Zn-based organic coordination nanoparticles, photoresist composition, and preparation method and application thereof

Abstract

The application relates to a Zn-based organic coordination nanoparticle, a photoresist composition and a preparation method and application thereof, the nanoparticle is a metal organic one-dimensional repeating chain structure, and the structural general formula is [ZnX2(CH3COO)Y] n wherein X is selected from benzoate or m-methylbenzoate, Y is selected from organic amine ligands, and n is a polymerization degree, and n is greater than or equal to 1. The Zn-based organic coordination nanoparticle can be used to form the photoresist composition and is used for middle ultraviolet, electron beam and extreme ultraviolet photoetching to obtain high-quality exposure patterns, so that the Zn-based organic coordination nanoparticle has significant application potential and value.

Description

Technical Field

[0001] This invention relates to the field of photoresist technology, and in particular to Zn-based organic coordination nanoparticles, photoresist compositions, their preparation methods and applications. Background Technology

[0002] Photolithography, also known as photoresist, is a technique that transfers patterns from a photomask onto a substrate using photoresist under certain energy conditions. It is the core of chip manufacturing. In integrated circuit manufacturing, photolithography costs account for one-third or more of the total cost; the size and quality of the photolithography significantly affect chip performance. With the continuous development of photolithography technology and the decreasing linewidth of light sources, extreme ultraviolet (EUV) light source exposure technology at 13.5nm has gradually become the main choice for photolithography nodes below 7nm.

[0003] Photoresist is a photosensitive material whose main function is to transfer chip design patterns from a photomask onto a substrate. During this process, the photoresist undergoes a chemical reaction under light irradiation, causing a change in its dissolution rate. As the exposure wavelength in photolithography decreases, the corresponding photoresist materials also change. Based on different photosensitive wavelengths, photoresists can be classified into G-line photoresists, I-line photoresists, 248nm photoresists, 193nm photoresists, and 13.5nm extreme ultraviolet (EUV) photoresists.

[0004] Extreme ultraviolet (EUV) lithography suffers from low light source power and low conversion efficiency. Therefore, traditional organic polymer photoresists and molecular glass photoresists, primarily composed of elements like carbon (C) and oxygen (O), are no longer suitable due to their low photon absorption rate and sensitivity. To improve the photon absorption rate of photoresists, metal elements with high light absorption cross-sections have been introduced. In recent years, research on metal-organic photoresists has deepened. The zirconia nanoparticle photoresist developed by Ober at Cornell University and Brainard's laboratory at the State University of New York achieved a photon absorption rate of 4.2 mJ / cm². 2It boasts ultra-high photosensitivity and a linewidth resolution of 26 nm. However, the nanoparticles prepared by the sol-gel method have a relatively wide size distribution, leading to differences in dissolution rates during organic development and resulting in a line edge roughness of 5.9 nm. In 2009, Inpria's patent WO2009 / 120169A also prepared a photoresist mixture of HfO2+ or ZrO2+ metal oxide organic ligands. After coating and exposure development processes, this composition can obtain patterns with an LER of 2.25 nm and an indirection of no more than 60 nm. Subsequently, Inpria also developed Sn-based metal oxide organic ligand compositions and organic-inorganic nanoclusters, and demonstrated their feasibility as EUV photoresists (TW1719360B, TW201943724A, TW202110863A, WO2019195522A). However, due to the unavoidable toxicity of Sn, Sn-based organic ligand photoresist compositions still face process safety risks, which restricts their industrial application and promotion.

[0005] To further obtain safer and more reliable metal-organic ligand photoresists, the Zn element system has become a promising option. This invention aims to develop a novel Zn-based organic ligand photoresist with lower roughness, higher resolution, wider applicability, and safety and environmental friendliness. Summary of the Invention

[0006] Therefore, it is necessary to address the problems of large edge roughness and low pattern resolution obtained by traditional photoresist lithography, and to propose a new Zn-based organic coordination nanoparticle, photoresist composition, its preparation method and application.

[0007] This invention first provides a Zn-based organic coordination nanoparticle, which is a one-dimensional repeating chain structure of metal-organic compounds with the general structural formula [ZnX2(CH3COO)Y]. n In this context, X is selected from benzoate or m-methylbenzoate, Y is selected from organic amine ligands, and n is the degree of polymerization, which is greater than or equal to 1. The prepared Zn-based organic coordination nanoparticles have a size of 1 nm to 4 nm.

[0008] Furthermore, the organic amine ligands are selected from N-methylpiperidine, N-methylpyrrolidine, cycloheximine, and methylpyrrolidine.

[0009] This invention also provides a method for preparing Zn-based organic coordination nanoparticles, comprising the following steps:

[0010] (1) A zinc metal salt solution is obtained by mixing a zinc metal salt with an organic solvent;

[0011] (2) The zinc metal salt solution is mixed with the first organic ligand and the second organic ligand, and the mixture is heated and stirred to carry out the reaction;

[0012] (3) Remove the residual solvent from the product after the reaction.

[0013] Furthermore, the first organic ligand is benzoic acid or m-methylbenzoic acid, and the second organic ligand is selected from N-methylpiperidine, N-methylpyrrolidine, cycloheximine, and methylpyrrolidine.

[0014] The molar ratio of the zinc metal salt, the first organic ligand, and the second organic ligand is (0.2-1):(0.4-1):(0.3-1); preferably, the molar ratio of the zinc metal salt, the first organic ligand, and the second organic ligand is 1:(3-5):(2-5).

[0015] Furthermore, in step (2), the heating and stirring temperature range is 50℃~80℃, and the time is 10h~40h.

[0016] Furthermore, in step (3), the solvent removal method can be vacuum rotary evaporation, with a temperature of 20℃~80℃, a vacuum rotary evaporation pressure of 20mbar~60mbar, and a vacuum rotary evaporation time of 30~60 minutes.

[0017] The present invention also provides a Zn-based organic coordination nanoparticle, which is obtained by the aforementioned preparation method.

[0018] The present invention also provides a Zn-based organic coordination nanoparticle photoresist composition, the photoresist composition comprising the aforementioned Zn-based organic coordination nanoparticles, a photoacid, and an organic dispersion solvent, wherein the Zn-based organic coordination nanoparticles have a mass percentage of 3-20%, and the photoacid has a mass percentage of 5-10%.

