WO2023246243A1 - 一种紫外光刻胶、紫外光刻胶图案化的方法及用途 - Google Patents

一种紫外光刻胶、紫外光刻胶图案化的方法及用途 Download PDF

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Publication number
WO2023246243A1
WO2023246243A1 PCT/CN2023/087668 CN2023087668W WO2023246243A1 WO 2023246243 A1 WO2023246243 A1 WO 2023246243A1 CN 2023087668 W CN2023087668 W CN 2023087668W WO 2023246243 A1 WO2023246243 A1 WO 2023246243A1
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Prior art keywords
ultraviolet
photoresist
exposure
wavelength
ethylene glycol
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PCT/CN2023/087668
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English (en)
French (fr)
Inventor
徐宏
何向明
刘天棋
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Beijing Vfortune New Energy Power Technology Development Co Ltd
Tsinghua University
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Beijing Vfortune New Energy Power Technology Development Co Ltd
Tsinghua University
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Priority claimed from CN202210701894.1A external-priority patent/CN117311087A/zh
Priority claimed from CN202210701897.5A external-priority patent/CN117311088A/zh
Application filed by Beijing Vfortune New Energy Power Technology Development Co Ltd, Tsinghua University filed Critical Beijing Vfortune New Energy Power Technology Development Co Ltd
Priority to KR1020247040304A priority Critical patent/KR20250005467A/ko
Priority to JP2024571260A priority patent/JP2025518845A/ja
Publication of WO2023246243A1 publication Critical patent/WO2023246243A1/zh
Anticipated expiration legal-status Critical
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    • 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
    • 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
    • G03F7/004—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
    • G03F7/16—Coating processes; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • 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

Definitions

  • the present invention relates to the technical field of photoresist, and specifically to an ultraviolet photoresist, a method and use of ultraviolet photoresist patterning.
  • Photolithography processing technology refers to a micro-nano processing technology that uses the change in solubility of photoresist under the exposure beam to transfer the pattern on the mask to the exposure substrate.
  • Photoresist is a type of hybrid material that is sensitive to light or radiation.
  • UV photoresist is mainly composed of film-forming resin, photosensitizer, solvent and other additives. Film-forming resin is the main component of photoresist.
  • the currently commercialized UV photoresist is a photosensitive material mainly based on polymer compounds as film-forming resins. It requires a large exposure dose and low sensitivity during use.
  • the present invention provides a UV photoresist with a small exposure dose and high sensitivity, a UV photoresist patterning method and use.
  • the present invention provides an ultraviolet photoresist, which includes an organic solvent, a photosensitizer and zirconium oxide nanoclusters.
  • the general chemical formula of the zirconium oxide nanoclusters is Zr x O y (OH) z L m , where 2 ⁇ x ⁇ 20, 2 ⁇ y ⁇ 40, 0 ⁇ z ⁇ 40, 4 ⁇ m ⁇ 40, L is an organic ligand containing carboxyl group;
  • the photosensitizer has the following structure:
  • R 1 is: * indicates the connection site.
  • R 2 and R 3 are independently selected from -F, -Cl, -Br or -I.
  • R 2 and R 3 are both -Cl.
  • the organic ligands containing carboxyl groups include acrylic acid ligands, methacrylate At least one of an acid ligand, a 1-hydroxy-2-naphthoic acid ligand and a salicylic acid ligand.
  • the mass percentage of zirconium oxide nanoclusters is 0.5% to 15%, and the mass percentage of the photosensitizer is 0.001% to 1 %.
  • the organic solvent includes at least one of ethyl lactate, anisole, propylene glycol monomethyl ether acetate, methyl isobutyl ketone and isopropyl alcohol.
  • the present invention also provides a method for patterning ultraviolet photoresist, which includes the following steps:
  • UV photoresist is spin-coated on the substrate, and then dried to form a UV photoresist film; the UV photoresist film is exposed to UV photolithography under a mask and then placed in a developer for development, to form photolithographic patterns.
  • the developer includes toluene, xylene, 1,2-diacetoxypropane, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, isopropyl alcohol, isobutanol, isopentyl Alcohol, 4-methyl-2-pentanol, isopropoxyethanol, 1-methoxy-2-propanol, 1-propoxy-2-propanol, 1-butoxy-2-propanol , at least one of ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, propylene glycol ethyl ether, 2-heptanone and 2-butanone.
  • the light source for UV photolithography exposure is ultraviolet light with a wavelength of 365 nm, deep ultraviolet light with a wavelength of 254 nm, or extreme ultraviolet light with a wavelength of 13.5 nm.
  • the exposure dose is greater than or equal to 7 mJ cm -2 ; when the light source for ultraviolet lithography exposure is ultraviolet light with a wavelength of 365 nm, the exposure dose is greater than or equal to 300 mJ cm -2 .
  • the ultraviolet photoresist as described above can also be used as the electron beam photoresist.
  • the present invention provides an ultraviolet photoresist, which includes an organic solvent, a photosensitizer and zirconium oxide nanoclusters.
  • the general chemical formula of the zirconium oxide nanoclusters is Zr x O y (OH) z L m , where 2 ⁇ x ⁇ 20, 2 ⁇ y ⁇ 40, 0 ⁇ z ⁇ 40, 4 ⁇ m ⁇ 40, L is an organic ligand containing carboxyl group;
  • the photosensitizer has the following structure:
  • R 1 is selected from Any one of them, * represents the connection site, and each occurrence of R 2 and R 3 is independently selected from -F, -Cl, -Br or -I.
  • R 2 and R 3 are both -Cl.
  • the organic ligands containing carboxyl groups include acrylic acid ligands, methacrylic acid ligands, 1-hydroxy-2-naphthoic acid ligands and salicylic acid ligands. at least one of the bases.
  • the mass percentage of zirconium oxide nanoclusters is 0.5% to 15%, and the mass percentage of the photosensitizer is 0.001% to 1 %.
  • the organic solvent includes at least one of ethyl lactate, anisole, propylene glycol monomethyl ether acetate, methyl isobutyl ketone and isopropyl alcohol.
  • the present invention also provides a method for patterning ultraviolet photoresist, which includes the following steps:
  • the UV photoresist film is exposed to UV photolithography under a mask and then developed in a developer to form a photolithography pattern. case.
  • the developer includes toluene, xylene, 1,2-diacetoxypropane, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, isopropyl alcohol, isobutanol, isopentyl Alcohol, 4-methyl-2-pentanol, isopropoxyethanol, 1-methoxy-2-propanol, 1-propoxy-2-propanol, 1-butoxy-2-propanol , at least one of ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, propylene glycol ethyl ether, 2-heptanone and 2-butanone.
  • the light source for UV photolithography exposure is ultraviolet light with a wavelength of 365 nm, deep ultraviolet light with a wavelength of 254 nm, or extreme ultraviolet light with a wavelength of 13.5 nm.
  • the exposure dose is greater than or equal to 12 mJ cm -2 ; when the light source for UV lithography exposure is ultraviolet light with a wavelength of 365 nm, the exposure dose is greater than or equal to 200 mJ cm -2 .
  • the UV photoresist of the present invention uses zirconium oxide nanoclusters as the film-forming resin, its single size is only 1 nm to 5 nm, which is much smaller than the size of the polymer chain (generally larger than 20 nm). Therefore, compared with traditional polymer resin-based photoresists, the ultraviolet photoresist of the present invention has the potential to photoetch patterns with smaller line widths.
  • the zirconium oxide nanocluster film-forming resin is effectively matched with the photosensitizer, the sensitivity of the UV photoresist is greatly improved and the exposure dose is significantly reduced, resulting in a significant increase in photolithography efficiency.
  • the presence of metal oxide makes the photoresist have excellent mechanical properties and etching resistance. The exposed pattern will hardly deform and peel off in the subsequent development process, and the pattern fidelity is high.
  • 1A and 1B are exposure patterns obtained by using an exposure wavelength of 254 nm in Example 1 of the present invention.
