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

Abstract

The present invention relates to Zn-based organic coordination nanoparticles, their preparation method, photoresist composition, and their use. Zinc acetate, m-methylbenzoic acid, and a nitrogen-containing organic ligand are mixed in an organic solvent, stirred, and then post-treated to form a compound having the chemical formula [Zn m X n (CH3COO) t Y p H q ] r Here, X is a m-methylbenzoate ion, CH3COO is an 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 an integer selected from 1 to 20, and t is an integer selected from 0 to 20. In the present invention, by using Zn-based organic coordination nanoparticles as a photoresist film-forming agent, the photoresist has photolithography performance with high resolution, high sensitivity, and low line roughness compared to photoresists produced using conventional photoresists.

Description

[Technical Field]

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

[0002] Photoresists are materials used to create integrated circuits by etching patterns on a mask onto a wafer using lithography. When exposed to ultraviolet light, electron beams, particle beams, extreme ultraviolet (EUV), or soft X-rays, a difference in solubility is created between the irradiated and unirradiated areas. The smaller the lithography line size of the photoresist, the more transistors can be manufactured per unit area, resulting in higher-performance chips. The most effective way to lower the limiting resolution of photolithography is to shorten the wavelength of the photolithography. Over the past 40 years, light sources for lithography equipment have evolved from 436 nm (G line), 365 nm (I line), and 248 nm (KrF) to 193 nm (ArF). A single exposure technology node at 193 nm is 65 nm. Increasing the numerical aperture using immersion lenses increases the single exposure technology node by 33 nm. Currently, most 5nm and 7nm process chips are manufactured using 193nm immersion technology and multiple exposure multiple overlay technology. However, this process is difficult to control in terms of overlay accuracy, has low yield, and is expensive. After nearly 10 years of research and development, the world's first 13.5nm extreme ultraviolet lithography system was developed in 2014. The theoretical technology node for a single exposure of 13.5nm photolithography is 8nm, and theoretically, it is possible to manufacture 1nm process chips.

[0003] Photoresist is essential for chip manufacturing. Conventional photoresists have complex components, including a photoresist resin body, photosensitizer, leveling agent, stabilizer, dispersant, thickener, and solvent. The production process is complicated, and the control process requirements for formulation and purity are extremely high. Conventional photoresists are mostly high molecular polymers and contain many functional additives. Due to their complex composition, the size distribution of photoresists becomes wide, with components of various sizes existing. Some size structures reach 10 nm - 20 nm, making it difficult to control the size of the photoresist pattern and increasing the possibility of numerous defects. Also, in the case of conventional photoresists, their range of use is greatly affected by the wavelength of the light source, and different photoresists are required for different light sources.

[0004] Extreme ultraviolet (EUV) lithography has attracted attention as a key technology for next-generation semiconductor device manufacturing. EUV lithography is a patterning technology that uses EUV light with a wavelength of about 13.5 nm as the exposure light source. As can be seen from EUV lithography, very fine patterns (e.g., about 20 nm or less) can be formed in the exposure process during semiconductor device manufacturing. However, in the prior art, the edge roughness of the patterns obtained by photolithography is large, and the resolution of the patterns is low, so it is not suitable for the application of photolithography technology and needs to be improved.

Summary of the Invention

Problems to be Solved by the Invention

[0005] Based on this, to address the problem that the edge roughness of the patterns obtained by conventional photoresist lithography is large and the resolution of the patterns is low, there is a need to provide a new Zn-based organic coordination nanoparticle, its manufacturing method, a photoresist composition containing the nanoparticle, and its use.

Means for Solving the Problems

[0006] According to the first aspect of the present invention, Zn-based organic coordination nanoparticles produced by the following method are provided. That is, the Zn-based organic coordination nanoparticles are obtained by mixing a zinc salt, m-methylbenzoic acid, and a nitrogen-containing organic ligand in an organic solvent, stirring, and then performing post-treatment. Here, the molar ratio of the zinc salt, m-methylbenzoic acid, and the nitrogen-containing organic ligand is (2-10):(4-10):(2-10).

[0007] The zinc salt can be selected from zinc acetate, zinc acetate dihydrate, zinc chloride, and zinc sulfate, and preferably zinc acetate or zinc acetate dihydrate.

[0008] Furthermore, the zinc salt is zinc acetate.

[0009] Furthermore, the nitrogen-containing organic ligand is any 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.

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

[0011] Furthermore, the post-treatment includes stirring at 45°C - 80°C for 5 - 24 h, then rotary evaporation at 40°C - 60°C for 20 min - 80 min using a rotary evaporator, and further vacuum pumping at 45°C - 75°C for 5 h in a vacuum oven.