[0019] The photoacid agent may be selected from any one or more of N-hydroxynaphthalimide trifluoromethanesulfonic acid, 1,4-aminonaphthalenesulfonic acid, 2-amino-5,7-naphthalenedisulfonic acid, tert-butylphenyliodonium salt perfluorooctanesulfonic acid, triphenylsulfonium perfluorobutanesulfonic acid, triphenylsulfonium perfluorobutyl, and triphenylsulfonium trifluorosulfonic acid; the organic dispersion solvent may be selected from any one or more of ethyl acetate, butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol methyl ether acetate, 1-ethoxy-2-propanol, methanol, ethanol, and propanol.

[0020] Furthermore, the preparation method of the above-mentioned Zn-based organic coordination nanoparticle photoresist composition specifically includes: dissolving the obtained nanoparticle composition in an organic dispersion solvent, adding a photoacid, stirring for 5 minutes until completely dissolved, and obtaining a photoresist mixed solution.

[0021] The present invention further provides a method for patterning photoresist, comprising the following steps:

[0022] (1) The above photoresist composition is coated on the substrate surface, the organic dispersion solvent is removed, and a pre-film layer is formed on the substrate surface;

[0023] (2) Exposure operation is performed by shining a light source through a mask onto the pre-formed film layer of the substrate, so that photoresist particle agglomerates are formed in the exposure area of ​​the pre-formed film layer.

[0024] (3) Apply developer to the exposed pre-film layer so that the unexposed area of ​​the pre-film layer that is covered by the mask dissolves in the developer, while the exposed area of ​​the pre-film layer remains on the substrate due to the formation of photoresist particle agglomerates.

[0025] Specifically, the exposure conditions can be selected from mid-ultraviolet, electron beam, or extreme ultraviolet, with an ultraviolet light exposure dose of 50 mJ / cm². 2 ~500mJ / cm 2 The electron beam exposure dose was 50 μC / cm. 2 ~500μC / cm 2 The thickness of the pre-formed film after removing the organic dispersion solvent can be 10 nm to 100 nm.

[0026] The Zn-based organic coordination nanoparticles and their photoresist composition of the present invention can be used to form printed circuit boards. The specific method includes the following steps:

[0027] (1) Prepare a pre-patterned substrate with a patterned photoresist layer on a silicon substrate according to the above-mentioned photoresist patterning method;

[0028] (2) The pre-patterned substrate is etched using a dry or wet method.

[0029] The Zn-based organic coordination nanoparticles designed and prepared in this invention possess a one-dimensional repeating chain structure of metal-organic compounds. Under illumination, these nanoparticles can interact with photoacids, causing a change in material polarity and aggregation, resulting in a change in their solubility before and after illumination. Due to these properties, using these coordination polymer nanoparticles as a component of photoresist can create a difference in the solubility of the photosensitive and light-shielding portions in the developer. The photosensitive portion aggregates and its solubility in the developer decreases, while the light-shielding portion does not aggregate and dissolves in the developer. This allows for the removal of unexposed areas after development, thereby obtaining a pattern of the desired shape.

[0030] In particular, due to the unique structure of Zn-based organic coordination nanoparticles, compared to traditional polymer-based photoresists and molecular glass photoresists, using these Zn-based organic coordination nanoparticles as a photoresist component can achieve superior photolithography performance, including high resolution, high sensitivity, and low line roughness. Currently, domestically produced photoresists are mostly used in integrated circuit processes above 350nm, while ArF photoresists used at 193nm are still in their early stages, and high-end ArF photoresists are basically dependent on imports. Therefore, when the Zn-based organic coordination nanoparticles provided in this invention are used as a photoresist material for photolithography, a higher pattern resolution can be obtained compared to existing technologies, representing a significant advancement in the localization of photoresist technology.

[0031] Furthermore, the coordination polymer nanoparticles of this invention, used as a photoresist component, can be used for pattern fabrication under various exposure conditions, including mid-ultraviolet, electron beam, and extreme ultraviolet, while also achieving extremely high photosensitivity and resolution. Moreover, compared to polymer photoresists and molecular glass photoresists, the presence of metal elements gives the photoresist of this invention superior etching resistance. Attached Figure Description

[0032] Figure 1 The particle size distribution curve of the product prepared in Example 1 was obtained by dynamic light scattering particle size analysis (DLS).

[0033] Figure 2 The basic structural unit of the product prepared in Example 1;

[0034] Figure 3 The product prepared in Example 1 has a one-dimensional repeating chain structure;

[0035] Figure 4 The exposure pattern of the photoresist prepared in Example 1 after exposure under mid-ultraviolet light;

[0036] Figure 5 The exposure pattern obtained after the photoresist prepared in Example 1 is exposed under an electron beam;

[0037] Figure 6 The particle size distribution curve of the product prepared in Example 2 is obtained by dynamic light scattering particle size analysis (DLS).

[0038] Figure 7 The product prepared in Example 2 and its 1H NMR spectrum compared with the raw materials fed in;

[0039] Figure 8 The basic structural unit of the product prepared in Example 2;

[0040] Figure 9 The product prepared in Example 2 has a one-dimensional repeating chain structure.

[0041] Figure 10 The photoresist prepared in Example 2 is exposed under mid-ultraviolet light;

[0042] Figure 11 The exposure pattern obtained after the photoresist prepared in Example 2 is exposed under an electron beam;

[0043] Figure 12 The particle size distribution curve of the product prepared in Example 3 was obtained by dynamic light scattering particle size analysis (DLS).

[0044] Figure 13 The product prepared in Example 3 and its 1H NMR spectrum compared with the raw materials fed in;

[0045] Figure 14 The basic structural unit of the product prepared in Example 3;

[0046] Figure 15 The product prepared in Example 3 has a one-dimensional repeating chain structure;

[0047] Figure 16 The photoresist prepared in Example 3 is exposed under mid-ultraviolet light;

[0048] Figure 17 The exposure pattern obtained after the photoresist prepared in Example 3 was exposed under an electron beam;

[0049] Figure 18 The particle size distribution curve of the product prepared in Example 4 was obtained by dynamic light scattering particle size analysis (DLS).

[0050] Figure 19 The product prepared in Example 4 and its 1H NMR spectrum compared with the raw materials fed in;

[0051] Figure 20 The photoresist prepared in Example 4 is exposed under mid-ultraviolet light;

[0052] Figure 21 The exposure pattern obtained after the photoresist prepared in Example 4 is exposed under an electron beam;

[0053] Figure 22 The particle size distribution curve of the product prepared in Example 5 was obtained by dynamic light scattering particle size analysis (DLS).