  • 2A and 2B are exposure patterns obtained by using an exposure wavelength of 365 nm in Example 1 of the present invention.
  • Figure 3 is an exposure pattern obtained by electron beam lithography exposure in Example 2 of the present invention.
  • 4A and 4B are exposure patterns obtained by using an exposure wavelength of 254 nm in Comparative Example 1 of the present invention.
  • 5A and 5B show the exposure pattern obtained by using the exposure wavelength of 365 nm in Comparative Example 1 of the present invention.
  • 6A and 6B are exposure patterns obtained by using an exposure wavelength of 254 nm in Example 3 of the present invention.
  • 7A and 7B are exposure patterns obtained by using an exposure wavelength of 365 nm in Example 3 of the present invention.
  • 8A and 8B are exposure patterns obtained by using an exposure wavelength of 254 nm in Example 4 of the present invention.
  • 9A and 9B are exposure patterns obtained by using an exposure wavelength of 365 nm in Example 4 of the present invention.
  • Figures 10A and 10B are exposure patterns obtained by using an exposure wavelength of 254 nm in Example 5 of the present invention.
  • 11A and 11B are exposure patterns obtained by using an exposure wavelength of 365 nm in Example 5 of the present invention.
  • 12A and 12B are exposure patterns obtained by using an exposure wavelength of 254 nm in Comparative Example 2 of the present invention.
  • 13A and 13B are the exposure patterns obtained by using the exposure wavelength of 365 nm in Comparative Example 2 of the present invention.
  • the "sensitivity" of photoresist refers to the minimum light energy or the minimum amount of charge (for electron beam glue) incident on a unit area that causes all photoresist reactions to occur.
  • the unit of UV photoresist sensitivity is expressed in mJ cm -2 (the smaller the value, the higher the photoresist sensitivity); the unit of electron beam photoresist sensitivity is expressed in ⁇ C cm -2 (the smaller the value, the higher the sensitivity of the photoresist). The higher the photoresist sensitivity).
  • the present invention provides an ultraviolet photoresist, which includes an organic solvent, a photosensitizer and zirconium oxide nanoclusters, wherein the general chemical formula of zirconium oxide nanoclusters is Zr x O y (OH) z L m , where 2 ⁇ x ⁇ 20, 2 ⁇ y ⁇ 40, 0 ⁇ z ⁇ 40, 4 ⁇ m ⁇ 40, L is an organic ligand containing carboxyl group;
  • the photosensitizer has the following structure:
  • R 1 is: * indicates the connection site
  • R 2 and R 3 are each independently selected from -F, -Cl, -Br or -I.
  • the photosensitizer in the UV photoresist has a high photolysis acid production efficiency.
  • the acid generated by photolysis can quickly trigger a chemical reaction of the zirconium oxide nanoclusters, making the UV photoresist highly sensitive, thus reducing the the exposure dose.
  • the UV photoresist of the present invention uses zirconium oxide nanoclusters as the film-forming resin, its single size is only 1 nm to 5 nm, which is much smaller than the size of the polymer chain (generally larger than 20 nm). Therefore, compared with traditional polymer resin-based photoresists, the ultraviolet photoresist of the present invention has the potential to photoetch patterns with smaller line widths.
  • the zirconium oxide nanocluster film-forming resin is effectively matched with the photosensitizer, the sensitivity of the UV photoresist is greatly improved and the exposure dose is significantly reduced, resulting in a significant increase in photolithography efficiency.
  • the presence of metal oxide makes the photoresist have excellent mechanical properties and etching resistance. The exposed pattern will hardly deform and peel off in the subsequent development process, and the pattern fidelity is high.
  • R 2 and R 3 are both -Cl.
  • organic ligands containing carboxyl groups include, but are not limited to, acrylic acid ligands, methacrylic acid ligands, 1-hydroxy-2-naphthoic acid ligands, salicylic acid ligands, and the like.
  • the mass percentage of zirconium oxide nanoclusters can be 0.5% to 15%, or 1%, 1.5%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 14.5%, etc.
  • the mass percentage of the photosensitizer in the organic solvent, can be 0.001% to 1%, or 0.002%, 0.003%, 0.005%, 0.006%, 0.008%, 0.01%, 0.02%, 0.05%, 0.08%, 0.1%, 0.12%, 0.15%, 0.3%, 0.5%, 0.8%, etc.
  • the organic solvent is a solvent with strong solubility for the photosensitizer and zirconium oxide nanoclusters, so that the photosensitizer and zirconium oxide nanoclusters can be better dissolved and uniformly dispersed in the organic solvent.
  • the organic solvent is any one commonly used in this field, including but not limited to ethyl lactate, anisole, propylene glycol monomethyl ether acetate, methyl isobutyl ketone, isopropyl alcohol, etc.
  • the present invention also provides a method for patterning ultraviolet photoresist, which includes the following steps:
  • the UV photoresist film is exposed to UV photolithography under a mask and then developed in a developer to form a photolithographic pattern.
  • developers include, but are not limited to, toluene, xylene, 1,2-diacetoxypropane, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, isopropyl alcohol, isobutanol , isoamyl alcohol, 4-methyl-2-pentanol, isopropoxyethanol, 1-methoxy-2-propanol, 1-propoxy-2-propanol, 1-butoxy-2 -At least one of propanol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, propylene glycol ethyl ether, 2-heptanone and 2-butanone.
  • the light source for UV lithography exposure is deep ultraviolet light with a wavelength of 254 nm or ultraviolet light with a wavelength of 365 nm.
  • the exposure dose can be greater than or equal to 7mJ cm -2 ; when the light source for UV lithography exposure is ultraviolet light with a wavelength of 365nm, the exposure dose can be greater than or equal to 300mJ cm -2 .
  • the above-mentioned UV photoresist can also be used as an electron beam photoresist.
  • the exposure dose can be as low as 120 ⁇ C cm -2 or less.
  • the substrate can be any substrate material commonly used in the art, such as silicon wafer, quartz wafer, glass wafer, etc.
  • a mask when forming a photolithography pattern, a mask needs to be applied to block light to form a UV photolithography pattern with a preset shape.
  • the present invention also provides an ultraviolet photoresist, which includes an organic solvent, a photosensitizer and zirconium oxide nanoclusters, wherein the general chemical formula of zirconium oxide nanoclusters is Zr x O y (OH) z L m , Among them, 2 ⁇ x ⁇ 20, 2 ⁇ y ⁇ 40, 0 ⁇ z ⁇ 40, 4 ⁇ m ⁇ 40, L is an organic ligand containing carboxyl group;
  • the photosensitizer has the following structure:
  • R 1 is an alkyl-substituted or unsubstituted furyl vinyl group or benzodioxolane group, and each occurrence of R 2 and R 3 is independently selected from -F, -Cl, -Br or -I.
  • the UV photoresist of the present invention uses zirconium oxide nanoclusters as the film-forming resin, its single size is only 1 nm to 5 nm, which is much smaller than the size of the polymer chain (generally larger than 20 nm). Therefore, compared with traditional polymer resin-based photoresists, the ultraviolet photoresist of the present invention has the potential to photoetch patterns with smaller line widths.
  • the zirconia nanocluster film-forming resin is effectively matched with the photosensitizer, the sensitivity of the UV photoresist is greatly improved and the exposure dose is significantly reduced, making the photolithography efficiency rate increased significantly.
  • the presence of metal oxide makes the photoresist have excellent mechanical properties and etching resistance. The exposed pattern will hardly deform and peel off in the subsequent development process, and the pattern fidelity is high.
  • R1 is selected from any one of the following groups:
  • * indicates the connection site.
  • R 2 and R 3 are both -Cl.
  • the photosensitizer is 2-(1,3-benzodioxolane-5-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2 -[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine and 2-[2-(5-methylfuran-2- (ethyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazines.
  • organic ligands containing carboxyl groups include, but are not limited to, acrylic acid ligands, methacrylic acid ligands, 1-hydroxy-2-naphthoic acid ligands, salicylic acid ligands, and the like.
