CN111965947B - Photoresist, patterning method of photoresist and etching method of integrated circuit board - Google Patents
Photoresist, patterning method of photoresist and etching method of integrated circuit board Download PDFInfo
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- CN111965947B CN111965947B CN202010811304.1A CN202010811304A CN111965947B CN 111965947 B CN111965947 B CN 111965947B CN 202010811304 A CN202010811304 A CN 202010811304A CN 111965947 B CN111965947 B CN 111965947B
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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
- G03F7/70—Microphotolithographic exposure; Apparatus therefor
- G03F7/70216—Mask projection systems
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
- H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
- H01L21/0274—Photolithographic processes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/308—Chemical or electrical treatment, e.g. electrolytic etching using masks
- H01L21/3081—Chemical or electrical treatment, e.g. electrolytic etching using masks characterised by their composition, e.g. multilayer masks, materials
Abstract
The invention discloses a photoresist which comprises, by weight, 1-50 parts of an organic solvent, 0-2 parts but not 0 part of a free radical quencher, and functional particles which comprise a free radical polymerizable metal oxide and an organic ligand coated on the surface of the metal oxide, wherein the organic ligand has a group capable of initiating polymerization by a free radical. The invention also discloses a patterning method of the photoresist. The invention also discloses an etching method of the integrated circuit board.
Description
Technical Field
The invention relates to the technical field of photoetching, in particular to a photoresist, a photoresist patterning method and an integrated circuit board etching method.
Background
As integration levels continue to increase and device dimensions continue to shrink, chip fabrication presents very demanding process conditions for lithographic processes, including critical feature sizes, edge roughness, dimensional uniformity, photoresist cross-sectional topography, defects, and the like. The overall performance of the photoresist can be evaluated using RLS, i.e., R (resolution-feature line width), L (LER or LWR edge roughness), S (sensitivity). In order to meet the requirements of industrial production, the photoresist needs to meet the following indexes: resolution ratio<16nm，LWR<15% sensitivity<20mJ/cm2. Extreme ultraviolet lithography (EUV) is known as the most promising next-generation lithography.
EUV lithography uses extreme ultraviolet light with a wavelength of 10-14nm as a light source, which can reduce the exposure wavelength to 13.5nm, which can extend the lithography technology to feature sizes below 32 nm. When EUV photons (about 92eV) with a wavelength of 13.5nm are incident on the photoresist, the photoresist molecules absorb the photons and ionize, producing secondary electrons, which in turn trigger various chemical reactions. However, the higher energy of secondary electrons tends to result in a high line edge roughness of the photoresist pattern, especially for high resolution lithographic imaging of nodes below 16 nm.
Disclosure of Invention
Based on the above, it is necessary to provide a photoresist, a patterning method of the photoresist and an etching method of an integrated circuit board capable of reducing the line edge roughness of the EUV lithography pattern.
The photoresist is characterized by comprising 1-50 parts of organic solvent, 0-2 parts of free radical quencher and not 0 part by weight of functional particles, wherein the functional particles comprise free radical polymerizable metal oxide and organic ligands coated on the surface of the metal oxide, and the organic ligands have groups capable of initiating polymerization by free radicals.
In one embodiment, the free radical quencher is selected from one or more of p-benzoquinone, hydroquinone, 2-methyl hydroquinone, 2-methoxy hydroquinone, phenothiazine, p-tert-butyl catechol, beta-phenyl naphthylamine, 1-diphenyl-2-picrylhydrazine, 5-dimethyl-1-pyrroline-N-oxide, and 2,2,6, 6-tetramethyl-1-piperidine oxide.
In one embodiment, the metal oxide is selected from any one or more of zirconium oxide, zinc oxide, hafnium oxide, nickel oxide, cobalt oxide, indium oxide, and tin oxide.
In one embodiment, the organic ligand is an organic ligand containing a carbon-carbon double bond.
In one embodiment, the organic ligand is selected from one or more of acrylic acid, methacrylic acid, and 3, 3-dimethylacrylic acid.
In one embodiment, the metal oxide is zirconium oxide, and the functional particles have a molecular formula of Zr6O4(OH)4X12Wherein X is selected from one or more of acrylic acid, methacrylic acid and 3, 3-dimethyl acrylic acid.
In one embodiment, the functional particles are 5 to 25 parts by weight.