[0054] Figure 23 The product prepared in Example 5 and its 1H NMR spectrum compared with the raw materials fed in;

[0055] Figure 24 The basic structural unit of the product prepared in Example 5;

[0056] Figure 25 The product prepared in Example 5 has a one-dimensional repeating chain structure;

[0057] Figure 26 The photoresist prepared in Example 5 is exposed under mid-ultraviolet light;

[0058] Figure 27 The exposure pattern is obtained after the photoresist prepared in Example 5 is exposed under an electron beam. Detailed Implementation

[0059] To facilitate understanding of the present invention, a more complete description will be given below with reference to the accompanying drawings. Preferred embodiments of the invention are shown in the drawings. However, the invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a thorough and complete understanding of the disclosure of the invention.

[0060] Unless otherwise defined, 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 pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0061] The following are specific embodiments, intended to provide a more detailed description of the present invention to help those skilled in the art and researchers to further understand it. The technical conditions described do not constitute any limitation on the present invention. Any modifications made within the scope of the claims of this invention are protected within the scope of the claims.

[0062] This invention provides a Zn-based organic coordination nanoparticle with the general chemical formula [ZnX2(CH3COO)Y]. n Wherein, X is selected from benzoic acid ligands or m-methylbenzoic acid ligands, Y is selected from N-methylpiperidine, N-methylpyrrolidine, cycloheximine, methylpyrrolidine, and n is the degree of polymerization, where n is greater than or equal to 1, and as the value of n increases, the nanoparticles are one-dimensional repeating chain structures of metal-organic compounds. Furthermore, the size of the nanoparticles is 1 nm to 4 nm.

[0063] This invention also provides a method for preparing Zn-based organic coordination nanoparticles, comprising the following steps:

[0064] (1) A zinc metal salt solution is obtained by mixing a zinc metal salt with an organic solvent;

[0065] (2) The zinc metal salt solution is mixed with the first organic ligand and the second organic ligand, and the mixture is heated and stirred to carry out the reaction;

[0066] (3) Remove the residual solvent from the product after the reaction;

[0067] Wherein, the first organic ligand is benzoic acid or m-methylbenzoic acid, and the second organic ligand is selected from N-methylpiperidine, N-methylpyrrolidine, cycloheximine, and methylpyrrolidine.

[0068] Furthermore, the molar ratio of the zinc metal salt, the first organic ligand, and the second organic ligand is (0.2–1):(0.4–1):(0.3–1);

[0069] Furthermore, in the preferred embodiment, Zn-based organic coordination nanoparticles can be obtained when the molar ratio of the zinc metal salt, the first organic ligand, and the second organic ligand is within the range of 1:(3-5):(2-5).

[0070] Furthermore, in step (2), the temperature range of the heating and stirring is 50℃~80℃, and the time is 10h~40h. If the temperature is too low, the reaction rate is too slow, and if the temperature is too high, the reaction is unstable and Zn-based organic coordination nanoparticles cannot be obtained.

[0071] Furthermore, in step (3), the solvent removal method can be any conventional method in the art, such as vacuum rotary evaporation; specifically, the temperature during vacuum rotary evaporation can be 20℃~80℃, for example, it can also be selected from 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 75℃. During vacuum rotary evaporation, if the temperature is too low, the reaction rate is too slow; if the temperature is too high, the properties of the coordination polymer nanoparticles are unstable under vacuum, and the groups are easily damaged; the pressure of vacuum rotary evaporation can be any value between 20mbar and 60mbar. For example, it can also be 25mbar, 30mbar, 35mbar, 40mbar, 45mbar, 50mbar, 55mbar; the time of vacuum rotary evaporation can be any value between 30 minutes and 60 minutes, for example, it can also be 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes.

[0072] This invention also provides a Zn-based organic coordination nanoparticle photoresist composition, which comprises the Zn-based organic coordination nanoparticles prepared above, a photoacidifying agent, and an organic dispersing solvent. The Zn-based organic coordination nanoparticles have a mass percentage of 3%-20%, and the photoacidifying agent has a mass percentage of 5%-10%.

[0073] The photoacidifier may be selected from any one or more of N-hydroxynaphthalimide trifluoromethanesulfonic acid, 1,4-aminonaphthalenesulfonic acid, 2-amino-5,7-naphthalenedisulfonic acid, tert-butylphenyliodonium salt perfluorooctanesulfonic acid, triphenylsulfonium perfluorobutanesulfonic acid, triphenylsulfonium perfluorobutyl, and triphenylsulfonium trifluorosulfonic acid. The organic dispersion solvent may be selected from any one or more of ethyl acetate, butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol methyl ether acetate, 1-ethoxy-2-propanol, methanol, ethanol, and propanol.

[0074] Furthermore, the preparation process of the Zn-based organic coordination nanoparticle photoresist composition involves dissolving the obtained nanoparticle composition in an organic dispersion solvent, adding a photoacid, stirring for 5 minutes until completely dissolved, and obtaining a photoresist mixed solution.

[0075] An example of the present invention also provides a method for patterning photoresist, comprising the following steps:

[0076] (1) The photoresist composition is coated on the substrate surface, the organic dispersion solvent is removed, and a pre-formed film layer is formed on the substrate surface;

[0077] (2) Exposure operation is performed by shining a light source through a mask onto the pre-formed film layer of the substrate, so that photoresist particle agglomerates are formed in the exposure area of ​​the pre-formed film layer.

[0078] (3) Apply developer to the exposed pre-film layer so that the unexposed area of ​​the pre-film layer that is covered by the mask dissolves in the developer, while the exposed area of ​​the pre-film layer remains on the substrate due to the formation of photoresist particle agglomerates.

[0079] In step (2), the exposure conditions can be selected from any one of mid-ultraviolet, electron beam, or extreme ultraviolet. Furthermore, regarding the mask, deep ultraviolet and longer wavelength light sources are used as transmission masks, extreme ultraviolet is used as a reflection mask, and the electron beam is used for exposure according to the pattern set in the software. The substrate is selected from silicon wafers, but other substrates insoluble in developer can also be selected according to actual needs.