  • the mass percentage of zirconium oxide nanoclusters can be 0.5% to 15%, or 1%, 1.5%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 14.5%, etc.
  • the mass percentage of the photosensitizer in the organic solvent, can be 0.001% to 1%, or 0.002%, 0.003%, 0.005%, 0.006%, 0.008%, 0.01%, 0.02%, 0.05%, 0.08%, 0.1%, 0.12%, 0.15%, 0.3%, 0.5%, 0.8%, etc.
  • the organic solvent is a solvent with strong solubility for the photosensitizer and zirconium oxide nanoclusters, so that the photosensitizer and zirconium oxide nanoclusters can be better dissolved and uniformly dispersed in the organic solvent.
  • the organic solvent is any one or more commonly used in the art, including but not limited to ethyl lactate, anisole, propylene glycol monomethyl ether acetate, methyl isobutyl ketone, isopropyl alcohol, etc.
  • the present invention also provides a method for patterning ultraviolet photoresist, which includes the following steps:
  • the UV photoresist film is exposed to UV photolithography under a mask and then developed in a developer to form a photolithography pattern.
  • developers include, but are not limited to, toluene, xylene, 1,2-diacetoxypropane, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, isopropyl alcohol, isobutanol , isoamyl alcohol, 4-methyl-2-pentanol, isopropoxyethanol, 1-methoxy-2-propanol, 1-propoxy-2-propanol, 1-butoxy-2 -At least one of propanol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, propylene glycol ethyl ether, 2-heptanone and 2-butanone.
  • the light source for UV lithography exposure is deep ultraviolet light with a wavelength of 254 nm or ultraviolet light with a wavelength of 365 nm.
  • the exposure dose can be greater than or equal to 12mJ cm -2 ; when the light source for UV lithography exposure is ultraviolet light with a wavelength of 365nm, the exposure dose can be greater than or equal to 200mJ cm -2 .
  • the substrate can be any substrate material commonly used in the art, such as silicon wafer, quartz wafer, glass wafer, etc.
  • a mask when forming a photolithography pattern, a mask needs to be applied to block light to form a UV photolithography pattern with a preset shape.
  • ultraviolet photoresist ultraviolet photoresist patterning method and application of the present invention will be further described in detail below with reference to specific embodiments.
  • the exposure doses are 7mJ cm -2 and 300mJ cm -2 respectively, and the development times are both 15s.
  • the UV exposure is completed, take out the base material and put it into 1,2-diacetoxypropane for development.
  • a nitrogen gun to blow dry the residual developer on the surface of the base material.
  • Use a metallographic microscope to observe the patterns obtained by photolithography exposure using light sources with wavelengths of 254 nm and 365 nm, as shown in Figures 1A, 1B, 2A, and 2B respectively.
  • the base material Take an appropriate amount of the prepared electron beam photoresist solution and drop it on the surface of the clean silicon wafer. Place the base material into a glue dispensing machine with a rotation speed of 2000 rpm and an acceleration of 500 rpm s -1 for 1 minute. Then take out the base material and put it into a glue drying machine to bake at 90°C for 1 minute. The base material is then placed into an electron beam lithography machine, and the electron beam is used as a light source for lithography exposure. When using electron beam as the light source for photolithography exposure, the exposure dose is 120 ⁇ C cm -2 and the development time is 25 s. After the electron beam exposure is completed, take out the base material and put it into 1,2-diacetoxypropane for development.
  • the pattern obtained by electron beam lithography exposure was observed using a high-resolution scanning electron microscope, as shown in Figure 3.
  • the resolution of the pattern obtained by this electron beam lithography exposure is 60nm.
  • the ultraviolet photoresist provided in Example 2 can be used for electron beam lithography, and a clear exposure pattern can be obtained.
  • the exposure dose can be as low as 120 ⁇ C cm -2 or less.
  • the exposure doses are 12mJ cm -2 and 200mJ cm -2 respectively, and the development time is 15s.
  • the UV exposure is completed, take out the base material and put it into 1,2-diacetoxypropane for development.
  • the development uses a nitrogen gun to blow dry the residual developer on the surface of the base material.
  • a metallographic microscope to observe the patterns obtained by photolithography exposure using light sources with wavelengths of 254 nm and 365 nm, as shown in Figures 6A and 6B and Figures 7A and 7B respectively.
  • the exposure doses are 54mJ cm -2 and 800mJ cm -2 respectively, and the development times are both 15s.
  • the UV exposure is completed, take out the base material and put it into 1,2-diacetoxypropane for development.
  • the development uses a nitrogen gun to blow dry the residual developer on the surface of the base material.
  • a metallographic microscope to observe the patterns obtained by photolithography exposure using light sources with wavelengths of 254 nm and 365 nm, as shown in Figures 8A and 8B and Figures 9A and 9B respectively.
  • the exposure doses are 72mJ cm -2 and 3600mJ cm -2 respectively, and the development time is 15s.
  • the UV exposure is completed, take out the base material and put it into 1,2-diacetoxypropane for development.
  • the development uses a nitrogen gun to blow dry the residual developer on the surface of the base material.
  • a metallographic microscope to observe the patterns obtained by photolithography exposure using light sources with wavelengths of 254 nm and 365 nm, as shown in Figures 10A, 10B, 11A, and 11B respectively.
  • the preparation method of this embodiment is basically the same as that of Example 1, except that the photosensitizer is 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3, 5-Triazine, exposure dose is different. Specific steps are as follows:
  • the exposure doses are 18mJ cm -2 and 400mJ cm -2 respectively, and the development times are both 15s.
  • the UV exposure is completed, take out the base material and put it into 1,2-diacetoxypropane for development.
  • the development uses a nitrogen gun to blow dry the residual developer on the surface of the base material.
  • a metallographic microscope to observe the patterns obtained by photolithography exposure using light sources with wavelengths of 254 nm and 365 nm, as shown in Figures 4A and 4B and Figures 5A and 5B respectively.
  • Example 1 selects 2-(4-methoxyphenyl)-4,6-bis( When trichloromethyl)-S-triazine acts as a photosensitizer with zirconium oxide nanoclusters, the exposure doses are 7mJ cm -2 and 300mJ cm -2 respectively; Comparative Example 1 selects 2-(4-methoxystyrene When methyl)-4,6-bis(trichloromethyl)-1,3,5-triazine was used as a photosensitizer to interact with zirconia nanoclusters, the exposure doses were 18mJ cm -2 and 400mJ cm -2 respectively.
  • Example 1 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-S-triazine is used as the photosensitizer and oxidation
  • the photosensitivity effect of zirconium nanoclusters is better, and the exposure dose is reduced by 61% and 25% respectively.
  • Embodiment 1 can significantly reduce the ultraviolet exposure dose of the photoresist and increase the photolithography speed.
  • the exposure doses are 144mJ cm -2 and 6000mJ cm -2 respectively, and the development time is 15s.
  • the UV exposure is completed, take out the base material and put it into 1,2-diacetoxypropane for development.
  • the development uses a nitrogen gun to blow dry the residual developer on the surface of the base material.
  • Use a metallographic microscope to observe the patterns obtained by photolithography exposure using light sources with wavelengths of 254 nm and 365 nm, as shown in Figures 12A and 12B and Figures 13A and 13B respectively.
  • Example 3-5 Under the condition that the exposure light source is ultraviolet light with wavelengths of 254nm and 365nm, 2-(1,3-benzodioxolane- 5-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloro Methyl)-1,3,5-triazine, 2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-1,3,5 -
  • the exposure doses are 12mJ cm -2 and 200mJ cm -2 , 54mJ cm -2 and 800mJ cm -2 , 72mJ cm -2 and 3600mJ cm -2 respectively;
  • Comparative Example 2 when a photosensitizer outside the limits of the exposure light source is ultraviolet light with wavelengths of 254nm and 365nm, 2-(1,3-benzodioxolane- 5-yl)
  • the zirconium oxide nanoclusters interact with the defined photosensitizer, which can significantly reduce the ultraviolet exposure dose of the photoresist and increase the photolithography speed.