In one embodiment, the organic solvent is selected from one or more of 1, 4-dioxane, propylene glycol methyl ether acetate, ethyl lactate, butyl lactate, acetone, gamma-butyrolactone, and cyclopentanone.
In one embodiment, the mass percentage of the functional particles in the photoresist is 1% to 50%, and the mass percentage of the radical quencher in the photoresist is 0% to 2% and is not 0.
In one embodiment, the mass percentage of the functional particles in the photoresist is 5-25%
The photoresist patterning method comprises the following steps:
coating the photoresist on the surface of a substrate, removing an organic solvent in the photoresist, and forming a pre-film forming layer on the surface of the substrate;
irradiating a light source on the pre-film forming layer of the substrate through a mask with a preset pattern to carry out exposure operation, so that an exposure area of the pre-film forming layer forms a functional particle aggregate;
and applying a developer to the exposed pre-film layer, so that an unexposed area on the pre-film layer, which is shielded by the mask, is dissolved in the developer, and an exposed area of the pre-film layer is remained on the substrate due to the formation of functional particle aggregates.
In one embodiment, the exposure dose of the exposure operation is 4.9mJ/cm2～150mJ/cm2。
In one embodiment, the developer is selected from one or more of isopropanol, toluene, o-xylene, m-xylene, p-xylene, acetone, cyclohexane, n-heptane, n-pentane, 4-methyl-2-pentanol, propylene glycol methyl ether acetate, ethyl acetate, 1, 4-dioxane, and butyl acetate.
In one embodiment, the substrate is selected from a silicon plate.
An etching method of an integrated circuit board comprises the following steps:
preparing a pre-patterned plate with a patterned photoresist layer on a silicon plate substrate according to the patterning method of the photoresist;
and etching the pre-patterned plate by using a dry method or a wet method, wherein the area of the silicon plate substrate with the photoresist layer is not etched, and the area without the photoresist layer is etched.
The photoresist can effectively improve the performance of the photoresist by inhibiting the diffusion distance of secondary electrons, and particularly improve the precision of EUV lithography with high sensitivity. The EUV light source has large single photon energy and the action mechanism is different from that only a photosensitizer reacts with light in the traditional ultraviolet photoetching, but all substances in the photoresist react with EUV photons, most of the reaction can generate secondary electrons, and the secondary electrons can further initiate the photochemical reaction of the photoresist. The secondary electron energy is high, the diffusion phenomenon of the secondary electrons in the traditional photoresist is serious, researches show that the mean free path of the photoresist can reach dozens of nanometers, and the diffusion of the secondary electrons causes the quality problem of the pattern, particularly the poor edge roughness of the pattern. According to the invention, a proper amount of free radical quencher is added into the photoresist, so that active ion fragments in a non-exposure area triggered by secondary electrons diffused in a film layer can be effectively quenched, and further reaction of the non-exposure area is inhibited. EUV irradiation of the functional particles causes dissociation of a small amount of organic ligands on the surface, changes in surface charge, further causes aggregation of the functional particles or aggregation of metal oxides to form aggregates, the exposed regions have reduced solubility in the developer, and the non-exposed regions are capable of dissolving in the developer because no reaction is initiated. The photoresist can control edge defects caused by secondary electron diffusion under the condition of higher photosensitivity, reduce edge roughness and improve resolution, and particularly has great improvement on the photoetching quality of devices with higher precision requirements.
In addition, the surface of the functional particle is provided with the organic ligand capable of free radical polymerization, so that on one hand, the dispersibility of the metal oxide in an organic solvent is improved, and on the other hand, the organic ligand can initiate the polymerization of the surface of the functional particle, thereby being beneficial to improving the solubility difference of an exposed area and a non-exposed area of the photoresist and being beneficial to improving the patterning sensitivity.
Drawings
FIG. 1 is an SEM of a patterned exposure of a photoresist of comparative example 1 of the present invention;
FIG. 2 is a patterned exposure electron micrograph of a photoresist of comparative example 2 of the present invention;
FIG. 3 is an SEM of a patterned exposure of a photoresist of comparative example 3 of the present invention;
FIG. 4 is an SEM of the patterning of a photoresist in example 3 of the present invention;
FIG. 5 is an SEM of the patterning of a photoresist in example 5 of the present invention;
FIG. 6 is an SEM image of a photoresist pattern obtained in example 7 of the present invention.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The term "feature line width" refers to the narrowest line width that can be achieved with a single exposure.
