Zn-based organic coordination nanoparticles, methods for producing the same, photoresist compositions containing the same, and uses thereof

Abstract

The present invention relates to Zn-based organic coordination nanoparticles, a method for producing the same, a photoresist composition containing the same, and use thereof. The Zn-based organic coordination nanoparticles are obtained by mixing and stirring a zinc-containing compound, preferably zinc acetate, benzoic acid, and a nitrogen-containing organic ligand in an organic solvent, followed by post-treatment. The nanoparticles are also prepared by the method described above. m X n (CH3COO) t Y p H q ] r Here, X is a benzoate ion, CH3COO is an acetate ion, Y is a nitrogen-containing organic ligand, r is the degree of polymerization, m, n, p, q, and r are each independently an integer selected from 1 to 20, and t is an integer selected from 0 to 20. By using the Zn-based organic coordination nanoparticles of the present invention as a photoresist component, better photolithography performance such as high resolution, high sensitivity, and low line roughness can be achieved.

Description

[Technical Field]

[0001] The present invention relates to the art of photoresists, and more particularly to Zn-based organic coordination nanoparticles, methods for producing the same, photoresist compositions containing the same, and uses thereof. [Background technology]

[0002] Photolithography is a core technology in chip manufacturing, accounting for more than one-third of the total cost of chip production. The photolithography process is as follows: Photoresist coated on a substrate is excited by light passing through a mask, causing a change in solubility between the irradiated and unirradiated areas. The mask pattern is then negatively or positively etched, and through subsequent processes, the pattern on the substrate is fabricated into an integrated circuit. When the wavelength of photolithography is fixed, the photoresist determines the quality of the photolithography. With the continuous development of photolithography technology, the linewidth of the light source continues to decrease, and for photolithography below 7nm, 13.5nm extreme ultraviolet light source exposure technology is gradually becoming the main option.

[0003] Photoresist is a corrosion-resistant thin-film material whose solubility changes upon irradiation with ultraviolet light, electron beams, particle beams, extreme ultraviolet (EUV), or soft X-rays. It is widely used for pattern transfer in the manufacturing processes of high-end micro- and nanostructures, such as semiconductor integrated circuits, liquid crystal panel processing, and the production of high-end optical devices. Due to the continuous advancement of semiconductor technology and the development of Moore's Law, semiconductor manufacturing processes are constantly becoming smaller, and as a result, there is a high demand for reducing the size of processed features. In order to meet the demands of more advanced semiconductor manufacturing processes and achieve smaller feature sizes, photolithography technology has also developed, progressing from I-line, G-line, deep ultraviolet (DUV), 193nm, and immersion 193nm to microfabrication techniques such as extreme ultraviolet lithography and electron beam lithography.

[0004] Conventional photoresists have complex compositions, including the photoresist resin itself, photosensitive agents, leveling agents, stabilizers, dispersants, thickeners, and solvents. This results in a complicated production process and extremely high control requirements for formulation and purity. Conventional photoresists are mostly high-molecular-weight polymers containing many functional additives. Their complex composition leads to a wide size distribution, with components of various sizes, some reaching 10nm to 20nm. This makes controlling the size of the photoresist pattern difficult and can result in numerous defects. Furthermore, the usability of conventional photoresists is heavily influenced by the wavelength of the light source, requiring different photoresists for different light sources.

[0005] Extreme ultraviolet (EUV) lithography is attracting attention as a fundamental technology for next-generation semiconductor device manufacturing. EUV lithography is a patterning technique that uses EUV light with a wavelength of approximately 13.5 nm as the exposure light source. As can be seen from EUV lithography, it is possible to form extremely fine patterns (for example, less than approximately 20 nm) in the exposure process during semiconductor device manufacturing.