[0012] Furthermore, the organic solvent is 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.

[0013] The method for producing the Zn-based organic coordination nanoparticles for the photoresist is as follows. Nanoparticles are obtained by mixing a zinc salt, m-methylbenzoic acid, and a nitrogen-containing organic ligand in an organic solvent, stirring the mixture, and then post-treating it. Here, the molar ratio of the zinc salt, m-methylbenzoic acid, and nitrogen-containing organic ligand is (2-10):(4-10):(2-10). 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.

[0014] The zinc salt can be selected from zinc acetate, zinc acetate dihydrate, zinc chloride, and zinc sulfate, and is preferably zinc acetate or zinc acetate dihydrate.

[0015] Furthermore, the zinc salt is zinc acetate.

[0016] According to a second aspect of the present invention, Zn-based organic coordination nanoparticles are further provided. Their chemical formula is [Zn m X n (CH3COO) t Y p H q ] r In this formula, X is m-methylbenzoic acid, CH3COO is an 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.

[0017] Y is further selected from one or more of the following: organoaliphatic 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, etc.

[0018] 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, α-pyridine, etc. 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.

[0019] In this invention, we have found that by introducing an m-methylbenzoic acid ligand to Zn-based organic coordination nanoparticles, the crystallinity of the complex can be effectively reduced, improving the solubility of the material in organic reagents and facilitating storage and application.

[0020] Furthermore, Y is selected from diethylamine, piperidine, diisopropylethylamine, and tetrahydropyrrole.

[0021] Furthermore, m, n, p, q, n, and r are each independently selected integers from 1 to 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.

[0022] Furthermore, the size of the Zn-based organic coordination nanoparticle crystals is 1 nm to 4 nm.

[0023] Furthermore, the Zn-based organic coordination nanoparticles may have the following structure. Zn2(CH3C6H4COO)5(C4H 11N)H (where C4H 11 N is diethylamine, and CH3C6H4COO is m-methylbenzoate ion); Zn4(CH3C6H4COO)6(CH3COO)6(C4H9N)4H4 (where C4H9N is tetrahydropyrrole); Zn3(CH3C6H4COO)7(CH3COO)(C5H 11 N)2H2 (where C5H 11 N is piperidine); Zn2(CH3C6H4COO)5(C8H 19 N)H (where C8H 19 N is diisopropylethylamine).

[0024] According to the present invention, there is further provided a method for producing Zn-based organic coordination nanoparticles, which comprises mixing zinc acetate, m-methylbenzoic acid and a nitrogen-containing organic ligand in an organic solvent, stirring, and then performing post-treatment to obtain Zn-based organic coordination nanoparticles. Here, the molar ratio of zinc acetate, m-methylbenzoic acid and the nitrogen-containing organic ligand is (2-10):(�-10):(2-10).

[0025] According to the present invention, there is further provided a photoresist composition containing the above nanoparticles.

[0026] 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.

[0027] 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.

[0028] 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.

[0029] 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.

[0030] 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.

[0031] The substrate is selected from silicon plates. Depending on the actual needs, other substrates insoluble in the developer may be used.

[0032] 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.

[0033] Furthermore, the exposure limit for medium ultraviolet, deep ultraviolet, or extreme ultraviolet radiation is 50 mJ / cm². 2 ~500mJ / cm 2 The electron beam exposure dose is 50 μC / cm². 2 ~500 μC / cm 2Therefore, 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.

[0034] Furthermore, the developer is a mixture of one or more selected from decalin, tetralin, indene, indan, quinoline, 1-methylnaphthalene, toluene, o-xylene, m-xylene, ethyl acetate, butyl acetate, ethanol, n-propanol, isopropanol, n-butanol, n-hexane, and cyclohexane, and the development temperature is room temperature or 20°C to 50°C.

[0035] 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.

[0036] Furthermore, the aforementioned nanoparticles are used in the field of photoresists, including electron beam, medium ultraviolet, deep ultraviolet, or extreme ultraviolet photoresists. [Effects of the Invention]

[0037] 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) to change the polarity of the material, causing aggregation and a change in 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 results in nanoparticles synthesized in this invention being only about 2 nm in size compared to conventional polymer-type photoresists and molecular glass photoresists. By using the Zn-based organic coordination nanoparticles of this invention as a photoresist component, superior photolithography performance such as high resolution, high sensitivity, and low line roughness can be achieved. Furthermore, the presence of m-methylbenzoic acid effectively reduces the crystallinity of the complex, improving the solubility of the material in organic reagents and facilitating storage and use. [Brief explanation of the drawing]