[0080] Furthermore, the exposure dose of the exposure operation is 50 mJ / cm². 2 ~500mJ / cm 2 The exposure dose should be controlled within a suitable range. Too low an exposure dose results in insufficient energy, which is detrimental to the polymerization of photoresist particles in the exposed area, hindering the formation of a solubility difference between the exposed and unexposed areas, leading to poor development. Compared to bare metal nanoparticles, nanoparticles containing organic ligands polymerize more easily. Excessive exposure dose may cause the organic ligands to detach directly from the metal oxide, forming fragments. This prevents the photoresist particles from undergoing the organic ligand exchange reaction, reducing the degree of polymerization in the exposed area.

[0081] In step (3), the developer is selected from any one or more mixtures of decahydronaphthalene, tetrahydronaphthalene, indene, indene, quinoline, 1-methylnaphthalene, toluene, o-xylene, m-xylene, p-xylene, ethyl acetate, butyl acetate, ethanol, n-propanol, isopropanol, n-butanol, n-hexane, and cyclohexane. In some embodiments, the developing temperature can be room temperature, for example, 20°C to 50°C.

[0082] The developer is primarily used to dissolve unaggregated coordination polymer nanoparticles. In the exposed area, the organic ligands in the coordination polymer nanoparticles interact with the ligands generated by the photoacid, causing a change in polarity and resulting in aggregation, forming aggregates. These aggregates in the exposed area are either insoluble in the developer or have low solubility in the developer, ensuring that even partial dissolution allows the exposed area to remain covered by the aggregates. The developer and the organic dispersion solvent in the photoresist composition can be the same or different. Preferably, the solubility of the coordination polymer in the developer is less than its solubility in the organic dispersion solvent, preventing insufficient polymerization of the coordination polymer after exposure, which could lead to dissolution or partial dissolution of the exposed area, resulting in inaccurate exposure patterns.

[0083] In step (3), the thickness of the pre-formed film after removing the organic dispersion solvent can be 10 nm to 100 nm. Specifically, the thickness of the pre-formed film can be 10 nm to 20 nm, 20 nm to 30 nm, 30 nm to 40 nm, 40 nm to 50 nm, 50 nm to 60 nm, 60 nm to 70 nm, 70 nm to 80 nm, 80 nm to 90 nm, or 90 nm to 100 nm.

[0084] The present invention also provides a method for forming a printed circuit board, comprising the following steps: (1) preparing a pre-patterned substrate having a patterned photoresist layer on a silicon substrate according to the patterning method of the photoresist described above; (2) etching the pre-patterned substrate using a dry or wet method.

[0085] The following detailed explanation is provided with reference to specific embodiments:

[0086] Example 1

[0087] (1) Preparation of Zn-based organic coordination nanoparticles: 4.396 g (36 mmol) of benzoic acid and 2.678 g (27 mmol) of N-methylpiperidine were added to a flask and mixed. 15 mL of ethyl acetate was added, and the mixture was stirred for 5 min to dissolve the particles. The resulting solution was defined as A. 3.951 g (18 mmol) of zinc acetate dihydrate was added to a flask, and 30 mL of ethyl acetate was added. The resulting solution was defined as B. Solution A was added dropwise to solution B in the flask, and the mixture was stirred at 65 °C for 16 h. After the reaction was completed, the mixture was rotary evaporated at 50 °C for 40 min under a pressure of 40 mbar to obtain the synthesized product. A suitable amount of the product was subjected to dynamic light scattering particle size distribution (DLS) testing, and the particle size distribution curve of the product was measured (e.g., ...). Figure 1 As shown), from Figure 1 It can be seen that the average particle size of the suspended particles in the synthesized product is 1.5 nm, and the particle size distribution range is relatively narrow, indicating that the particle size uniformity of the nanoparticles is good. Furthermore, the structural composition of the synthesized product was determined. Figure 2 The basic structural unit of the synthesized product is Zn(C6H5COO)2(CH3COO)(CH3C5H 10 N)H, Figure 3 This is a one-dimensional repeating chain structure formed by the aggregation of this basic structural unit, with the structure [Zn(C6H5COO)2(CH3COO)(CH3C5H 10 N)H] n .

[0088] (2) Preparation of Zn-based organic coordination nanoparticle photoresist composition: Take 0.5g of the Zn-based organic coordination nanoparticles prepared above, select 0.05g of N-hydroxynaphthalimide trifluoromethanesulfonic acid, dissolve the Zn-based organic coordination nanoparticles and N-hydroxynaphthalimide trifluoromethanesulfonic acid in 9.45g of propylene glycol monomethyl ether acetate, and prepare Zn-based organic coordination nanoparticle photoresist composition.

[0089] (3) Preparation of Zn-based organic coordination nanoparticle photoresist coating: Take the Zn-based organic coordination nanoparticle photoresist solution prepared in step (2), coat it on a 2-inch silicon wafer at a speed of 2000 rpm for 1 min, and then bake it at 80℃ for 1 min to obtain a Zn-based organic coordination nanoparticle photoresist pre-film layer with a thickness of 30 nm.

[0090] (4) Exposure of Zn-based organic coordination nanoparticle photoresist coating: Exposure is performed under 254 nm medium ultraviolet light. The light source is irradiated onto the pre-formed film layer on the substrate through a mask to perform the exposure operation, so that photoresist particle agglomerates are formed in the exposure area of ​​the pre-formed film layer. The substrate is selected from silicon substrate, and the exposure dose of the exposure operation is 150 mJ / cm. 2Alternatively, exposure can be performed under an electron beam at a dose of 190 μC / cm². 2 .

[0091] (5) Development: Decahydronaphthalene is selected as the developer and applied to the pre-formed film after exposure. This allows the unexposed areas of the pre-formed film that are covered by the mask to dissolve in the developer, while the exposed areas of the pre-formed film remain on the substrate due to the formation of photoresist particle agglomerates. The development temperature is room temperature 26°C.

[0092] Figure 4 The exposure pattern of the photoresist prepared in this example after exposure under mid-ultraviolet light is shown. It can be seen that the exposure linewidth is 10μm, the exposure pattern lines are clear, the edge roughness is low, which fully meets the requirements of mid-ultraviolet lithography, and the exposure quality is higher than that of the traditional CAR system. Figure 5 The image shows the 50nm linewidth exposure lines obtained after electron beam exposure of photoresist prepared from Zn-based organic coordination nanoparticles. As can be seen from the image, the lithographic patterns are very clear and can meet the requirements of 50nm exposure patterns, making it suitable for use as an electron beam photoresist.