[0006] However, conventional photolithography techniques produce patterns with high edge roughness and low resolution, making them unsuitable for application, and this needs to be improved. [Overview of the project] [Problems that the invention aims to solve]

[0007] Based on this, there is a need to provide Zn-based organic coordination nanoparticles, a method for producing the same, a photoresist composition containing the nanoparticles, and a use thereof, in order to address the problem of high edge roughness and low pattern resolution in patterns obtained by conventional photoresistography. [Means for solving the problem]

[0008] According to a first aspect of the present invention, Zn-based organic coordination nanoparticles are provided that are produced by the following method. Specifically, a zinc-containing compound, benzoic acid, and a nitrogen-containing organic ligand are mixed and stirred in an organic solvent, and then post-treated to obtain the nanoparticles. Here, the molar ratio of the zinc-containing compound, benzoic acid, and nitrogen-containing organic ligand is (2-10):(4-10):(2-10). Furthermore, the nitrogen-containing organic ligand is one or more selected from organoliphatic amines and their derivatives, pyridine and its derivatives, pyrrole and its derivatives, pyrimidine and its derivatives, pyridazine and its derivatives, piperidine and its derivatives, amides and their derivatives. The zinc-containing compound, for example, a soluble salt containing zinc, is, for example, zinc acetate, zinc acetate dihydrate, zinc chloride, or zinc sulfate, and is preferably zinc acetate or zinc acetate dihydrate.

[0009] Furthermore, the organoaliphatic amines are one or more selected from triisopropylamine, triethanolamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, and diisopropylethylamine. The pyridine and its derivatives are one or more selected from methylpyridine, vinylpyridine, methylpyrrolidine, perhydropyridine, and α-pyridine. The pyrrole and its derivatives are one or more selected from tetrahydropyrrole, methylpyrrole, and vinylpyrrole. The pyridazine and its derivatives are one or more selected from vinylpyridazine and divinylpyridazine. The piperidine and its derivatives are one or more selected from piperidine, vinylpiperidine, and 3-methylpiperidine. The amide and its derivatives are one or more selected from formamide, stearamide, succinamide, oxamide, acrylamide, and nicotinamide.

[0010] Furthermore, the nitrogen-containing organic ligand is selected from diethylamine, piperidine, diisopropylethylamine, or tetrahydropyrrole.

[0011] Furthermore, the post-processing includes stirring at 45°C-80°C for 5-24 hours, followed by rotary evaporation at 40°C-60°C for 20-80 minutes using a rotary evaporator, and then vacuuming in a vacuum oven at 45°C-75°C for 5 hours.

[0012] Furthermore, the organic solvent is one or more selected from ethyl acetate, butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol methyl ether acetate, 1-ethoxy-2 propanol, methanol, ethanol, and propanol.

[0013] The method for producing the Zn-based organic coordination nanoparticles for the aforementioned photoresist is as follows. The zinc-containing compound, benzoic acid, and nitrogen-containing organic ligand are mixed and stirred in an organic solvent, and then post-treated to obtain the nanoparticles. Here, the molar ratio of the zinc-containing compound, benzoic acid, and nitrogen-containing organic ligand is (2-10):(4-10):(2-10). The nitrogen-containing organic ligand is one or more selected from organic aliphatic amines and their derivatives, pyridine and its derivatives, pyrrole and its derivatives, pyrimidine and its derivatives, pyridazine and its derivatives, piperidine and its derivatives, amides and their derivatives. The zinc-containing compound, for example, a soluble salt containing zinc, is, for example, zinc acetate, zinc acetate dihydrate, zinc chloride, or zinc sulfate, and is preferably zinc acetate or zinc acetate dihydrate.

[0014] The present invention provides Zn-based organic coordination nanoparticles. Its chemical formula is [Zn m X n (CH3COO) t Y p H q ] r Here, X is benzoic acid, CH3COO represents the acetate ion, Y is a nitrogen-containing organic ligand, r is the degree of polymerization, m, n, p, q, n, and r are each independently selected integers from 1 to 20, and t is an integer selected from 0 to 20.

[0015] Y is further one or more selected from organic aliphatic amines and their derivatives, pyridine and its derivatives, pyrrole and its derivatives, pyrimidine and its derivatives, pyridazine and its derivatives, piperidine and its derivatives, amides and their derivatives.

