酮、甲基乙基酮、丙二醇单甲醚醋酸酯、丙二醇乙醚、丙二醇单醋酸酯、乙二醇甲醚醋酸酯、2-丁酮、2-庚酮、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、正己烷及环己烷中的任意一种或多种。
  14. 一种光刻胶的图案化方法，包括以下步骤：
    将权利要求6～11任一项所述光刻胶涂布在基底表面，除去所述光刻胶中的有机溶剂，在所述基底表面上形成预成膜层；
    将光源透过掩膜照射在所述基底的预成膜层上进行曝光操作，使得预成膜层的曝光区域形成钛锆氧化物纳米粒子团聚体；以及
    将显影剂施加在曝光后的预成膜层上，使得预成膜层上被掩膜遮挡的未曝光区域溶解于显影剂中，而预成膜层的曝光区域由于形成钛锆氧化物纳米粒子而保留在基底上。
  15. 根据权利要求14所述的光刻胶的图案化方法，其特征在于，所述曝光操作所用的光源为紫外、深紫外或极紫外光源，曝光剂量为4mJ/cm 2～1000mJ/cm 2。
  16. 根据权利要求14所述的光刻胶的图案化方法，其特征在于，所述曝光操作所用的光源为电子束源，剂量为10μC/cm 2～10mC/cm 2。
  17. 根据权利要求14～16任一项所述的光刻胶的图案化方法，其特征在于，所述基底选自硅板。
  18. 生成印刷电路板的方法，其特征在于，包括如下步骤：
    通过根据权利要求14～17任一项所述的光刻胶的图案化方法制备硅板基底上具有图案化光刻胶层的预图案化板材；以及
    利用干法或湿法刻蚀所述预图案化板材。
PCT/CN2021/136049 2020-12-09 2021-12-07 钛锆氧化物纳米粒子、光刻胶、光刻胶的图案化方法及生成印刷电路板的方法 WO2022121888A1 (zh)

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