[0093] Example 2

[0094] (1) Preparation of Zn-based organic coordination nanoparticles: 4.396 g (36 mmol) of benzoic acid and 2.299 g (27 mmol) of N-methylpyrrolidine were added to a flask and mixed. 15 mL of ethyl acetate was added, and the mixture was stirred for 5 min to dissolve the particles. The resulting solution was defined as A. 3.951 g (18 mmol) of zinc acetate dihydrate was added to the flask, and 30 mL of ethyl acetate was added. The resulting solution was defined as B. Solution A was added dropwise to solution B in the flask, and the mixture was stirred at 65 °C for 16 h. After the reaction was completed, the mixture was rotary evaporated at 50 °C for 40 min under a pressure of 40 mbar to obtain the synthesized product. A suitable amount of the product was subjected to dynamic light scattering particle size distribution (DLS) testing, and the particle size distribution curve of the product was measured (e.g., ...). Figure 6 As shown), from Figure 6 It can be seen that the average particle size of the suspended particles in the synthesized product is 1.9 nm, and the particle size distribution range is relatively narrow, indicating good particle size uniformity. Nuclear magnetic resonance (NMR) tests were performed on the prepared nanoparticles; the 1H NMR data are shown in the appendix. Figure 7 )for: 1¹H NMR (400MHz, DMSO-d⁶) δ 7.97–7.89 (m), 7.51–7.35 (m), 2.68 (d, J = 6.9 Hz), 2.41 (s), 1.86 (s), 1.59 (p, J = 5.7 Hz), 1.45–1.36 (m); the peaks in the N-methylpiperidine structure shifted from 1.34, 1.47, 2.10, and 2.22 to 1.40 and 1.5, respectively. The positions of 9, 2.41, and 2.68; the peak of the methyl group in zinc acetate shifted from 1.82 to 1.86; the peak of the benzene ring in benzoic acid also shifted from 7.51, 7.63, and 7.95 to 7.39, 7.47, and 7.93. In the prepared nanoparticles, each monomer is coordinated separately. Calculations show that the basic structural unit of the prepared nanoparticles is Zn(C6H5COO)2(CH3COO)(CH3C4H8N) (as shown in the figure). Figure 8 As shown in the figure, the formed one-dimensional repeating chain-like nano-organic structure is [Zn(C6H5COO)2(CH3COO)(CH3C4H8N)]. n like Figure 9 As shown.

[0095] (2) Preparation of Zn-based organic coordination nanoparticle photoresist composition: Take 0.5g of the Zn-based organic coordination nanoparticles prepared above, select 0.05g of N-hydroxynaphthalimide trifluoromethanesulfonic acid, dissolve the Zn-based organic coordination nanoparticles and N-hydroxynaphthalimide trifluoromethanesulfonic acid in 9.45g of propylene glycol monomethyl ether acetate, and prepare Zn-based organic coordination nanoparticle photoresist composition.

[0096] (3) Preparation of Zn-based organic coordination nanoparticle photoresist coating: Take the Zn-based organic coordination nanoparticle photoresist solution prepared in step (2), coat it on a 2-inch silicon wafer at a speed of 2000 rpm for 1 min, and then bake it at 80℃ for 1 min to obtain a Zn-based organic coordination nanoparticle photoresist pre-film layer with a thickness of 30 nm.

[0097] (4) Exposure of Zn-based organic coordination nanoparticle photoresist coating: Exposure is performed under 254 nm medium ultraviolet light. The light source is irradiated onto the pre-formed film layer on the substrate through a mask to perform the exposure operation, so that photoresist particle agglomerates are formed in the exposure area of ​​the pre-formed film layer. The substrate is selected from silicon substrate, and the exposure dose of the exposure operation is 150 mJ / cm. 2 Alternatively, exposure can be performed under an electron beam at a dose of 190 μC / cm². 2 .

[0098] (5) Development: Decahydronaphthalene is selected as the developer and applied to the pre-formed film after exposure. This allows the unexposed areas of the pre-formed film that are covered by the mask to dissolve in the developer, while the exposed areas of the pre-formed film remain on the substrate due to the formation of photoresist particle agglomerates. The development temperature is room temperature 26°C.

[0099] Figure 10 The exposure pattern of the photoresist prepared in this example after exposure under mid-ultraviolet light is shown. It can be seen that the exposure linewidth is 10μm, the exposure pattern lines are clear, the edge roughness is low, which fully meets the requirements of mid-ultraviolet lithography, and the exposure quality is higher than that of the traditional CAR system. Figure 11 The image shows the 50nm linewidth exposure lines obtained after electron beam exposure of photoresist prepared from Zn-based organic coordination nanoparticles. As can be seen from the image, the lithographic patterns are very clear and can meet the requirements of 50nm exposure patterns, making it suitable for use as an electron beam photoresist.

[0100] Example 3

[0101] (1) Preparation of Zn-based organic coordination nanoparticles: 4.936 g (36 mmol) of m-methylbenzoic acid and 2.678 g (27 mmol) of N-methylpiperidine were added to a flask and mixed. 15 mL of ethyl acetate was added, and the mixture was stirred for 5 min to dissolve the particles. The resulting solution was defined as A. 3.951 g (18 mmol) of zinc acetate dihydrate was added to a flask, and 30 mL of ethyl acetate was added. The resulting solution was defined as B. Solution A was added dropwise to solution B in the flask, and the mixture was stirred at 65 °C for 16 h. After the reaction was completed, the mixture was rotary evaporated at 50 °C for 40 min under a pressure of 40 mbar to obtain the synthesized product. A suitable amount of the product was subjected to dynamic light scattering particle size distribution (DLS) testing, and the particle size distribution curve of the product was measured (e.g., ...). Figure 12 As shown), from Figure 12 It can be seen that the average particle size of the suspended particles in the synthesized product is 1.7 nm, and the particle size distribution range is relatively narrow, indicating good particle size uniformity. Nuclear magnetic resonance (NMR) tests were performed on the prepared nanoparticles; the 1H NMR data are shown in the appendix. Figure 13 )for: 1¹H NMR (400MHz, DMSO-d⁶) δ 7.96–7.89 (m), 7.52–7.43 (m), 7.40 (ddt, J = 8.3, 6.7, 1.4 Hz), 2.68 (d, J = 6.9 Hz), 2.41 (s), 1.86 (s), 1.59 (p, J = 5.7 Hz), 1.46–1.33 (m); N-methylpiperidine structure The peaks in the [unspecified] group shifted from 1.34, 1.47, 2.10, and 2.22 to 1.40, 1.58, 2.39, and 2.65, respectively; the methyl peak in zinc acetate shifted from 1.82 to 1.86; and the methyl peak in m-methylbenzoic acid shifted from 2.37 to 2.33, while the benzene ring peak shifted from 7.39, 7.44, and 7.76 to 7.40, 7.46, and 7.93. In the prepared nanoparticles, each monomer was coordinated separately. Calculations showed that the basic structural unit of the prepared nanoparticles was Zn(CH3C6H5COO)2(CH3COO)(CH3C5H 10 N)( Figure 14 As shown), the one-dimensional repeating chain-like nano-organic structure formed is [Zn(CH3C6H5COO)2(CH3COO)(CH3C5H 10 N)] n like Figure 15 As shown.