The embodiment of the invention provides a photoresist which comprises, by weight, 1-50 parts of an organic solvent, 0-2 parts but not 0 part of a free radical quencher, and the functional particles comprise a free radical polymerizable metal oxide and an organic ligand coated on the surface of the metal oxide, wherein the organic ligand has a group capable of initiating polymerization by a free radical.
The photoresist can effectively improve the performance of the photoresist by inhibiting the diffusion distance of secondary electrons, and particularly improve the precision of EUV lithography with high sensitivity. The EUV light source has large single photon energy and the action mechanism is different from that only a photosensitizer reacts with light in the traditional ultraviolet photoetching, but all substances in the photoresist react with EUV photons, most of the reaction can generate secondary electrons, and the secondary electrons can further initiate the photochemical reaction of the photoresist. The secondary electron energy is high, the diffusion phenomenon of the secondary electrons in the traditional photoresist is serious, researches show that the mean free path of the photoresist can reach dozens of nanometers, and the diffusion of the secondary electrons causes the quality problem of the pattern, particularly the poor edge roughness of the pattern. According to the invention, a proper amount of free radical quencher is added into the photoresist, so that active ion fragments in a non-exposure area triggered by secondary electrons diffused in a film layer can be effectively quenched, and further reaction of the non-exposure area is inhibited. EUV irradiation of the functional particles causes dissociation of a small amount of organic ligands on the surface, changes in surface charge, further causes aggregation of the functional particles or aggregation of metal oxides to form aggregates, the exposed regions have reduced solubility in the developer, and the non-exposed regions are capable of dissolving in the developer because no reaction is initiated. The photoresist can control edge defects caused by secondary electron diffusion under the condition of higher photosensitivity, reduce edge roughness and improve resolution, and particularly has great improvement on the photoetching quality of devices with higher precision requirements.
In addition, the surface of the functional particle is provided with the organic ligand capable of free radical polymerization, so that on one hand, the dispersibility of the metal oxide in an organic solvent is improved, and on the other hand, the organic ligand can initiate the polymerization of the surface of the functional particle, thereby being beneficial to improving the solubility difference of an exposed area and a non-exposed area of the photoresist and being beneficial to improving the patterning sensitivity.
In some embodiments, the free radical quencher can be selected from one or more of p-benzoquinone, hydroquinone, 2-methyl hydroquinone, 2-methoxy hydroquinone, phenothiazine, p-tert-butyl catechol, β -phenyl naphthylamine, 1-diphenyl-2-picrylhydrazine, 5-dimethyl-1-pyrroline-N-oxide, and 2,2,6, 6-tetramethyl-1-piperidine oxide, as shown in the following structural formulas (1) - (10):
in some embodiments, the metal oxide may be selected from any one or more of zirconium oxide, zinc oxide, hafnium oxide, nickel oxide, cobalt oxide, indium oxide, and tin oxide.
In some embodiments, the organic ligand is an organic ligand containing a carbon-carbon double bond.
In some embodiments, the organic ligand is selected from one or more of acrylic acid, methacrylic acid, and 3, 3-dimethylacrylic acid. Specifically, in one functional particle, the organic ligand may be one, two or three of the above molecules. For example, in one functional particle, the organic ligand may be methacrylic acid. In one functional particle, the organic ligand may be 3, 3-dimethylacrylic acid. In one functional particle, the organic ligand may be acrylic acid or methacrylic acid. In one functional particle, the organic ligand may be acrylic acid and 3, 3-dimethylacrylic acid. In one functional particle, the organic ligand may be methacrylic acid and 3, 3-dimethylacrylic acid. In one functional particle, the organic ligand may be acrylic acid, methacrylic acid, and 3, 3-dimethylacrylic acid.
In some embodiments, the metal oxide is selected from zirconia, and the functional particles have a molecular formula of Zr6O4(OH)4X12Wherein X is selected from one or more of acrylic acid, methacrylic acid and 3, 3-dimethyl acrylic acid.
In some embodiments, the functional particles have a particle size on the order of nanometers.
In some embodiments, the organic solvent is selected from one or more of 1, 4-dioxane, propylene glycol methyl ether acetate, ethyl lactate, butyl lactate, acetone, γ -butyrolactone, and cyclopentanone.