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Abstract

一种紫外光刻胶、紫外光刻胶图案化的方法及用途。紫外光刻胶包括有机溶剂、光敏剂及氧化锆纳米团簇，氧化锆纳米团簇的化学通式为Zr xO y(OH) zL m，其中2≤x≤20，2≤y≤40，0≤z≤40，4≤m≤40，L为含有羧基的有机配体；光敏剂具有（I）所示结构，其中，R 1为（II），*表示连接位点；R 2及R 3每次出现分别独立地选自-F、-Cl、-Br或-I。光敏剂的选择能够大幅降低曝光剂量、提高光刻速度。

Description

一种紫外光刻胶、紫外光刻胶图案化的方法及用途
相关申请
本申请要求2022年06月21日申请的，申请号为202210701897.5，名称为“一种紫外光刻胶、紫外光刻胶图案化的方法及用途”的中国专利申请的优先权，以及要求2022年06月21日申请的，申请号为202210701894.1，名称为“一种紫外光刻胶及紫外光刻胶图案化的方法”的中国专利申请的优先权，在此将其原文引入作为参考。
技术领域
本发明涉及光刻胶技术领域，具体而言，涉及一种紫外光刻胶、紫外光刻胶图案化的方法及用途。
背景技术
现阶段，半导体行业中的极大规模集成电路均由光刻技术进行加工制造，光刻加工技术的分辨率和线宽直接决定了集成电路的集成度、良率和成本。光刻加工技术是指利用光刻胶在曝光光束下发生溶解度的变化，从而将掩膜版上的图形转移到曝光衬底上的一种微纳加工技术。光刻胶是一类对光或者射线敏感的混合材料，当前紫外光刻胶主要由成膜树脂、光敏剂、溶剂和其他一些添加剂等组成，其中成膜树脂是光刻胶的主体成分。
目前已商业化的紫外光刻胶是一种主要基于高分子化合物作为成膜树脂的感光材料，在使用过程中所需的曝光剂量较大、灵敏度较低。
技术问题
基于此，本发明提供了一种曝光剂量小、灵敏度高的紫外光刻胶、紫外光刻胶图案化的方法及用途。
技术解决方案
本发明一方面，提供一种紫外光刻胶，包括有机溶剂、光敏剂及氧化锆纳米团簇，所述氧化锆纳米团簇的化学通式为ZrxOy(OH)zLm，其中2≤x≤20，2≤y≤40，0≤z≤40，4≤m≤40，L为含有羧基的有机配体；
所述光敏剂具有如下所示结构：
其中，如上述所述的紫外光刻胶，R1为：*表示连接位点。
R2及R3每次出现分别独立地选自-F、-Cl、-Br或-I。
可选的，如上述所述的紫外光刻胶，R2及R3均为-Cl。
可选的，如上述所述的紫外光刻胶，含有羧基的有机配体包括丙烯酸配位基、甲基丙烯 酸配位基、1-羟基-2-萘甲酸配位基及水杨酸配位基中的至少一种。
可选的，如上述所述的紫外光刻胶，在所述有机溶剂中，氧化锆纳米团簇的质量百分含量为0.5％～15％，光敏剂的质量百分含量为0.001％～1％。
可选的，如上述所述的紫外光刻胶，有机溶剂包括乳酸乙酯、苯甲醚、丙二醇单甲醚醋酸酯、甲基异丁酮及异丙醇中的至少一种。
本发明另一方面，还提供一种紫外光刻胶图案化的方法，包括以下步骤：
将上述所述的紫外光刻胶旋涂于基底上，之后干燥形成紫外光刻胶膜；将所述紫外光刻胶膜在掩膜版下进行紫外光刻曝光后置于显影剂中显影，以形成光刻图案。
可选的，所述显影剂包括甲苯、二甲苯、1,2-二乙酰氧基丙烷、丙二醇单甲醚醋酸酯、乙二醇单丁醚醋酸酯、异丙醇、异丁醇、异戊醇、4-甲基-2-戊醇、异丙氧基乙醇、1-甲氧基-2-丙醇、1-丙氧基-2-丙醇、1-丁氧基-2-丙醇、乙二醇甲醚、乙二醇乙醚、乙二醇丙醚、乙二醇丁醚、丙二醇乙醚、2-庚酮及2-丁酮中的至少一种。
可选的，如上述所述的紫外光刻胶图案化的方法，紫外光刻曝光的光源为365nm波长的紫外光、254nm波长的深紫外光或13.5nm波长的极紫外光。进一步地，紫外光刻曝光的光源为254nm波长的深紫外光时，曝光剂量大于等于7mJ cm-2；紫外光刻曝光的光源为365nm波长的紫外光时，曝光剂量大于等于300mJ cm-2。
可选的，如上述所述的紫外光刻胶也可以作为电子束光刻胶。
本发明一方面，提供一种紫外光刻胶，包括有机溶剂、光敏剂及氧化锆纳米团簇，所述氧化锆纳米团簇的化学通式为ZrxOy(OH)zLm，其中2≤x≤20，2≤y≤40，0≤z≤40，4≤m≤40，L为含有羧基的有机配体；
所述光敏剂具有如下所示结构：
其中，R1选自中任意一种，*表示连接位点，R2及R3每次出现分别独立地选自-F、-Cl、-Br或-I。
可选的，如上述所述的紫外光刻胶，R2及R3均为-Cl。
可选的，如上述所述的紫外光刻胶，含有羧基的有机配体包括丙烯酸配位基、甲基丙烯酸配位基、1-羟基-2-萘甲酸配位基及水杨酸配位基中的至少一种。
可选的，如上述所述的紫外光刻胶，在所述有机溶剂中，氧化锆纳米团簇的质量百分含量为0.5％～15％，光敏剂的质量百分含量为0.001％～1％。
可选的，如上述所述的紫外光刻胶，有机溶剂包括乳酸乙酯、苯甲醚、丙二醇单甲醚醋酸酯、甲基异丁酮及异丙醇中的至少一种。
本发明另一方面，还提供一种紫外光刻胶图案化的方法，包括以下步骤：
将上述所述的紫外光刻胶旋涂于基底上，之后干燥形成紫外光刻胶膜；
将所述紫外光刻胶膜在掩膜版下进行紫外光刻曝光后置于显影剂中显影，以形成光刻图案。
可选的，所述显影剂包括甲苯、二甲苯、1,2-二乙酰氧基丙烷、丙二醇单甲醚醋酸酯、乙二醇单丁醚醋酸酯、异丙醇、异丁醇、异戊醇、4-甲基-2-戊醇、异丙氧基乙醇、1-甲氧基-2-丙醇、1-丙氧基-2-丙醇、1-丁氧基-2-丙醇、乙二醇甲醚、乙二醇乙醚、乙二醇丙醚、乙二醇丁醚、丙二醇乙醚、2-庚酮及2-丁酮中的至少一种。
可选的，如上述所述的紫外光刻胶图案化的方法，紫外光刻曝光的光源为365nm波长的紫外光、254nm波长的深紫外光或13.5nm波长的极紫外光。进一步地，紫外光刻曝光的光源为254nm波长的深紫外光时，曝光剂量大于等于12mJ cm-2；紫外光刻曝光的光源为365nm波长的紫外光时，曝光剂量大于等于200mJ cm-2。
有益效果
本发明的紫外光刻胶因采用氧化锆纳米团簇作为成膜树脂，其单一尺度仅为1nm-5nm，远小于高分子链的尺寸(一般大于20nm)。因此，相较于传统的高分子树脂型光刻胶，本发明的紫外光刻胶具有光刻出更小线宽图形的潜力。氧化锆纳米团簇成膜树脂在与光敏剂进行有效匹配后，紫外光刻胶的灵敏度得到了大幅度提高、曝光剂量大幅度下降，使得光刻效率大幅度提升。并且金属氧化物的存在使得光刻胶的力学性能和抗刻蚀性能优异，曝光图案在后续的显影工艺中几乎不发生变形和剥离，图案保真度高。
附图说明
图1A和图1B为本发明实施例1中曝光波长为254nm所得的曝光图案。
图2A和图2B为本发明实施例1中曝光波长为365nm所得的曝光图案。
图3为本发明实施例2中电子束光刻曝光所得的曝光图案。