[0038] [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 the infrared light spectrum of the Zn-based organic coordination nanoparticles of 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 4A] This shows the nuclear magnetic resonance hydrogen spectra of the Zn-based organic coordination nanoparticles and raw materials of Example 2 of the present invention. [Figure 4B] This is the infrared light spectrum of the Zn-based organic coordination nanoparticles of 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 the infrared light spectrum of the Zn-based organic coordination nanoparticles of 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 the infrared light spectrum of the Zn-based organic coordination nanoparticles of Example 4 of the present invention. [Figure 9] Figures 9A and 9B show the exposure patterns of Zn-based organic coordination nanoparticles of Example 1 of the present invention using deep ultraviolet photolithography and electron beam photolithography at 254 nm. [Figure 10] Figures 10A and 10B show the exposure patterns of Zn-based organic coordination nanoparticles of Example 2 of the present invention using deep ultraviolet photolithography and electron beam photolithography at 254 nm. [Figure 11] Figures 11A and 11B show the exposure patterns of Zn-based organic coordination nanoparticles of Example 3 of the present invention using deep ultraviolet photolithography and electron beam photolithography at 254 nm. [Figure 12] Figures 12A and 12B show the exposure patterns of Zn-based organic coordination nanoparticles of Example 4 of the present invention using deep ultraviolet photolithography and electron beam photolithography at 254 nm. [Figure 13] This shows the difference in extreme ultraviolet exposure performance immediately after synthesis and after being left for two months in Example 1 of the present invention. [Figure 14] This shows the difference in extreme ultraviolet exposure performance immediately after synthesis and after being left for two months in Comparative Example 1 of the present invention. [Figure 15] This shows the difference in exposure performance immediately after synthesis and after being left for two months in Comparative Example 2 of the present invention. [Modes for carrying out the invention]

[0039] Example 1 0.02 mol of zinc acetate, 0.04 mol of m-methylbenzoic 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 then vacuum-conditioned in a vacuum oven at 65°C for 5 hours to obtain the synthesis product of Example 1. Analysis revealed that the nanoparticles obtained in Example 1 contained Zn2(CH3C6H4COO)5(C8H 19 N)H was present in these nanoparticles 1 The 1H NMR (600 MHz, DMSO-d6) results were δ7.77-7.75(m), 7.75-7.70(m), 7.31-7.26(m), 3.29-3.21(m), 2.73(q), 2.34(s), 1.87(s), and 1.08(d). The raw materials used, the particle size of the obtained nanoparticles, the nuclear magnetic resonance hydrogen spectrum, and the infrared light spectrum were characterized. 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 of the diisopropylethylamine structure shifted from 0.94, 2.42, and 2.96 to 1.08, 2.73, and 3.24, respectively. The methyl peak of zinc acetate shifted from 1.82 to 1.87. The methyl peak of m-methylbenzoic acid shifted from 2.37 to 2.34. The benzene ring peaks also shifted from 7.39, 7.44, and 7.76 to 7.29, 7.73, and 7.76. As can be seen from Figure 2B, at 1630 cm⁻¹ -1 , 1558cm -1 and 1370cm -1 The peak corresponds to the COO symmetric and asymmetric stretching of the carboxyl group. 820cm -1 -650cm -1 This is the CH bending vibration peak of the aromatic ring of m-methylbenzoic acid. The vibration signal of the benzene ring skeleton is at 1600 cm⁻¹. -1 and 1500cm -1 -1450cm -1 Observed at 621 cm. -1The peak is due to stretching vibrations of the Zn-O bond.

[0040] Example 2 The synthesis product of Example 2 was obtained in the same manner as in Example 1, except that the organic amine in Example 1 was changed to diethylamine. Analysis revealed that the obtained nanoparticles contained Zn2(CH3C6H4COO)5(C4H 11 N)H was present. The particle size and nuclear magnetic resonance hydrogen spectrum of the raw materials used and the obtained nanoparticles were characterized. Specifically, these are shown in Figures 3, 4A, and 4B. From the results of nuclear magnetic detection, 1 The 1H NMR (400 MHz, DMSO-d6) showed δ values ​​of 7.74 (d), 7.71 (dt), 7.30-7.22 (m), 2.86 (q), 2.33 (s), 1.83 (s), and 1.14 (t). After the synthesis of the photoresist nanoparticles in Example 2, each monomer coordinated, resulting in peak shifts. The peaks in the diethylamine structure shifted from 0.98 and 2.50 to 1.14 and 2.86, respectively. The methyl peak of zinc acetate shifted from 1.82 to 1.83. The methyl peak of m-methylbenzoic acid shifted from 2.37 to 2.33, and the benzene ring peaks also shifted from 7.39, 7.44, and 7.76 to 7.25, 7.71, and 7.74. As can be seen from Figure 4B, at 1630 cm⁻¹ -1 , 1558cm -1 and 1370cm -1 The peak corresponds to the COO symmetric and asymmetric stretching of the carboxyl group. 820cm -1 -650cm -1 This is the CH bending vibration peak of the aromatic ring of m-methylbenzoic acid. The vibration signal of the benzene ring skeleton is at 1600 cm⁻¹. -1 and 1500cm -1 -1450cm -1 Observed at 621 cm. -1 The peak is due to stretching vibrations of the Zn-O bond.