In some embodiments, the functional particles may be present in an amount of 1 to 5 parts, 5 to 10 parts, 10 to 20 parts, 20 to 30 parts, 30 to 40 parts, or 40 to 50 parts by weight, preferably 5 to 25 parts by weight. In some embodiments, the free radical quencher can be 0.1 to 0.5, 0.5 to 1,1 to 1.5, or 1.5 to 2 parts by weight.
In some embodiments, the mass percentage of the functional particles in the photoresist may be 1% to 50%. Specifically, the mass percentage of the functional particles in the photoresist is 1% -5%, 5% -10%, 10% -20%, 20% -30%, 30% -40% or 40% -50%. Preferably 5% to 25%.
In some embodiments, the weight fraction of the free radical quencher can be 0-0.5 parts (excluding 0), 0.5-10 parts, 1-1.5 parts, or 1.5-2 parts.
In some embodiments, the mass percent of the free radical quencher in the photoresist is 0% to 2% (excluding 0). Specifically, the mass percentage of the free radical quencher in the photoresist is 0-0.5% (excluding 0), 0.5-1%, 1-1.5% or 1.5-2%.
The embodiment of the invention also provides a patterning method of the photoresist, which comprises the following steps:
coating the photoresist on the surface of a substrate, removing an organic solvent in the photoresist, and forming a pre-film forming layer on the surface of the substrate;
irradiating an EUV light source on the pre-film forming layer of the substrate through a mask with a preset pattern to perform exposure operation, so that an exposure area of the pre-film forming layer forms functional particle aggregates;
and applying a developer to the exposed pre-film layer, so that an unexposed area on the pre-film layer, which is shielded by the mask, is dissolved in the developer, and an exposed area of the pre-film layer is remained on the substrate due to the formation of functional particle aggregates.
In some embodiments, the exposure operation has an exposure dose of 4.9mJ/cm2～150mJ/cm2. The exposure dose should be controlled within a proper range, if the exposure dose is too small, the energy is too low to be beneficial to the formation of secondary electrons, and the polymerization degree of functional particles in an exposure area is poor to be beneficial to the development of the exposure area and a non-exposure area. Compared with exposed metal oxide, the polymerization of the functional particles is easier to carry out, and the organic matter ligand on the surface of the functional particles can directly fall off from the metal oxide to form fragments if the exposure dose is too large, so that the surface of the functional particles can not generate free radical addition reaction of carbon-carbon double bonds any more, and the polymerization degree of an exposure area is reduced.
In some embodiments, the developer is selected from one or more of isopropanol, toluene, o-xylene, m-xylene, p-xylene, acetone, cyclohexane, n-heptane, n-pentane, 4-methyl-2-pentanol, propylene glycol methyl ether acetate, ethyl acetate, 1, 4-dioxane, and butyl acetate. The developer is mainly used to dissolve unpolymerized functional particles. Organic matter ligands on the surfaces of the functional particles in the exposure areas undergo carbon-carbon double bond free radical polymerization to form aggregates or metal oxides with the organic matter ligands removed are polymerized into metal oxides under the initiation of free radicals to form the aggregates. The agglomerates in the exposed areas are insoluble in the developer or have a low solubility in the developer, even if partly dissolved, so that the exposed areas remain covered by the agglomerates. In some embodiments, the temperature of development may be room temperature, for example, from 20 ℃ to 30 ℃.
In one embodiment, the thickness of the pre-film layer after removing the organic solvent may be 10nm to 500 nm. Specifically, the thickness of the pre-film forming layer may be 10nm to 50nm, 50nm to 100nm, 100nm to 150nm, 150nm to 200nm, 200nm to 250nm, 250nm to 300nm, 300nm to 350nm, 350nm to 400nm, 400nm to 450nm or 450nm to 500 nm.
In some embodiments, the substrate may be selected from a silicon plate.
The embodiment of the invention also provides an etching method of the integrated circuit board, which comprises the following steps:
preparing a pre-patterned plate with a patterned photoresist layer on a silicon plate substrate according to the patterning method of the photoresist;
and etching the pre-patterned plate by using a dry method or a wet method, wherein the area of the silicon plate substrate with the photoresist layer is not etched, and the area without the photoresist layer is etched.
The following are specific examples.