[0016] The organic aliphatic amines are one or more selected from triisopropylamine, triethanolamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, diisopropylethylamine. Pyridine and its derivatives are one or more selected from methylpyridine, vinylpyridine, methylpyrrolidine, perhydropyridine, α-pyridine, etc. Pyrrole and its derivatives are one or more selected from tetrahydropyrrole, methylpyrrole, vinylpyrrole. Pyridazine and its derivatives are one or more selected from vinylpyridazine, divinylpyridazine. Piperidine and its derivatives are one or more selected from piperidine, vinylpiperidine, 3-methylpiperidine. Amides and their derivatives are one or more selected from formamide, stearic acid amide, succinic acid amide, oxamide, acrylamide, nicotinamide.

[0017] The Zn-based organic coordination nanoparticles obtained in the present invention have a special structure. Under light irradiation conditions, by interacting with a photoacid generator (photoacid agent), the polarity of the material changes, aggregation occurs, and the solubility of the Zn-based organic coordination nanoparticles changes before and after irradiation. Due to these characteristics, by using the Zn-based organic coordination nanoparticles as a photoresist component, a difference in the solubility of the photoresist in the developer between the photosensitive part and the light-blocking part occurs. The photosensitive part aggregates and its solubility in the developer decreases, while the light-blocking part does not aggregate and dissolves in the developer. After development, the non-exposed area can be removed to obtain a pattern with a desired shape. In particular, this special structure of the Zn-based organic coordination nanoparticles can achieve better photolithography performance such as high resolution, high sensitivity, and low line roughness by using the Zn-based organic coordination nanoparticles of the present invention as a photoresist component compared with conventional polymer-type photoresists and molecular glass photoresists. Also, in the present invention, by introducing a benzoic acid ligand into the Zn-based organic coordination nanoparticles, it was found that the crystallinity of the complex can be effectively reduced, the solubility of the material in organic reagents can be improved, and storage and application become easier.

[0018] Furthermore, Y is selected from diethylamine, piperidine, diisopropylethylamine, and tetrahydropyrrole.

[0019] Furthermore, m, n, p, q, n, r are each independently an integer of 1 - 10, for example, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, and t is 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10.

[0020] Furthermore, the crystal size of the Zn-based organic coordination nanoparticles is 1 nm - 4 nm.

[0021] Furthermore, the Zn-based organic coordination nanoparticles may have the following structure. Zn2(C6H5COO)5(C4H 11 N)H (where C4H 11 N is diethylamine and C6H5COO is a benzoate ion); Zn4(C6H5COO)6(CH3COO)6(C4H9N)4H4 (where C4H9N is tetrahydropyrrole); Zn3(C6H5COO)7(CH3COO)(C5H 11 N)2H2 (where C5H 11 N is piperidine); Zn2(C6H5COO)5(C8H 19 N)H (where C8H 19 N is diisopropylethylamine).

[0022] According to the present invention, a method for manufacturing Zn-based organic coordination nanoparticles is further provided. This manufacturing method includes the following steps. That is, after mixing and stirring a zinc-containing compound, benzoic acid, and a nitrogen-containing organic ligand in an organic solvent, post-treatment is performed to obtain the nanoparticles. Here, the molar ratio of the zinc-containing compound, benzoic acid, and the nitrogen-containing organic ligand is (2-10):(4-10):(2-10). The zinc-containing compound is preferably zinc acetate.

[0023] According to the present invention, a photoresist composition containing the nanoparticles is further provided.

[0024] Furthermore, the photoresist composition further contains a photoacid generator and an organic dispersion solvent. The photoacid generator is preferably 5 wt%-10 wt% of the composition, and the nanoparticles are preferably 3 wt%-20 wt% of the composition.

[0025] Furthermore, the photoacid generator is any one or more selected from N-hydroxynaphthalimide trifluoromethanesulfonic acid, 1,4-aminonaphthalenesulfonic acid, 2-amino-5,7-naphthalenedisulfonic acid, tert-butylphenyl iodonium perfluorooctanesulfonate, triphenylsulfonium perfluorobutanesulfonate, triphenylsulfonium perfluorobutyl, and triphenylsulfonium trifluoromethanesulfonate.