[0102] (2) Preparation of Zn-based organic coordination nanoparticle photoresist composition: Take 0.5g of the Zn-based organic coordination nanoparticles prepared above, select 0.05g of N-hydroxynaphthalimide trifluoromethanesulfonic acid, dissolve the Zn-based organic coordination nanoparticles and N-hydroxynaphthalimide trifluoromethanesulfonic acid in 9.45g of propylene glycol monomethyl ether acetate, and prepare Zn-based organic coordination nanoparticle photoresist composition.

[0103] (3) Preparation of Zn-based organic coordination nanoparticle photoresist coating: Take the Zn-based organic coordination nanoparticle photoresist solution prepared in step (2), coat it on a 2-inch silicon wafer at a speed of 2000 rpm for 1 min, and then bake it at 80℃ for 1 min to obtain a Zn-based organic coordination nanoparticle photoresist pre-film layer with a thickness of 30 nm.

[0104] (4) Exposure of Zn-based organic coordination nanoparticle photoresist coating: Exposure is performed under 254 nm medium ultraviolet light. The light source is irradiated onto the pre-formed film layer on the substrate through a mask to perform the exposure operation, so that photoresist particle agglomerates are formed in the exposure area of ​​the pre-formed film layer. The substrate is selected from silicon substrate, and the exposure dose of the exposure operation is 150 mJ / cm. 2 Alternatively, exposure can be performed under an electron beam at a dose of 150 μC / cm². 2 .

[0105] (5) Development: Decahydronaphthalene is selected as the developer and applied to the pre-formed film after exposure. This allows the unexposed areas of the pre-formed film that are covered by the mask to dissolve in the developer, while the exposed areas of the pre-formed film remain on the substrate due to the formation of photoresist particle agglomerates. The development temperature is room temperature 26°C.

[0106] Figure 16 The exposure pattern of the photoresist prepared in this example after exposure under mid-ultraviolet light is shown. It can be seen that the exposure linewidth is 10μm, the exposure pattern lines are clear, the edge roughness is low, which fully meets the requirements of mid-ultraviolet lithography, and the exposure quality is higher than that of the traditional CAR system. Figure 17 The image shows the 50nm linewidth exposure lines obtained after electron beam exposure of photoresist prepared from Zn-based organic coordination nanoparticles. As can be seen from the image, the lithographic patterns are very clear and can meet the requirements of 50nm exposure patterns, making it suitable for use as an electron beam photoresist.

[0107] Example 4

[0108] (1) Preparation of Zn-based organic coordination nanoparticles: 4.936 g (36 mmol) of m-methylbenzoic acid and 2.705 g (27 mmol) of cyclohexylimine were added to a flask and mixed. 15 mL of ethyl acetate was added, and the mixture was stirred for 5 min to dissolve the nanoparticles. The resulting solution was defined as A. 3.951 g (18 mmol) of zinc acetate dihydrate was added to a flask, and 30 mL of ethyl acetate was added. The resulting solution was defined as B. Solution A was added dropwise to solution B in the flask, and the mixture was stirred at 65 °C for 16 h. After the reaction was completed, the mixture was rotary evaporated at 50 °C for 40 min under a pressure of 40 mbar to obtain the synthesized product. A suitable amount of the product was subjected to dynamic light scattering particle size distribution (DLS) testing, and the particle size distribution curve of the product was obtained (e.g., ...). Figure 18 As shown), from Figure 18 It can be seen that the average particle size of the suspended particles in the synthesized product is 2.4 nm, and the particle size distribution range is relatively narrow, indicating good particle size uniformity. Nuclear magnetic resonance (NMR) tests were performed on the prepared nanoparticles; the 1H NMR data are shown in the appendix. Figure 19 )for: 1¹H NMR (400MHz, DMSO-d⁶) δ 7.75 (d, J = 1.9Hz), 7.71 (tt, J = 4.4, 3.4Hz), 7.30–7.20 (m), 3.07–3.00 (m), 2.33 (s), 1.84 (s), 1.75–1.64 (m), 1.62–1.51 (m); The NMR spectra show that after the synthesis of nanoparticles, each… The monomers underwent coordination, resulting in peak shifts. The peaks in the cyclohexylimine structure shifted from 1.52 and 2.68 to 1.56, 1.70, and 3.03, respectively; the methyl peak in zinc acetate shifted from 1.82 to 1.84; and the methyl peak in m-methylbenzoic acid shifted from 2.37 to 2.33, while the benzene ring peaks shifted from 7.39, 7.44, and 7.76 to 7.25, 7.75, and 7.71. In the prepared nanoparticles, each monomer underwent coordination. Calculations showed that the basic structural unit of the prepared Zn-based organic coordination nanoparticles was Zn(CH3C6H5COO)2(CH3COO)(C6H 14 N).

[0109] (2) Preparation of Zn-based organic coordination nanoparticle photoresist composition: Take 0.5g of the Zn-based organic coordination nanoparticles prepared above, select 0.05g of N-hydroxynaphthalimide trifluoromethanesulfonic acid, dissolve the Zn-based organic coordination nanoparticles and N-hydroxynaphthalimide trifluoromethanesulfonic acid in 9.45g of propylene glycol monomethyl ether acetate, and prepare Zn-based organic coordination nanoparticle photoresist composition.

[0110] (3) Preparation of Zn-based organic coordination nanoparticle photoresist coating: Take the Zn-based organic coordination nanoparticle photoresist solution prepared in step (2), coat it on a 2-inch silicon wafer at a speed of 2000 rpm for 1 min, and then bake it at 80℃ for 1 min to obtain a Zn-based organic coordination nanoparticle photoresist pre-film layer with a thickness of 30 nm.