1. Weighing a proper amount of functional particles (formed by metal oxide and organic matter ligand coated outside the metal oxide, wherein the metal oxide is selected from any one, any two, any three, any four, any five, any six or all seven of zirconium oxide, zinc oxide, hafnium oxide, nickel oxide, cobalt oxide, indium oxide and tin oxide, the organic matter ligand is organic matter ligand containing carbon-carbon double bond, and comprises acrylic acid AA, methacrylic acid MAA or 3, 3-dimethylacrylic acid DMAA and the like), free radical quenching agent (comprising p-benzoquinone, hydroquinone, 2-methyl hydroquinone, 2-methoxy hydroquinone, phenothiazine, p-tert-butyl catechol, beta-phenyl naphthylamine, 1-diphenyl-2-picrylhydrazine (DPPH), 5-dimethyl-1-pyrroline-N-oxide (DMPO)), and/or zinc oxide, 2,2,6, 6-tetramethyl-1-piperidinyloxy (TEMPO), etc.) and an organic solvent (including: 1, 4-dioxane, Propylene Glycol Methyl Ether Acetate (PGMEA), ethyl lactate, butyl lactate, acetone, gamma-butyrolactone, cyclopentanone and the like) in a certain proportion (wherein the mass percentage of the functional particles is 1-50%; the mass percentage of the free radical quenching agent is 0.1-2%. Preparing a photoresist solution with a certain concentration (the solid content of the solution is 1-50 wt%, preferably 5-25 wt%), shaking for dissolution, and filtering the photoresist for later use.
2. Setting the rotating speed and time of a spin coater (related to the thickness of a coated photoresist film), taking a small amount of photoresist solution to spin-coat the surface of a silicon wafer, and prebaking (the temperature is 60-100 ℃) to remove an organic solvent to obtain a pre-formed film layer.
3. And (3) exposing the pre-formed film layer by using an extreme ultraviolet exposure machine, a deep ultraviolet light source or an electron beam light source through a mask (a preset pattern).
4. After the exposure, the silicon wafer is taken out and developed with an organic solvent (the developer can be selected from isopropanol, toluene, o-xylene, m-xylene, p-xylene, acetone, cyclohexane, n-heptane, n-pentane, 4-methyl-2-pentanol, propylene glycol methyl ether acetate, ethyl acetate, 1, 4-dioxane, butyl acetate and the like) at room temperature.
5. And after the development is finished, drying the silicon wafer by a nitrogen gun for observation.
6. And observing the photoetching imaging result under a scanning electron microscope.
The compositions of the photoresist compositions of the specific examples and comparative examples are shown in table 1 below.
Fig. 1 to 6 are electron micrographs of comparative example 1, comparative example 2, comparative example 3, example 5 and example 7 in this order.
The line width of the exposed area measured in FIG. 1 was 526 nm; the line width of the exposed area measured in FIG. 2 was 60 nm; the non-exposed areas in fig. 3 appear diffusely exposed over a large range; the line width of the exposed region measured in FIG. 4 was 80 nm; the line width of the exposed area measured in FIG. 5 was 34 nm; the line width of the exposed area measured in fig. 6 was 38 nm.
TABLE 1
The exposure dose is light intensity x exposure time, and the smaller the exposure dose, the higher the sensitivity of the photoresist.
The characteristic line width refers to the narrowest line width obtained by single exposure, and the smaller the characteristic line width is, the higher the resolution of the photoresist is.
A smaller edge roughness indicates a higher lithographic accuracy of the photoresist.
The exposure dose, the characteristic line width and the edge roughness jointly represent the performance of the photoresist.
The imaging results of the examples and comparative examples show that:
compared with other light source etching (comparison of comparative examples 1-3), the extreme ultraviolet lithography is easier to cause secondary electron diffusion, and is easy to cause the problems of high edge roughness and low resolution.