图4A和图4B为本发明对比例1中曝光波长为254nm所得的曝光图案。
图5A和图5B为本发明对比例1中曝光波长为365nm所得的曝光图案。
图6A和图6B为本发明实施例3中曝光波长为254nm所得的曝光图案。
图7A和图7B为本发明实施例3中曝光波长为365nm所得的曝光图案。
图8A和图8B为本发明实施例4中曝光波长为254nm所得的曝光图案。
图9A和图9B为本发明实施例4中曝光波长为365nm所得的曝光图案。
图10A和图10B为本发明实施例5中曝光波长为254nm所得的曝光图案。
图11A和图11B为本发明实施例5中曝光波长为365nm所得的曝光图案。
图12A和图12B为本发明对比例2中曝光波长为254nm所得的曝光图案。
图13A和图13B为本发明对比例2中曝光波长为365nm所得的曝光图案。
本发明的实施方式
现将详细地提供本发明实施方式的参考，其一个或多个实例描述于下文。提供每一实例作为解释而非限制本发明。实际上，对本领域技术人员而言，显而易见的是，可以对本发明进行多种修改和变化而不背离本发明的范围或精神。例如，作为一个实施方式的部分而说明或描述的特征可以用于另一实施方式中，来产生更进一步的实施方式。
因此，旨在本发明覆盖落入所附权利要求的范围及其等同范围中的此类修改和变化。本发明的其它对象、特征和方面公开于以下详细描述中或从中是显而易见的。本领域普通技术人员应理解本讨论仅是示例性实施方式的描述，而非意在限制本发明更广阔的方面。
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发明的技术领域的技术人员通常理解的含义相同。本文中在本发明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，不是旨在于限制本发明。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。本文中所用的术语“包含”、“包括”、“具有”、“含有”或其任何其它变形，意在覆盖非排它性的包括。例如，包含所列要素的组合物、步骤、方法、制品或装置不必仅限于那些要素，而是可以包括未明确列出的其它要素或此种组合物、步骤、方法、制品或装置所固有的要素。
除了在操作实施例中所示以外或另外表明之外，所有在说明书和权利要求中表示成分的量、物化性质等所使用的数字理解为在所有情况下通过术语“约”来调整。例如，因此，除非有相反的说明，否则上述说明书和所附权利要求书中列出的数值参数均是近似值，本领域的技术人员能够利用本文所公开的教导内容寻求获得的所需特性，适当改变这些近似值。用端点表示的数值范围的使用包括该范围内的所有数字以及该范围内的任何范围，例如，1至5包括1、1.1、1.3、1.5、2、2.75、3、3.80、4和5等等。
光刻胶“灵敏度”是指：单位面积上入射的使光刻胶全部发生反应的最小光能量或最小电荷量(对电子束胶)。本发明中，紫外光刻胶灵敏度的单位用mJ cm-2表示(数值越小，其光刻胶灵敏度越高)；电子束光刻胶灵敏度的单位用μC cm-2表示(数值越小，其光刻胶灵敏度越高)。光刻胶灵敏度也可以用最小曝光剂量来反映，曝光剂量＝光强×曝光时间。
本发明一方面，提供一种紫外光刻胶，包括有机溶剂、光敏剂及氧化锆纳米团簇，其中氧化锆纳米团簇的化学通式为ZrxOy(OH)zLm，其中2≤x≤20，2≤y≤40，0≤z≤40，4≤m≤40，L为含有羧基的有机配体；
所述光敏剂具有如下所示结构：
其中，R1为：*表示连接位点；
R2及R3分别独立地选自-F、-Cl、-Br或-I。
所述紫外光刻胶中的光敏剂具有很高的光解产酸效率，光解产生的酸能够快速引发氧化锆纳米团簇发生化学反应，使得紫外光刻胶具有很高的灵敏度，从而降低了曝光剂量。
本发明的紫外光刻胶因采用氧化锆纳米团簇作为成膜树脂，其单一尺度仅为1nm-5nm，远小于高分子链的尺寸(一般大于20nm)。因此，相较于传统的高分子树脂型光刻胶，本发明的紫外光刻胶具有光刻出更小线宽图形的潜力。氧化锆纳米团簇成膜树脂在与光敏剂进行有效匹配后，紫外光刻胶的灵敏度得到了大幅度提高、曝光剂量大幅度下降，使得光刻效率大幅度提升。并且金属氧化物的存在使得光刻胶的力学性能和抗刻蚀性能优异，曝光图案在后续的显影工艺中几乎不发生变形和剥离，图案保真度高。
在一些实施方式中，R2及R3均为-Cl。
在一些实施方式中，含有羧基的有机配体包括但不限于丙烯酸配位基、甲基丙烯酸配位基、1-羟基-2-萘甲酸配位基、水杨酸配位基等。
在一些实施方式中，在有机溶剂中，氧化锆纳米团簇的质量百分含量可以为0.5％～15％，还可以为1％、1.5％、2％、3％、4％、5％、6％、7％、8％、9％、10％、11％、12％、13％、14％、14.5％等。
在一些实施方式中，在有机溶剂中，光敏剂的质量百分含量可以为0.001％～1％，还可以为0.002％、0.003％、0.005％、0.006％、0.008％、0.01％、0.02％、0.05％、0.08％、0.1％、0.12％、0.15％、0.3％、0.5％、0.8％等。
在一些实施方式中，有机溶剂选用对光敏剂及氧化锆纳米团簇有较强溶解性的溶剂，以使光敏剂及氧化锆纳米团簇能够较好的溶解并均匀分散于有机溶剂中。将紫外光刻胶旋涂于基底上并干燥形成紫外光刻胶膜后，可以保证光敏剂及氧化锆纳米团簇能够均匀分散于紫外光刻胶膜中。在光刻曝光后，紫外光刻胶曝光区难以溶解于显影剂中，而紫外光刻胶非曝光区能够准确快速溶解。优选的，有机溶剂为本领域常用的任意一种即可，包括但不限于乳酸乙酯、苯甲醚、丙二醇单甲醚醋酸酯、甲基异丁酮及异丙醇等。
本发明另一方面，还提供一种紫外光刻胶图案化的方法，包括以下步骤：
将上述所述的紫外光刻胶旋涂于基底上，之后干燥形成紫外光刻胶膜；
将所述紫外光刻胶膜在掩膜版下进行紫外光刻曝光后置于显影剂中显影，以形成光刻图案。
在一些实施方式中，显影剂包括但不限于甲苯、二甲苯、1,2-二乙酰氧基丙烷、丙二醇单甲醚醋酸酯、乙二醇单丁醚醋酸酯、异丙醇、异丁醇、异戊醇、4-甲基-2-戊醇、异丙氧基乙醇、1-甲氧基-2-丙醇、1-丙氧基-2-丙醇、1-丁氧基-2-丙醇、乙二醇甲醚、乙二醇乙醚、乙二醇丙醚、乙二醇丁醚、丙二醇乙醚、2-庚酮及2-丁酮中的至少一种。
在一些实施方式中，紫外光刻曝光的光源为254nm波长的深紫外光或365nm波长的紫外光。紫外光刻曝光的光源为254nm波长的深紫外光时，曝光剂量可以大于等于7mJ cm-2；紫外光刻曝光的光源为365nm波长的紫外光时，曝光剂量可以大于等于300mJ cm-2。
在一些实施方式中，上述的紫外光刻胶还可以作为电子束光刻胶，使用电子束作为光源进行光刻曝光时，曝光剂量可以低至120μC cm-2以下。