[0026] Furthermore, the organic dispersion solvent is one or more selected from ethyl acetate, butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol methyl ether acetate, 1-ethoxy-2 propanol, methanol, ethanol, and propanol. The solvent is preferably ethyl acetate.

[0027] The present invention further provides a photolithography method that includes using the photoresist composition, dropping the photoresist composition onto a substrate, rotating it, heating it, exposing it with an electron beam, medium ultraviolet light, deep ultraviolet light, or extreme ultraviolet light, and developing it with a developer.

[0028] The exposure limit for medium ultraviolet, deep ultraviolet, or extreme ultraviolet radiation is 50 mJ / cm². 2 ~500 mJ / cm 2 The electron beam exposure dose is 50 μC / cm². 2 ~500 μC / cm 2 Therefore, the exposure level needs to be controlled within an appropriate range. Too little exposure and too little energy are detrimental to the polymerization of photoresist particles in the exposed region, detrimental to the formation of differences in solubility between the exposed and unexposed regions, and result in poor development. Nanoparticles containing organic ligands polymerize more easily than bare metal nanoparticles. If the exposure level is too high, the organic ligands may detach from the metal oxide and become fragments, preventing the photoresist particles from undergoing the exchange reaction with the organic ligand, and reducing the degree of polymerization in the exposed region.

[0029] Furthermore, the developer is a mixture of one or more selected from indene, indan, quinoline, 1-methylnaphthalene, toluene, o-xylene, m-xylene, ethyl acetate, butyl acetate, ethanol, n-propanol, decalin, tetralin, isopropanol, n-butanol, n-hexane, and cyclohexane, and the development temperature is 20°C to 50°C.

[0030] The thickness of the pre-deposited layer after removal of the organic dispersion solvent may be 10 nm to 100 nm. Specifically, the thickness of the pre-deposited layer may 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.

[0031] Furthermore, the aforementioned nanoparticles are used in the field of photoresists, including electron beam, medium ultraviolet, deep ultraviolet, or extreme ultraviolet photoresists.

[0032] The exposure conditions are selected from one of the following: medium ultraviolet, deep ultraviolet, electron beam, or extreme ultraviolet. The photoresist composition of the present invention can be applied to any of these exposure conditions.

[0033] The substrate is selected from silicon plates, and other substrates insoluble in the developer may be used depending on the actual needs.

[0034] Regarding the masks, long-wavelength light sources above deep ultraviolet use transmission masks, and extreme ultraviolet light sources use reflection masks. Electron beams are exposed according to patterns set in the software. [Effects of the Invention]

[0035] The Zn-based organic coordination nanoparticles obtained in this invention have a special structure and, under light irradiation conditions, interact with a photoacid generator (photoacid agent), changing the polarity of the material, causing aggregation, and altering the solubility of the Zn-based organic coordination nanoparticles before and after irradiation. Due to these properties, using Zn-based organic coordination nanoparticles as a photoresist component results in a difference in solubility in the developer between the photosensitive and light-shielded portions of the photoresist. While the photosensitive portion aggregates and its solubility in the developer decreases, the light-shielded portion does not aggregate and dissolves in the developer, allowing for the removal of unexposed areas after development and obtaining a pattern of the desired shape. In particular, the special structure of these Zn-based organic coordination nanoparticles enables superior photolithography performance, such as high resolution, high sensitivity, and low line roughness, compared to conventional polymer-type photoresists and molecular glass photoresists, when using the Zn-based organic coordination nanoparticles of this invention as a photoresist component. Furthermore, in this invention, because benzoic acid and a nitrogen-containing ligand are present together, its stability is improved to some extent compared to benzoic acid and triethylamine ligands, making storage and application easier. [Brief explanation of the drawing]