[0111] (4) Exposure of Zn-based organic coordination nanoparticle photoresist coating: Exposure is performed under 254 nm medium ultraviolet light. The light source is irradiated onto the pre-formed film layer on the substrate through a mask to perform the exposure operation, so that photoresist particle agglomerates are formed in the exposure area of ​​the pre-formed film layer. The substrate is selected from silicon substrate, and the exposure dose of the exposure operation is 150 mJ / cm. 2 Alternatively, exposure can be performed under an electron beam, with an exposure dose of 200 μC / cm². 2 .

[0112] (5) Development: Decahydronaphthalene is selected as the developer and applied to the pre-formed film after exposure. This allows the unexposed areas of the pre-formed film that are covered by the mask to dissolve in the developer, while the exposed areas of the pre-formed film remain on the substrate due to the formation of photoresist particle agglomerates. The development temperature is room temperature 26°C.

[0113] Figure 20 The exposure pattern of the photoresist prepared in this example after exposure under mid-ultraviolet light is shown. It can be seen that the exposure linewidth is 10μm, the exposure pattern lines are clear, the edge roughness is low, which fully meets the requirements of mid-ultraviolet lithography, and the exposure quality is higher than that of the traditional CAR system. Figure 21 The image shows the 50nm linewidth exposure lines obtained after electron beam exposure of photoresist prepared from Zn-based organic coordination nanoparticles. As can be seen from the image, the lithographic patterns are very clear and can meet the requirements of 50nm exposure patterns, making it suitable for use as an electron beam photoresist.

[0114] Example 5

[0115] (1) Preparation of Zn-based organic coordination nanoparticles: 4.936 g (36 mmol) of m-methylbenzoic acid and 2.299 g (27 mmol) of N-methylpyrrolidine were added to a flask and mixed. 15 mL of ethyl acetate was added, and the mixture was stirred for 5 min to dissolve the particles. The resulting solution was defined as A. 3.951 g (18 mmol) of zinc acetate dihydrate was added to a flask, and 30 mL of ethyl acetate was added. The resulting solution was defined as B. Solution A was added dropwise to solution B in the flask, and the mixture was stirred at 65 °C for 16 h. After the reaction was completed, the mixture was rotary evaporated at 50 °C for 40 min under a pressure of 40 mbar to obtain the synthesized product. A suitable amount of the product was subjected to dynamic light scattering particle size distribution (DLS) testing, and the particle size distribution curve of the product was measured (e.g., ...). Figure 22 As shown), from Figure 22 It can be seen that the average particle size of the suspended particles in the synthesized product is 2.0 nm, and the particle size distribution range is relatively narrow, indicating good particle size uniformity. Nuclear magnetic resonance (NMR) tests were performed on the prepared nanoparticles; the 1H NMR data are shown in the appendix. Figure 23 )for: 1¹H NMR (400MHz, DMSO-d⁶) δ 7.75(s), 7.72(t, J=4.7Hz), 7.29(d, J=4.7Hz), 2.77(d, J=6.5Hz), 2.50–2.42(m), 2.34(s), 1.86(s), 1.84–1.75(m); The NMR spectra show that after the synthesis of nanoparticles, each monomer was separately formulated... The peaks shifted, with the peaks in the methylpyrrolidine structure shifting from 1.67, 2.22, and 2.34 to 1.80, 2.46, and 2.77, respectively; the methyl peak in zinc acetate shifted from 1.82 to 1.86; and the methyl peak in m-methylbenzoic acid shifted from 2.35 to 2.34, while the benzene ring peak shifted from 7.39, 7.44, and 7.76 to 7.29, 7.72, and 7.75. In the prepared nanoparticles, each monomer was coordinated separately. Calculations showed that the basic structural unit of the prepared nanoparticles was Zn(CH3C6H5COO)2(CH3COO)(CH3C4H8N)H (see Appendix). Figure 24 The resulting one-dimensional repeating chain-like nano-organic structure is shown in the appendix. Figure 25 .

[0116] (2) Preparation of Zn-based organic coordination nanoparticle photoresist composition: Take 0.5g of the Zn-based organic coordination nanoparticles prepared above, select 0.05g of N-hydroxynaphthalimide trifluoromethanesulfonic acid, dissolve the Zn-based organic coordination nanoparticles and N-hydroxynaphthalimide trifluoromethanesulfonic acid in 9.45g of propylene glycol monomethyl ether acetate, and prepare Zn-based organic coordination nanoparticle photoresist composition.

[0117] (3) Preparation of Zn-based organic coordination nanoparticle photoresist coating: Take the Zn-based organic coordination nanoparticle photoresist solution prepared in step (2), coat it on a 2-inch silicon wafer at a speed of 2000 rpm for 1 min, and then bake it at 80℃ for 1 min to obtain a Zn-based organic coordination nanoparticle photoresist pre-film layer with a thickness of 30 nm.

[0118] (4) Exposure of Zn-based organic coordination nanoparticle photoresist coating: Exposure is performed under 254 nm medium ultraviolet light. The light source is irradiated onto the pre-formed film layer on the substrate through a mask to perform the exposure operation, so that photoresist particle agglomerates are formed in the exposure area of ​​the pre-formed film layer. The substrate is selected from silicon substrate, and the exposure dose of the exposure operation is 150 mJ / cm. 2 Alternatively, exposure can be performed under an electron beam at a dose of 270 μC / cm². 2 .

[0119] (5) Development: Decahydronaphthalene is selected as the developer and applied to the pre-formed film after exposure. This allows the unexposed areas of the pre-formed film that are covered by the mask to dissolve in the developer, while the exposed areas of the pre-formed film remain on the substrate due to the formation of photoresist particle agglomerates. The development temperature is room temperature 26°C.

[0120] Figure 26 The exposure pattern of the photoresist prepared in this example after exposure under mid-ultraviolet light is shown. It can be seen that the exposure linewidth is 10μm, the exposure pattern lines are clear, the edge roughness is low, which fully meets the requirements of mid-ultraviolet lithography, and the exposure quality is higher than that of the traditional CAR system. Figure 27 The image shows the 50nm linewidth exposure lines obtained after electron beam exposure of photoresist prepared from Zn-based organic coordination nanoparticles. As can be seen from the image, the lithographic patterns are very clear and can meet the requirements of 50nm exposure patterns, making it suitable for use as an electron beam photoresist.