在一些实施方式中，基底可以选用本领域常用的任意一种基底材料，例如硅晶片、石英片、玻璃片等。
在一些实施方式中，在形成光刻图案时，需要施加掩膜版对光线进行遮挡，以形成具有预设形状的紫外光刻图案。
本发明另一方面，还提供一种紫外光刻胶，包括有机溶剂、光敏剂及氧化锆纳米团簇，其中氧化锆纳米团簇的化学通式为ZrxOy(OH)zLm，其中2≤x≤20，2≤y≤40，0≤z≤40，4≤m≤40，L为含有羧基的有机配体；
所述光敏剂具有如下所示结构：
其中，R1为烷基取代或未取代的呋喃乙烯基或苯并二氧戊环基，R2及R3每次出现分别独立地选自-F、-Cl、-Br或-I。
本发明的紫外光刻胶因采用氧化锆纳米团簇作为成膜树脂，其单一尺度仅为1nm-5nm，远小于高分子链的尺寸(一般大于20nm)。因此，相较于传统的高分子树脂型光刻胶，本发明的紫外光刻胶具有光刻出更小线宽图形的潜力。氧化锆纳米团簇成膜树脂在与光敏剂进行有效匹配后，紫外光刻胶的灵敏度得到了大幅度提高、曝光剂量大幅度下降，使得光刻效 率大幅度提升。并且金属氧化物的存在使得光刻胶的力学性能和抗刻蚀性能优异，曝光图案在后续的显影工艺中几乎不发生变形和剥离，图案保真度高。
在一些实施方式中，R1选自以下基团中的任意一种：
其中，*表示连接位点。
在一些实施方式中，R2及R3均为-Cl。
在一些实施方式中，光敏剂为2-(1,3-苯并二氧戊环-5-基)-4,6-双(三氯甲基)-1,3,5-三嗪、2-[2-(呋喃-2-基)乙烯基]-4,6-双(三氯甲基)-1,3,5-三嗪及2-[2-(5-甲基呋喃-2-基)乙烯基]-4,6-双(三氯甲基)-1,3,5-三嗪中的一种或多种。
在一些实施方式中，含有羧基的有机配体包括但不限于丙烯酸配位基、甲基丙烯酸配位基、1-羟基-2-萘甲酸配位基、水杨酸配位基等。
在一些实施方式中，在有机溶剂中，氧化锆纳米团簇的质量百分含量可以为0.5％～15％，还可以为1％、1.5％、2％、3％、4％、5％、6％、7％、8％、9％、10％、11％、12％、13％、14％、14.5％等。
在一些实施方式中，在有机溶剂中，光敏剂的质量百分含量可以为0.001％～1％，还可以为0.002％、0.003％、0.005％、0.006％、0.008％、0.01％、0.02％、0.05％、0.08％、0.1％、0.12％、0.15％、0.3％、0.5％、0.8％等。
在一些实施方式中，有机溶剂选用对光敏剂及氧化锆纳米团簇有较强溶解性的溶剂，以使光敏剂及氧化锆纳米团簇能够较好的溶解并均匀分散于有机溶剂中。将紫外光刻胶旋涂于基底上并干燥形成紫外光刻胶膜后，可以保证光敏剂及氧化锆纳米团簇能够均匀分散于紫外光刻胶膜中。在光刻曝光后，紫外光刻胶曝光区难以溶解于显影剂中，而紫外光刻胶非曝光区能够准确快速溶解。优选的，有机溶剂为本领域常用的任意一种或多种即可，包括但不限于乳酸乙酯、苯甲醚、丙二醇单甲醚醋酸酯、甲基异丁酮及异丙醇等。
本发明另一方面，还提供一种紫外光刻胶图案化的方法，包括以下步骤：
将上述所述的紫外光刻胶旋涂于基底上，之后干燥形成紫外光刻胶膜；
将所述紫外光刻胶膜在掩膜版下进行紫外光刻曝光后置于显影剂中显影，以形成光刻图案。
在一些实施方式中，显影剂包括但不限于甲苯、二甲苯、1,2-二乙酰氧基丙烷、丙二醇单甲醚醋酸酯、乙二醇单丁醚醋酸酯、异丙醇、异丁醇、异戊醇、4-甲基-2-戊醇、异丙氧基乙醇、1-甲氧基-2-丙醇、1-丙氧基-2-丙醇、1-丁氧基-2-丙醇、乙二醇甲醚、乙二醇乙醚、乙二醇丙醚、乙二醇丁醚、丙二醇乙醚、2-庚酮及2-丁酮中的至少一种。
在一些实施方式中，紫外光刻曝光的光源为254nm波长的深紫外光或365nm波长的紫外光。紫外光刻曝光的光源为254nm波长的深紫外光时，曝光剂量可以大于等于12mJ cm-2；紫外光刻曝光的光源为365nm波长的紫外光时，曝光剂量可以大于等于200mJ cm-2。
在一些实施方式中，基底可以选用本领域常用的任意一种基底材料，例如硅晶片、石英片、玻璃片等。
在一些实施方式中，在形成光刻图案时，需要施加掩膜版对光线进行遮挡，以形成具有预设形状的紫外光刻图案。
以下结合具体实施例对本发明的紫外光刻胶、紫外光刻胶图案化的方法及用途作进一步详细的说明。
实施例1
分别取0.03g 2-(4-甲氧基苯基)-4,6-双(三氯甲基)-S-三嗪和0.75g氧化锆纳米团簇(Zr6O4(OH)4(CH2＝CCH3COO)12)溶于14.25g丙二醇单甲醚醋酸酯溶剂中，搅拌使其完全溶解。随后利用孔径为0.22μm的滤膜将紫外光刻胶溶液过滤两次。过滤完毕后，将紫外光刻胶溶液装于棕色玻璃瓶中，并于室温环境下避光保存。
取适量制备好的紫外光刻胶溶液滴于干净的硅晶片表面，将基底材料放入转速为2000rpm，加速度为500rpm s-1的匀胶机中匀胶1min。随后取出基底材料，放入烘胶机中于90℃烘1min。随后将基底材料放入紫外接触式光刻机中，并施加掩膜版，分别使用254nm和365nm波长的紫外光作为光源进行光刻曝光。使用254nm和365nm波长的紫外光作为光源进行光刻曝光时，曝光剂量分别为7mJ cm-2和300mJ cm-2，显影时间均为15s。紫外曝光结束后，取出基底材料，放入1,2-二乙酰氧基丙烷中显影，显影结束后用氮气枪将基底材料表面的残余显影剂吹干。利用金相显微镜观察254nm和365nm波长的光源光刻曝光所得图案，分别如图1A、图1B以及图2A、图2B所示。
实施例2
分别取0.01g 2-(4-甲氧基苯基)-4,6-双(三氯甲基)-S-三嗪和0.5g氧化锆纳米团簇(Zr6O4(OH)4(CH2＝CCH3COO)12)溶于9.5g丙二醇单甲醚醋酸酯溶剂中，搅拌使其完全溶解。随后利用孔径为0.22μm的滤膜将电子束光刻胶溶液过滤两次。过滤完毕后，将电子束光刻胶溶液装于棕色玻璃瓶中，并于室温环境下避光保存。
取适量制备好的电子束光刻胶溶液滴于干净的硅晶片表面，将基底材料放入转速为2000rpm，加速度为500rpm s-1的匀胶机中匀胶1min。随后取出基底材料，放入烘胶机中于90℃烘1min。随后将基底材料放入电子束光刻机中，使用电子束作为光源进行光刻曝光。使用电子束作为光源进行光刻曝光时，曝光剂量为120μC cm-2，显影时间为25s。电子束曝光结束后，取出基底材料，放入1,2-二乙酰氧基丙烷中显影，显影结束后用氮气枪将基底材料表面的残余显影剂吹干。利用高分辨扫描电子显微镜观察电子束光刻曝光所得图案，如图3所示。该电子束光刻曝光所得图案的分辨率为60nm。
可以看出，实施例2所提供的紫外光刻胶可用于电子束光刻，并获得清晰的曝光图案，使用电子束作为光源进行光刻曝光时，曝光剂量可以低至120μC cm-2以下。
实施例3