[0036] [Figure 1] This is a dynamic light scattering diagram of the Zn-based organic coordination nanoparticles of Example 1 of the present invention. [Figure 2A] This shows the nuclear magnetic resonance hydrogen spectra of the Zn-based organic coordination nanoparticles and raw materials of Example 1 of the present invention. [Figure 2B] This is a single crystal pattern of the Zn-based organic coordination nanoparticles according to Example 1 of the present invention. [Figure 3] This is a dynamic light scattering diagram of the Zn-based organic coordination nanoparticles of Example 2 of the present invention. [Figure 4] This is the single crystal pattern of the Zn-based organic coordination nanoparticles in Example 2 of the present invention. [Figure 5] This is a dynamic light scattering diagram of the Zn-based organic coordination nanoparticles of Example 3 of the present invention. [Figure 6A] This shows the nuclear magnetic resonance hydrogen spectra of the Zn-based organic coordination nanoparticles and raw materials of Example 3 of the present invention. [Figure 6B]This is a single crystal pattern of the Zn-based organic coordination nanoparticles according to Example 3 of the present invention. [Figure 7] This is a dynamic light scattering diagram of the Zn-based organic coordination nanoparticles of Example 4 of the present invention. [Figure 8A] This shows the nuclear magnetic resonance hydrogen spectra of the Zn-based organic coordination nanoparticles and raw materials of Example 4 of the present invention. [Figure 8B] This is a single crystal pattern of the Zn-based organic coordination nanoparticles according to Example 4 of the present invention. [Figure 9A] This is the exposure pattern at 254 nm of the Zn-based organic coordination nanoparticles of Example 1 of the present invention. [Figure 9B] This is the exposure pattern of Zn-based organic coordination nanoparticles using an electron beam (E-beam) according to Example 1 of the present invention. [Figure 10A] This is the exposure pattern at 254 nm of the Zn-based organic coordination nanoparticles of Example 2 of the present invention. [Figure 10B] This is the exposure pattern of Zn-based organic coordination nanoparticles using an electron beam (E-beam) in Example 2 of the present invention. [Figure 11A] This is the exposure pattern at 254 nm of the Zn-based organic coordination nanoparticles of Example 3 of the present invention. [Figure 11B] This is the exposure pattern of Zn-based organic coordination nanoparticles using an electron beam (E-beam) according to Example 3 of the present invention. [Figure 12A] This is the exposure pattern at 254 nm of the Zn-based organic coordination nanoparticles of Example 4 of the present invention. [Figure 12B] This is the exposure pattern of Zn-based organic coordination nanoparticles using an electron beam (E-beam) according to Example 4 of the present invention. [Figure 13] This shows the difference in exposure performance between immediately after synthesis and after 2 months of storage of Example 1 of the present invention. [Figure 14] This shows the difference in exposure performance between immediately after synthesis and after being left for two months in Comparative Example 1 of the present invention. [Modes for carrying out the invention]

[0037] Example 1 0.02 mol of zinc acetate, 0.04 mol of benzoic acid, 0.03 mol of the organic amine diisopropylethylamine, and 45 mL of ethyl acetate solvent were mixed and stirred uniformly. The mixture was stirred at 65°C for 8 hours. Then, it was evaporated using a rotary evaporator at 50°C for 30 minutes, and further evacuated in a vacuum oven at 65°C for 5 hours. Analysis revealed that the nanoparticles obtained in Example 1 contained Zn2(C6H5COO)5(C8H 19 N)H was present in these nanoparticles. 1 The 1H NMR (400 MHz, DMSO-d6) values ​​were δ7.97-7.89 (m), 7.51-7.44 (m), 7.43-7.35 (m), 3.34-3.17 (m), 2.74 (q), 1.86 (d), 1.17 (td), and 1.08 (d).

[0038] The raw materials used, the particle size of the obtained nanoparticles, and the characteristics of the nuclear magnetic resonance hydrogen spectra and single crystal patterns were evaluated. Specifically, these are shown in Figures 1, 2A, and 2B. From the nuclear magnetic detection results, it was confirmed that after the synthesis of the photoresist nanoparticles in Example 1, each monomer coordinated individually, resulting in a peak shift. The peaks in the diisopropylethylamine structure shifted from 2.96, 2.42, and 0.94 to 3.26, 2.74, and 1.08, respectively. The methyl peak of zinc acetate shifted from 1.82 to 1.85. The benzene ring peak of benzoic acid also shifted from 7.51, 7.63, and 7.95 to 7.40, 7.46, and 7.93.