[0041] Example 3 The synthesis product of Example 3 was obtained in the same manner as in Example 1, except that the organic amine in Example 1 was replaced with piperidine. Analysis revealed that the obtained nanoparticles contained Zn3(CH3C6H4COO)7(CH3COO)(C5H 11 N)2H2 was present. The particle size and nuclear magnetic resonance hydrogen spectrum of the raw materials used and the obtained nanoparticles 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) showed δ values ​​of 7.77-7.74 (m), 7.75-7.70 (m), 7.29-7.23 (m), 2.96 (t, J=5.5 Hz), 2.33 (s), 1.85 (s), 1.63-1.54 (m), and 1.53 (s). After the synthesis of the photoresist nanoparticles in Example 3, each monomer coordinated, resulting in peak shifts. The peaks in the piperidine structure shifted from 1.35, 1.43, and 2.58 to 1.53, 1.59, and 2.96, respectively. The methyl peak of zinc acetate shifted from 1.82 to 1.85. The methyl peak of m-methylbenzoic acid shifted from 2.37 to 2.33. The benzene ring peaks also shifted from 7.39, 7.44, and 7.76 to 7.26, 7.73, and 7.75. As can be seen in Figure 6B, at 1630 cm⁻¹ -1 , 1558cm -1 and 1370cm -1 The peak corresponds to the COO symmetric and asymmetric stretching of the carboxyl group. 820cm -1 -650cm -1 This is the CH bending vibration peak of the aromatic ring of m-methylbenzoic acid. The vibration signal of the benzene ring skeleton is at 1600 cm⁻¹. -1 and 1500cm -1 -1450cm -1 Observed at 621 cm. -1 The peak is due to stretching vibrations of the Zn-O bond.

[0042] Example 4 The synthesis product of Example 4 was obtained in the same manner as in Example 1, except that the organic amine in Example 1 was replaced with tetrahydropyrrole. Analysis revealed that the obtained nanoparticles contained Zn4(CH3C6H4COO)6(CH3COO)6(C4H9N)4H. The particle size and nuclear magnetic resonance hydrogen spectrum of the raw materials used and the obtained nanoparticles were characterized. Specifically, these are shown in Figures 7, 8A, and 8B. From the results of nuclear magnetic detection, 1 The 1H NMR (600 MHz, DMSO-d6) showed δ values ​​of 7.75 (dd), 7.72 (ddd), 7.32-7.24 (m), 3.03 (d), 2.34 (s), 1.85 (s), and 1.75 (q). Each monomer coordinated, resulting in peak shifts. The peaks in the tetrahydropyrrole structure shifted from 1.54 and 2.66 to 1.75 and 3.03, respectively. The methyl peak of zinc acetate shifted from 1.82 to 1.85. The methyl peak of m-methylbenzoic acid shifted from 2.37 to 2.34, and the benzene ring peaks also moved from 7.39, 7.44, and 7.76 to 7.27, 7.72, and 7.75. As can be seen from Figure 8B, at 1630 cm⁻¹ -1 , 1558cm -1 and 1370cm -1 The peak corresponds to the COO symmetric and asymmetric stretching of the carboxyl group. 820cm -1 -650cm -1 This is the CH bending vibration peak of the aromatic ring of m-methylbenzoic acid. The vibration signal of the benzene ring skeleton is at 1600 cm⁻¹. -1 and 1500cm -1 -1450cm -1 Observed at 621 cm. -1 The peak is due to stretching vibrations of the Zn-O bond.

[0043] Example 5 The nanoparticles from Example 1 were dissolved using propylene glycol methyl ether acetate, and the mass ratio of nanoparticles in the composition was controlled to 5%. Furthermore, the photoacid generator N-hydroxynaphthalimide trifluoromethanesulfonic acid 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.