分别取0.03g 2-(1,3-苯并二氧戊环-5-基)-4,6-双(三氯甲基)-1,3,5-三嗪和0.75g氧化锆纳米团簇(Zr6O4(OH)4(CH2＝CCH3COO)12)溶于14.25g丙二醇单甲醚醋酸酯溶剂中，搅拌使其完全溶解。随后利用孔径为0.22μm的滤膜将紫外光刻胶溶液过滤两次。过滤完毕后，将紫外光刻胶溶液装于棕色玻璃瓶中，并于室温环境下避光保存。
取适量制备好的紫外光刻胶溶液滴于干净的硅晶片表面，将基底材料放入转速为2000rpm，加速度为500rpm s-1的匀胶机中匀胶1min。随后取出基底材料，放入烘胶机中于90℃烘1min。随后将基底材料放入紫外接触式光刻机中，并施加掩膜版，分别使用254nm和365nm波长的紫外光作为光源进行光刻曝光。使用254nm和365nm波长的紫外光作为光源进行光刻曝光时，曝光剂量分别为12mJ cm-2和200mJ cm-2，显影时间均为15s。紫外曝光结束后，取出基底材料，放入1,2-二乙酰氧基丙烷中显影，显影结束后用氮气枪将基底材料表面的残余显影剂吹干。利用金相显微镜观察254nm和365nm波长的光源光刻曝光所得图案，分别如图6A、图6B和图7A、图7B所示。
实施例4
分别取0.03g 2-[2-(呋喃-2-基)乙烯基]-4,6-双(三氯甲基)-1,3,5-三嗪和0.75g氧化锆纳米团簇(Zr6O4(OH)4(CH2＝CCH3COO)12)溶于14.25g丙二醇单甲醚醋酸酯溶剂中，搅拌使其完全溶解。随后利用孔径为0.22μm的滤膜将紫外光刻胶溶液过滤两次。过滤完毕后，将紫外光刻胶溶液装于棕色玻璃瓶中，并于室温环境下避光保存。
取适量制备好的紫外光刻胶溶液滴于干净的硅晶片表面，将基底材料放入转速为2000rpm，加速度为500rpm s-1的匀胶机中匀胶1min。随后取出基底材料，放入烘胶机中于90℃烘1min。随后将基底材料放入紫外接触式光刻机中，并施加掩膜版，分别使用254nm和365nm波长的紫外光作为光源进行光刻曝光。使用254nm和365nm波长的紫外光作为光源进行光刻曝光时，曝光剂量分别为54mJ cm-2和800mJ cm-2，显影时间均为15s。紫外曝光结束后，取出基底材料，放入1,2-二乙酰氧基丙烷中显影，显影结束后用氮气枪将基底材料表面的残余显影剂吹干。利用金相显微镜观察254nm和365nm波长的光源光刻曝光所得图案，分别如图8A、图8B和图9A、图9B所示。
实施例5
分别取0.03g 2-[2-(5-甲基呋喃-2-基)乙烯基]-4,6-双(三氯甲基)-1,3,5-三嗪和0.75g氧化锆纳米团簇(Zr6O4(OH)4(CH2＝CCH3COO)12)溶于14.25g丙二醇单甲醚醋酸酯溶剂中，搅拌使其完全溶解。随后利用孔径为0.22μm的滤膜将紫外光刻胶溶液过滤两次。过滤完毕后，将紫外光刻胶溶液装于棕色玻璃瓶中，并于室温环境下避光保存。
取适量制备好的紫外光刻胶溶液滴于干净的硅晶片表面，将基底材料放入转速为2000rpm，加速度为500rpm s-1的匀胶机中匀胶1min。随后取出基底材料，放入烘胶机中于90℃烘1min。随后将基底材料放入紫外接触式光刻机中，并施加掩膜版，分别使用254nm和365nm波长的紫外光作为光源进行光刻曝光。使用254nm和365nm波长的紫外光作为光源进行光刻曝光时，曝光剂量分别为72mJ cm-2和3600mJ cm-2，显影时间均为15s。紫外曝光结束后，取出基底材料，放入1,2-二乙酰氧基丙烷中显影，显影结束后用氮气枪将基底材料表面的残余显影剂吹干。利用金相显微镜观察254nm和365nm波长的光源光刻曝光所得图案，分别如图10A、图10B和图11A、图11B所示。
对比例1
本实施例与实施例1的制备方法基本相同，不同之处在于：光敏剂为2-(4-甲氧基苯乙烯基)-4,6-双(三氯甲基)-1,3,5-三嗪、曝光剂量不同。具体步骤如下：
分别取0.03g 2-(4-甲氧基苯乙烯基)-4,6-双(三氯甲基)-1,3,5-三嗪和0.75g氧化锆纳米团簇(Zr6O4(OH)4(CH2＝CCH3COO)12)溶于14.25g丙二醇单甲醚醋酸酯溶剂中，搅拌使其完全溶解。随后利用孔径为0.22μm的滤膜将紫外光刻胶溶液过滤两次。过滤完毕后，将紫外光刻胶溶液装于棕色玻璃瓶中，并于室温环境下避光保存。
取适量制备好的紫外光刻胶溶液滴于干净的硅晶片表面，将基底材料放入转速为2000rpm，加速度为500rpm s-1的匀胶机中匀胶1min。随后取出基底材料，放入烘胶机中于90℃烘1min。随后将基底材料放入紫外接触式光刻机中，并施加掩膜版，分别使用254nm和365nm波长的紫外光作为光源进行光刻曝光。使用254nm和365nm波长的紫外光作为光源进行光刻曝光时，曝光剂量分别为18mJ cm-2和400mJ cm-2，显影时间均为15s。紫外曝光结束后，取出基底材料，放入1,2-二乙酰氧基丙烷中显影，显影结束后用氮气枪将基底材料表面的残余显影剂吹干。利用金相显微镜观察254nm和365nm波长的光源光刻曝光所得图案，分别如图4A、图4B和图5A、图5B所示。
从上述实施例1和对比例1可以看出，在曝光光源为254nm和365nm波长的紫外光的条件下，实施例1选用2-(4-甲氧基苯基)-4,6-双(三氯甲基)-S-三嗪作为光敏剂与氧化锆纳米团簇作用时，曝光剂量分别为7mJ cm-2和300mJ cm-2；对比例1选用2-(4-甲氧基苯乙烯基)-4,6-双(三氯甲基)-1,3,5-三嗪作为光敏剂与氧化锆纳米团簇作用时，曝光剂量分别为18mJ cm-2和400mJ cm-2。由此可得，与对比例1相较，实施例1中将2-(4-甲氧基苯基)-4,6-双(三氯甲基)-S-三嗪作为光敏剂与氧化锆纳米团簇作用的感光效果更好，曝光剂量分别降低了61％和25％，实施例1能够大幅降低光刻胶的紫外曝光剂量、提高光刻速度。
对比例2
分别取0.03g N-羟基萘酰亚胺三氟甲磺酸酯和0.75g氧化锆纳米团簇(Zr6O4(OH)4(CH2＝CCH3COO)12)溶于14.25g丙二醇单甲醚醋酸酯溶剂中，搅拌使其完全溶解。随后利用孔径为0.22μm的滤膜将紫外光刻胶溶液过滤两次。过滤完毕后，将紫外光刻胶溶液装于棕色玻璃瓶中，并于室温环境下避光保存。
取适量制备好的紫外光刻胶溶液滴于干净的硅晶片表面，将基底材料放入转速为2000rpm，加速度为500rpm s-1的匀胶机中匀胶1min。随后取出基底材料，放入烘胶机中于90℃烘1min。随后将基底材料放入紫外接触式光刻机中，并施加掩膜版，分别使用254nm和365nm波长的紫外光作为光源进行光刻曝光。使用254nm和365nm波长的紫外光作为光源进行光刻曝光时，曝光剂量分别为144mJ cm-2和6000mJ cm-2，显影时间均为15s。紫外曝光结束后，取出基底材料，放入1,2-二乙酰氧基丙烷中显影，显影结束后用氮气枪将基底材料表面的残余显影剂吹干。利用金相显微镜观察254nm和365nm波长的光源光刻曝光所得图案，分别如图12A、图12B和图13A、图13B所示。