[0039] Example 2 The procedure is the same as in Example 1, except that the organic amine was changed to diethylamine. Analysis revealed that the obtained nanoparticles contained Zn2(C6H5COO)5(C4H 11 N)H was present. The characteristics of the raw materials used, the particle size, and the single-crystal pattern of the obtained nanoparticles were evaluated. Specifically, these are shown in Figure 3-4.

[0040] Example 3 The procedure is the same as in Example 1, except that the organic amine was replaced with piperidine. Analysis revealed that the resulting nanoparticles contained Zn3(C6H5COO)7(CH3COO)(C5H 11 N)2H2 was present. The raw materials used, the particle size of the obtained nanoparticles, and the nuclear magnetic resonance hydrogen spectra and single crystal patterns were characterized. Specifically, these are shown in Figures 5, 6A, and 6B. From the results of nuclear magnetic detection, 1 The 1H NMR (400 MHz, DMSO-d6) δ values ​​were 7.98-7.91 (m), 7.49-7.43 (m), 7.42-7.35 (m), 2.99 (d), 1.86 (s), 1.60 (dq), and 1.53 (q). After the synthesis of the photoresist nanoparticles in Example 3, each monomer coordinated individually, resulting in peak shifts. The peaks in the piperidine structure shifted from 1.35, 1.43, and 2.58 to 1.53, 1.60, and 2.99, respectively. The methyl peak of zinc acetate shifted from 1.82 to 1.86. The benzene ring peak of benzoic acid also shifted from 7.51, 7.63, and 7.95 to 7.40, 7.45, and 7.94.

[0041] Example 4 The procedure was the same as in Example 1, except that the organic amine was replaced with tetrahydropyrrole. Analysis revealed that the obtained nanoparticles contained Zn4(C6H5COO)6(CH3COO)6(C4H9N)4H. The particle size, nuclear magnetic resonance hydrogen spectrum, and single crystal pattern characteristics of the raw materials used and the obtained nanoparticles were evaluated. Specifically, these are shown in Figures 7, 8A, and 8B. From the results of nuclear magnetic detection, 1The 1H NMR spectrum (600 MHz, DMSO-d6) showed the following peaks: δ7.96-7.90(m), 7.48-7.41(m), 7.41-7.32(m), 3.18-2.94(m), 1.86(d), and 1.80-1.70(m). Each monomer coordinated individually, resulting in peak shifts. The peaks in the tetrahydropyrrole structure shifted from 1.54 and 2.66 to 1.77 and 3.06, respectively. The methyl peak of zinc acetate shifted from 1.82 to 1.86. The benzene ring peak of benzoic acid also shifted from 7.51, 7.63, and 7.95 to 7.38, 7.44, and 7.93.

[0042] Example 5 The nanoparticles from Example 1 were dissolved in propylene glycol methyl ether acetate to control the mass ratio of nanoparticles in the composition to 5%, and then the photoacid generator triphenylsulfonium perfluorobutanesulfonate was added. The mass of the photoacid generator was 10% of the composition, and the mixture was stirred for 5 minutes until completely dissolved to obtain a photoresist mixed solution.

[0043] The photoresist mixture was filtered twice using a filter head. Then, the silicon wafer was placed in a spin coater, photoresist was dropped onto the silicon wafer, and the rotation speed was set to 2000 r / min for 1 minute. Afterward, it was heated on a heating plate at 80°C for 1 minute. This allowed for exposure using electron beam or medium ultraviolet, deep ultraviolet, or extreme ultraviolet light. The exposed silicon wafer was developed with decalin for 10-40 seconds. It was then dried by blowing nitrogen.