In extreme ultraviolet lithography, the photoresist without added radical quencher was very low in exposure dose (comparative example 34.9 mJ/cm)2) Under the condition of (2), a large amount of secondary electrons are diffused, so that the non-exposure area is also reacted, patterns which are obviously distinguished from the exposure area and the non-exposure area cannot be obtained, and the photoresist cannot be patterned. The photoresist of the embodiment can still obtain the photoresist pattern with low edge roughness and small line width under the condition of larger exposure dose than that of the embodiment 3, which shows that the photoresist of the invention can realize the reduction of the edge roughness and the improvement of the resolution ratio on the basis of ensuring the photoetching sensitivity.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (8)
1. A method of patterning a photoresist comprising the steps of:
coating the photoresist on the surface of a substrate, removing an organic solvent in the photoresist, and forming a pre-film forming layer on the surface of the substrate, wherein the photoresist comprises the organic solvent, 5-25 parts of functional particles and 0-2 parts but not 0 part of free radical quenching agent, the functional particles comprise free radical polymerizable metal oxide and organic ligands coated on the surface of the metal oxide, the organic ligands have groups capable of initiating polymerization by free radicals, and the molecular general formula of the functional particles is Hf4O2(AA)12Or Hf4O2(MAA)6(AA)6；
Irradiating an extreme ultraviolet light source on the pre-film layer of the substrate through a mask with a preset pattern for exposure operation, so that the exposure area of the pre-film layer forms functional particle aggregates, wherein the exposure dose of the exposure operation is 4.9mJ/cm2～150mJ/cm2；
And applying a developer to the exposed pre-film layer, so that an unexposed area on the pre-film layer, which is shielded by the mask, is dissolved in the developer, and an exposed area of the pre-film layer is remained on the substrate due to the formation of functional particle aggregates.
2. The method of claim 1, wherein the developer is selected from one or more of isopropanol, toluene, o-xylene, m-xylene, p-xylene, acetone, cyclohexane, n-heptane, n-pentane, 4-methyl-2-pentanol, propylene glycol methyl ether acetate, ethyl acetate, 1, 4-dioxane, and butyl acetate.
3. The method of claim 1, wherein the substrate is selected from a silicon plate.
4. The method of claim 1, wherein the radical quencher is one or more selected from the group consisting of p-benzoquinone, hydroquinone, 2-methyl hydroquinone, 2-methoxy hydroquinone, phenothiazine, p-tert-butyl catechol, β -phenyl naphthylamine, 1-diphenyl-2-picrylhydrazine, 5-dimethyl-1-pyrroline-N-oxide, and 2,2,6, 6-tetramethyl-1-piperidine oxide.
5. The method of claim 1, wherein the organic solvent is one or more selected from the group consisting of 1, 4-dioxane, propylene glycol methyl ether acetate, ethyl lactate, butyl lactate, acetone, gamma-butyrolactone, and cyclopentanone.
6. The method of claim 1, wherein the functional particles are present in the photoresist in an amount of 1 to 50% by mass; the mass percentage of the free radical quenching agent in the photoresist is 0-2% and is not 0.
7. The method of claim 6, wherein the functional particles are present in the photoresist in an amount of 5 to 25% by mass.
8. An etching method of an integrated circuit board is characterized by comprising the following steps:
preparing a pre-patterned plate having a patterned photoresist layer on a silicon plate substrate according to the method for patterning a photoresist of any one of claims 1 to 7;
and etching the pre-patterned plate by using a dry method or a wet method, wherein the area of the silicon plate substrate with the photoresist layer is not etched, and the area without the photoresist layer is etched.
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| WO2019005161A1 (en) * | 2017-06-30 | 2019-01-03 | Intel Corporation | Method and compound for controlling patterning of a resist material |
| WO2019220835A1 (en) * | 2018-05-14 | 2019-11-21 | Jsr株式会社 | Pattern forming method and radiation sensitive composition |
| US20210149299A1 (en) * | 2018-06-29 | 2021-05-20 | National Institute Of Advanced Industrial Science And Technology | Organically modified metal oxide nanoparticle, method for producing the same, euv photoresist material, and method for producing etching mask |
| DE102019126271B4 (en) * | 2018-10-08 | 2023-01-12 | Taiwan Semiconductor Manufacturing Co., Ltd. | Photoresist composition and method of forming a photoresist pattern |
| WO2020264059A1 (en) * | 2019-06-24 | 2020-12-30 | Cornell University | Light patterning of inorganic materials |
| CN111766762A (en) * | 2020-06-24 | 2020-10-13 | 清华大学 | Photoresist composition and method for forming thin film pattern and array substrate using the same |
| CN111948904B (en) * | 2020-08-13 | 2022-04-01 | 常州华睿芯材科技有限公司 | Photoresist composition, method for forming photolithographic pattern using the same, and use thereof |
| CN111965947B (en) * | 2020-08-13 | 2022-04-01 | 常州华睿芯材科技有限公司 | Photoresist, patterning method of photoresist and etching method of integrated circuit board |
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2020
- 2020-08-13 CN CN202010811304.1A patent/CN111965947B/en active Active
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| WO2022033367A1 (en) | 2022-02-17 |
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