从上述实施例3-5和对比例2可以看出，在曝光光源为254nm和365nm波长的紫外光的条件下，实施例3-5选用2-(1,3-苯并二氧戊环-5-基)-4,6-双(三氯甲基)-1,3,5-三嗪、2-[2-(呋喃-2-基)乙烯基]-4,6-双(三氯甲基)-1,3,5-三嗪、2-[2-(5-甲基呋喃-2-基)乙烯基]-4,6-双(三氯甲基)-1,3,5-三嗪分别作为光敏剂与氧化锆纳米团簇作用时，曝光剂量分别为12mJ cm-2和200mJ cm-2、54mJ cm-2和800mJ cm-2、72mJ cm-2和3600mJ cm-2；对比例2中，当选用本发明限定之外的光敏剂与氧化锆纳米团簇反应时，曝光剂量分别为144mJ cm-2和6000mJ cm-2。由此可得，本发明实施例提供的紫外光刻胶，在曝光过程中，氧化锆纳米团簇与限定的光敏剂相互作用，能够大幅降低光刻胶的紫外曝光剂量、提高光刻速度。
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发明的几种实施方式，其描述较为具体和详细，但并不能因此而理解为对发明专利范围的限制。应当指出的是，对于本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进，这些都属于本发明的保护范围。因此，本发明专利的保护范围应以所附权利要求为准。

Claims (21)

  1. 一种紫外光刻胶，其特征在于，包括有机溶剂、光敏剂及氧化锆纳米团簇，所述氧化锆纳米团簇的化学通式为ZrxOy(OH)zLm，其中2≤x≤20，2≤y≤40，0≤z≤40，4≤m≤40，L为含有羧基的有机配体；
    所述光敏剂具有如下所示结构：
    其中，R1为*表示连接位点；R2及R3每次出现分别独立地选自-F、-Cl、-Br或-I。
  2. 根据权利要求1所述的紫外光刻胶，其特征在于，所述R2及R3均为-Cl。
  3. 根据权利要求1或2所述的紫外光刻胶，其特征在于，所述含有羧基的有机配体包括丙烯酸配位基、甲基丙烯酸配位基、1-羟基-2-萘甲酸配位基及水杨酸配位基中的至少一种。
  4. 根据权利要求1或2所述的紫外光刻胶，其特征在于，所述光敏剂的质量百分含量为0.001％～1％。
  5. 根据权利要求1或2所述的紫外光刻胶，其特征在于，在所述有机溶剂中，所述氧化锆纳米团簇的质量百分含量为0.5％～15％。
  6. 根据权利要求1或2所述的紫外光刻胶，其特征在于，所述有机溶剂包括乳酸乙酯、苯甲醚、丙二醇单甲醚醋酸酯、甲基异丁酮及异丙醇中的至少一种。
  7. 一种紫外光刻胶图案化的方法，其特征在于，包括以下步骤：
    将权利要求1-6之一所述的紫外光刻胶旋涂于基底上，之后干燥形成紫外光刻胶膜；
    将所述紫外光刻胶膜在掩模版下进行紫外光刻曝光后置于显影剂中显影，以形成光刻图案。
  8. 根据权利要求7所述的紫外光刻胶图案化的方法，其特征在于，所述显影剂包括甲苯、二甲苯、1,2-二乙酰氧基丙烷、丙二醇单甲醚醋酸酯、乙二醇单丁醚醋酸酯、 异丙醇、异丁醇、异戊醇、4-甲基-2-戊醇、异丙氧基乙醇、1-甲氧基-2-丙醇、1-丙氧基-2-丙醇、1-丁氧基-2-丙醇、乙二醇甲醚、乙二醇乙醚、乙二醇丙醚、乙二醇丁醚、丙二醇乙醚、2-庚酮及2-丁酮中的至少一种。
  9. 根据权利要求7所述的紫外光刻胶图案化的方法，其特征在于，所述紫外光刻曝光的光源为365nm波长的紫外光、254nm波长的深紫外光或13.5nm波长的极紫外光。
  10. 根据权利要求7所述的紫外光刻胶图案化的方法，其特征在于，紫外光刻曝光的光源为254nm波长的深紫外光时，曝光剂量大于等于7mJ cm-2；紫外光刻曝光的光源为365nm波长的紫外光时，曝光剂量大于等于300mJ cm-2。
  11. 一种电子束光刻胶，其特征在于，权利要求1-6任一项所述的紫外光刻胶作为电子束光刻胶。
  12. 一种紫外光刻胶，其特征在于，包括有机溶剂、光敏剂及氧化锆纳米团簇，所述氧化锆纳米团簇的化学通式为ZrxOy(OH)zLm，其中2≤x≤20，2≤y≤40，0≤z≤40，4≤m≤40，L为含有羧基的有机配体；
    所述光敏剂具有如下所示结构：
    其中，R1选自
    中任意一种，*表示连接位点，R2及R3每次出现分别独立地选自-F、-Cl、-Br或-I。
  13. 根据权利要求12所述的紫外光刻胶，其特征在于，所述R2及R3均为-Cl。
  14. 根据权利要求12或13所述的紫外光刻胶，其特征在于，所述含有羧基的有机配体包括丙烯酸配位基、甲基丙烯酸配位基、1-羟基-2-萘甲酸配位基及水杨酸配位基中的至少一种。
  15. 根据权利要求12或13所述的紫外光刻胶，其特征在于，在所述有机溶剂中，所述光敏剂的质量百分含量为0.001％～1％。
  16. 根据权利要求12或13所述的紫外光刻胶，其特征在于，在所述有机溶剂中，所述氧化锆纳米团簇的质量百分含量为0.5％～15％。
  17. 根据权利要求12或13所述的紫外光刻胶，其特征在于，所述有机溶剂包括乳酸乙酯、苯甲醚、丙二醇单甲醚醋酸酯、甲基异丁酮及异丙醇中的至少一种。
  18. 一种紫外光刻胶图案化的方法，其特征在于，包括以下步骤：
    将权利要求12-17之一所述的紫外光刻胶旋涂于基底上，之后干燥形成紫外光刻胶膜；
    将所述紫外光刻胶膜在掩模版下进行紫外光刻曝光后置于显影剂中显影，以形成光刻图案。
  19. 根据权利要求18所述的紫外光刻胶图案化的方法，其特征在于，所述显影剂包括甲苯、二甲苯、1,2-二乙酰氧基丙烷、丙二醇单甲醚醋酸酯、乙二醇单丁醚醋酸酯、异丙醇、异丁醇、异戊醇、4-甲基-2-戊醇、异丙氧基乙醇、1-甲氧基-2-丙醇、1-丙氧基-2-丙醇、1-丁氧基-2-丙醇、乙二醇甲醚、乙二醇乙醚、乙二醇丙醚、乙二醇丁醚、丙二醇乙醚、2-庚酮及2-丁酮中的至少一种。
  20. 根据权利要求18所述的紫外光刻胶图案化的方法，其特征在于，所述紫外光刻曝光的光源为365nm波长的紫外光、254nm波长的深紫外光或13.5nm波长的极紫外光。
  21. 根据权利要求18所述的紫外光刻胶图案化的方法，其特征在于，紫外光刻曝光的光源为254nm波长的深紫外光时，曝光剂量大于等于12mJ cm-2；紫外光刻曝光的光源为365nm波长的紫外光时，曝光剂量大于等于200mJ cm-2。
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