[0044] The patterns obtained in the test are shown in Figures 9A and 9B. Figure 9A shows the composition of Example 5 under medium ultraviolet light (150 mJ / cm²). 2 ) Conditions and electron beam (200 μC / cm 2 This is a clear exposure pattern obtained under the conditions of 50 nm (Figure 9B).

[0045] Examples 6-8 The nanoparticles obtained in Examples 2-4 were used to prepare corresponding compositions by referring to Example 5, and each was subjected to photolithography testing. The resulting patterns are shown in Figures 10A-12B. Figures 10A and 10B show the composition of Example 6 under ultraviolet light (150 mJ / cm²), respectively. 2 ) Conditions and electron beam (150 μC / cm 2 These are the exposure patterns under medium ultraviolet (150 mJ / cm²) conditions. Figures 11A and 11B show the exposure patterns under medium ultraviolet (150 mJ / cm²) conditions, respectively. 2 ) Conditions and electron beam (200 μC / cm 2 Figures 12A and 12B show the exposure patterns of the composition of Example 7 under medium ultraviolet (150 mJ / cm²) conditions. 2 ) Conditions and electron beam (150 μC / cm 2 This is the exposure pattern of the composition of Example 8 under the conditions of 50 nm.

[0046] Comparative Example 1 The procedure is the same as in Example 1, except that the organic amine in Example 1 was replaced with triethylamine to obtain nanoparticles. Furthermore, a corresponding photoresist composition was obtained by referring to Example 5.

[0047] Example 10 For Example 5 and Comparative Example 1, exposure was performed under EUV conditions (exposure condition 90 mJ / cm²). 2 ) and two months later, the exposure pattern shown in Figure 13-14 was obtained.

[0048] As can be seen from the patterns, in the nanoparticles of Example 1, there were no bridges in the lines and good contrast immediately after synthesis, and after 2 months the lines were relatively sharp, the bridges were relatively small, and the contrast was relatively good. In contrast, in the nanoparticles of Comparative Example 1, there were bridges in the lines and the contrast was slightly worse immediately after synthesis, and after 2 months the bridging of the lines became severe and the contrast was relatively poor. As can be seen from the above, the nanoparticles of the present invention have higher stability than those of Comparative Example 1.

[0049] Based on the above, the present invention yielded four types of effective nanoparticles and corresponding compositions, exhibiting good lithography performance under 254 nm wavelength and electron beam exposure conditions, enabling superior photolithography performance such as high resolution, high sensitivity, and low line roughness. Furthermore, it was demonstrated that benzoic acid, as a ligand, can improve the stability of nanoparticles in photolithography.

Claims

1. The chemical formula is [Zn ｍ X ｎ (CH ３ COO) ｔ Y ｐ H ｑ ] ｒ These are Zn-based organic coordination nanoparticles, In the formula, X is the benzoate ion, CH ３ COO represents the acetate ion, Y is a nitrogen-containing organic ligand, r is the degree of polymerization, m, n, p, q, and r are each independently selected integers from 1 to 20, and t is an integer selected from 0 to 20. The nanoparticle is characterized in that the nitrogen-containing organic ligand is selected from diethylamine, tetrahydropyrrole, piperidine, and diisopropylethylamine.

2. The structural formula of the aforementioned Zn-based organic coordination nanoparticle is, Zn ２ (C ６ H ５ COO) ５ (C ４ H １１ N)H, wherein C ４ H １１ N is diethylamine, C ６ H ５ COO is benzoate ion, or Zn ４ (C ６ H ５ COO)) ６ (CH ３ COO) ６ (C ４ H ９ N) ４ H ４ And in the formula, C ４ H ９ N is tetrahydropyrrole, or Zn ３ (C ６ H ５ COO) ７ (CH ３ COO) (C ５ H １１ N) ２ H ２ And in the formula, C ５ H １１ N is piperidine, or Zn ２ (C ６ H ５ COO) ５ (C ８ H １９ N)H is, and in the formula, C ８ H １９ The nanoparticle according to claim 1, characterized in that N is diisopropylethylamine.