[0121] Table 1. Characteristics of Zn-based organic coordination nanoparticles prepared in Examples 1-5 of this invention.

[0122]

[0123]

[0124] Table 2. Photolithographic properties of the Zn-based organic coordination nanoparticle photoresist compositions prepared in Examples 1-5 of this invention.

[0125]

[0126] Currently, domestic companies engaged in the R&D and industrialization of semiconductor photoresists primarily produce photoresists used in integrated circuit processes of 350nm and above. However, ArF photoresists used in 193nm processes are still in their early stages, and high-end ArF photoresists are largely dependent on imports. Therefore, the Zn-based organic coordination nanoparticles provided in this invention, when used as photoresist materials for photolithography, can achieve superior pattern resolution compared to existing technologies, representing a significant advancement in the self-sufficiency of photoresists.

[0127] In addition, compared with polymer photoresists and molecular glass photoresists, the presence of metal elements gives the photoresist of the present invention superior etching resistance.

[0128] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0129] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A Zn-based organic coordination nanoparticle, characterized in that, The nanoparticles are metal-organic one-dimensional repeating chain structures with the general formula [ZnX2(CH3COO)Y]. n Wherein, X is selected from benzoate or m-methylbenzoate, Y is selected from organic amine ligands, the size of the nanoparticles is 1nm~4nm, n is the degree of polymerization, n is greater than or equal to 1, and the organic amine ligands are selected from N-methylpiperidine, N-methylpyrrolidine, cycloheximine or methylpyrrolidine; The nanoparticles have one of the following general structural formulas: [Zn(C6H5COO)2(CH3COO)(CH3C5H 10 N)H] n ; [Zn(C6H5COO)2(CH3COO)(CH3C4H8N)] n ; [Zn(CH3C6H5COO)2(CH3COO)(CH3C5H 10 N)] n ; [Zn(CH3C6H5COO)2(CH3COO)(C6H 14 N)] n ; [Zn(CH3C6H5COO)2(CH3COO)(CH3C4H8N)H] n 。 2. A method for preparing Zn-based organic coordination nanoparticles as described in claim 1, characterized in that, Includes the following steps: (1) A zinc metal salt solution is obtained by mixing a zinc metal salt with an organic solvent; (2) The zinc metal salt solution is mixed with the first organic ligand and the second organic ligand, and the mixture is heated and stirred to carry out the reaction; (3) Remove residual solvent from the product after the reaction; In step (3), the solvent removal method is vacuum rotary evaporation, the temperature is 20℃~80℃, the vacuum rotary evaporation pressure is 20mbar~60mbar, and the vacuum rotary evaporation time is 30 min~60 min.

3. The method according to claim 2, characterized in that, The first organic ligand is benzoic acid or m-methylbenzoic acid, and the second organic ligand is selected from N-methylpiperidine, N-methylpyrrolidine, cycloheximine or methylpyrrolidine.

4. The method according to claim 2, characterized in that, The molar ratio of the zinc metal salt, the first organic ligand, and the second organic ligand is (0.2~1):(0.4~1):(0.3~1).

5. The method according to claim 2, characterized in that, The molar ratio of the zinc metal salt, the first organic ligand, and the second organic ligand is 1:(3~5):(2~5).

6. The method according to claim 2, characterized in that, In step (2), the heating and stirring temperature range is 50℃~80℃, and the time is 10h~40h.

7. The method according to claim 2, characterized in that, In step (3), the solvent removal method is vacuum rotary evaporation, the temperature is 30℃~70℃, the vacuum rotary evaporation pressure is 30mbar~50mbar, and the vacuum rotary evaporation time is 30 min~50 min.

8. A Zn-based organic coordination nanoparticle, characterized in that, Obtained by the preparation method according to any one of claims 2-7.

9. A Zn-based organic coordination nanoparticle photoresist composition, characterized in that, The mixture includes the Zn-based organic coordination nanoparticles as described in claim 1 or 8, a photoacidifying agent, and an organic dispersing solvent, wherein the Zn-based organic coordination nanoparticles have a mass percentage of 3%-20%, and the photoacidifying agent has a mass percentage of 5%-10%.

10. The photoresist composition according to claim 9, characterized in that, The photoacid is selected from any one or more of N-hydroxynaphthalimide trifluoromethanesulfonic acid, 1,4-aminonaphthalenesulfonic acid, 2-amino-5,7-naphthalenedisulfonic acid, tert-butylphenyliodonium salt perfluorooctanesulfonic acid, triphenylsulfonium perfluorobutanesulfonic acid, triphenylsulfonium perfluorobutyl, and triphenylsulfonium trifluorosulfonic acid; the organic dispersion solvent is selected from any one or more of ethyl acetate, butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol methyl ether acetate, 1-ethoxy-2-propanol, methanol, ethanol, and propanol.

11. A method for preparing a Zn-based organic coordination nanoparticle photoresist composition, characterized in that, include: Dissolve the nanoparticles described in claim 1 or 8 in an organic dispersion solvent, then add a photoacid, stir for 5 minutes until completely dissolved, to obtain a photoresist composition.

12. A method for patterning photoresist, characterized in that, Includes the following steps: (1) The photoresist composition of claim 9 or 10 is coated on the substrate surface, the organic dispersion solvent is removed, and a pre-formed film layer is formed on the substrate surface; (2) Exposure operation is performed by shining a light source through a mask onto the pre-formed film layer of the substrate, so that photoresist particles agglomerate in the exposure area of ​​the pre-formed film layer; (3) Apply developer to the pre-formed film after exposure, so that the unexposed area of ​​the pre-formed film that is covered by the mask dissolves in the developer, while the exposed area of ​​the pre-formed film remains on the substrate due to the formation of photoresist particle agglomerates.

13. The method of claim 12, characterized in that, Exposure conditions are selected from any one of mid-ultraviolet, electron beam, or extreme ultraviolet, with an ultraviolet light exposure dose of 50 mJ / cm². 2 ~500 mJ / cm 2 The electron beam exposure dose was 50 μC / cm. 2 ~500μC / cm 2 The thickness of the pre-formed film after removing the organic dispersion solvent is 10nm~100nm.

14. A method for forming a printed circuit board, characterized in that, Includes the following steps: (1) A pre-patterned substrate having a patterned photoresist layer on a silicon substrate is prepared according to the patterning method of photoresist according to claim 12 or 13; (2) The pre-patterned substrate is etched using a dry or wet method.

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