3. The nanoparticle according to claim 2, characterized in that the crystal size of the Zn-based organic coordination nanoparticle is 1 nm to 4 nm.

4. A method for producing nanoparticles according to any one of claims 1 to 3, A method for producing nanoparticles, characterized in that nanoparticles are obtained by mixing a zinc-containing compound, benzoic acid, and a nitrogen-containing organic ligand in an organic solvent, stirring the mixture, and then performing a post-treatment, wherein the molar ratio of the zinc-containing compound, benzoic acid, and nitrogen-containing organic ligand is (2-10):(4-10):(2-10).

5. The method for producing nanoparticles according to Claim 4, characterized in that the post-treatment includes stirring at 45°C-80°C for 5h-24h, then rotating and evaporating at 40°C-60°C for 20min-80min using a rotary evaporator, and further evacuating in a vacuum oven at 45°C-75°C for 5h.

6. The method for producing nanoparticles according to claim 4, characterized in that the zinc-containing compound is zinc acetate.

7. A photoresist composition characterized by comprising nanoparticles according to any one of claims 1 to 3.

8. The photoresist composition according to claim 7, further comprising a photoacid generator and an organic dispersion solvent, wherein the photoacid generator is present in an amount of 5 wt% to 10 wt% of the photoresist composition, and the nanoparticles are present in an amount of 3 wt% to 20 wt% of the photoresist composition.

9. The photoresist composition according to claim 8, characterized in that the photoacid generator is one or more selected from N-hydroxynaphthalimidetrifluoromethanesulfonic acid, 1,4-aminonaphthalenesulfonic acid, 2-amino-5,7-naphthalenedisulfonic acid, tert-butylphenyliodonium salt of perfluorooctanesulfonic acid, triphenylsulfonium perfluorobutanesulfonate, triphenylsulfonium perfluorobutyl, and triphenylsulfonium trifluorosulfonate.

10. The photoresist composition according to claim 8, characterized in that the organic dispersion solvent is one or more selected from ethyl acetate, butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol methyl ether acetate, 1-ethoxy-2-propanol, methanol, ethanol, and propanol.

11. A photolithography method characterized by using the photoresist composition described in claim 7, dropping the photoresist composition onto a substrate, rotating it, heating it, further exposing it with an electron beam, medium ultraviolet light, deep ultraviolet light or extreme ultraviolet light, and developing it with a developer.

12. A photolithography method characterized by using the photoresist composition described in claim 8, dropping the photoresist composition onto a substrate, rotating it, heating it, further exposing it with an electron beam, medium ultraviolet light, deep ultraviolet light or extreme ultraviolet light, and developing it with a developer.

13. A photolithography method characterized by using the photoresist composition described in claim 9, dropping the photoresist composition onto a substrate, rotating it, heating it, further exposing it with an electron beam, medium ultraviolet light, deep ultraviolet light or extreme ultraviolet light, and developing it with a developer.

14. A photolithography method characterized by using the photoresist composition described in claim 10, dropping the photoresist composition onto a substrate, rotating it, heating it, further exposing it with an electron beam, medium ultraviolet light, deep ultraviolet light or extreme ultraviolet light, and developing it with a developer.

15. The exposure limit for medium ultraviolet, deep ultraviolet, or extreme ultraviolet radiation is 50 mJ / cm². ２ ~500 mJ / cm ２ The electron beam exposure dose is 50 μC / cm². ２ ~500 μC / cm ２ The photolithography method according to claim 11, characterized in that...

16. The photolithography method according to claim 11, characterized in that the developer is a mixture of one or more selected from indene, indan, quinoline, 1-methylnaphthalene, toluene, o-xylene, m-xylene, ethyl acetate, butyl acetate, ethanol, n-propanol, tetralin, decalin, isopropanol, n-butanol, n-hexane, and cyclohexane, and the development temperature is 20°C to 50°C.

17. The use of nanoparticles according to any one of claims 1 to 3, characterized in that they are used in the field of photoresists including electron beam, medium ultraviolet, deep ultraviolet, or extreme ultraviolet photoresists.

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