[0044] 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.

[0045] The patterns obtained from the test are shown in Figures 9A and 9B. Figure 9A shows the synthesis product of Example 1 under medium ultraviolet light (150 mJ / cm²). 2 ) Conditions and electron beam (150 μC / cm 2 (Figure 9B) This is a clear exposure pattern obtained under the specified conditions.

[0046] Examples 6-9 Photolithography tests were performed on the nanoparticles obtained in Examples 2-4. The obtained patterns are shown in Figures 10A-12B. Figures 10A and 10B were obtained under medium ultraviolet light (150 mJ / cm²). 2 ) Conditions and electron beam (150 μC / cm 2 Figures 11A and 11B show the exposure patterns of the nanoparticle photoresist synthesized in Example 2 under medium ultraviolet (150 mJ / cm²) conditions. 2 ) Conditions and electron beam (270 μC / cm 2 Figures 12A and 12B show the exposure patterns of the nanoparticle photoresist synthesized in Example 3 under medium ultraviolet (150 mJ / cm²) conditions. 2 ) Conditions and electron beam (120 μC / cm 2 This is the exposure pattern of the nanoparticle photoresist synthesized in Example 4 under the conditions of 50 nm.

[0047] Comparative Example 1 The method is the same as in Example 1, except that m-methylbenzoic acid in the manufacturing method of Example 1 is replaced with benzoic acid to obtain nanoparticles.

[0048] Comparative Example 2 The method is the same as in Example 1, except that the organic amine in the manufacturing method of Example 1 was changed to triethylamine to obtain nanoparticles.

[0049] Example 10 Example 1, Comparative Example 1, and Comparative Example 2 were exposed under EUV (exposure condition: 200 mJ / cm²). 2 ) and the exposure patterns shown in Figure 13-15 were obtained after two months. As can be seen from the patterns, the nanoparticles of Example 1 had no bridges in the lines and good contrast immediately after synthesis, and after two months, there were basically no bridges in the lines and the contrast was good.

[0050] In Comparative Example 1, immediately after synthesis, there were basically no bridges in the lines and the contrast was good. However, after two months, bridges appeared in the lines and the contrast slightly deteriorated. In Comparative Example 2, immediately after synthesis, there were bridges in the lines and the contrast was slightly worse. After two months, the bridging in the lines worsened and the contrast deteriorated further. As can be seen from the above, the nanoparticles of the present invention have higher stability than those of Comparative Examples 1 and 2.

[0051] Based on the above, the present invention yielded four types of effective nanoparticles, exhibiting good particle size distribution and lithography performance under deep ultraviolet lithography and electron beam lithography conditions at a wavelength of 254 nm. It was demonstrated that these nanoparticles could achieve superior photolithography performance such as high resolution, high sensitivity, and low line roughness, and that m-methylbenzoic acid, as a ligand, could improve the stability of the 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 complex nanoparticles, In the formula, X is the m-methylbenzoate ion, CH ３ COO represents the acetate ion, Y is a nitrogen-containing organic ligand selected from diethylamine, piperidine, diisopropylethylamine, and tetrahydropyrrole, r is the degree of polymerization, m, n, p, q, and r are each independently integers selected from 1 to 20, where q=p, r=1, and t is an integer selected from 0 to 20. The structural formula of the Zn-based organic coordination complex nanoparticle is as follows: Zn ２ (CH ３ C ６ H ４ COO) ５ (C ４ H １１ N)H, wherein C ４ H １１ N is diethylamine, CH ３ C ６ H ４ COO is m-methylbenzoate ion, or Zn ４ (CH ３ C ６ H ４ 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 (CH ３ C ６ H ４ 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 (CH ３ C ６ H ４ COO) ５ (C ８ H １９ N)H is, and in the formula, C ８ H １９ Nanoparticles characterized in that N is diisopropylethylamine.

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

3. A method for producing nanoparticles according to claim 1 or 2, A method for producing nanoparticles, characterized by mixing zinc acetate, m-methylbenzoic acid, and a nitrogen-containing organic ligand in an organic solvent, stirring, and then performing a post-treatment, wherein the molar ratio of zinc acetate, m-methylbenzoic acid, and nitrogen-containing organic ligand is (2-10):(4-10):(2-10).

4. A photoresist composition characterized by comprising the nanoparticles described in claim 1 or 2.

5. The photoresist composition according to claim 4, 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.

6. The photoresist composition according to claim 5, 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.

7. The photoresist composition according to claim 5, 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.

8. A photolithography method characterized by using the photoresist composition described in claim 4, 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.

9. 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 8, characterized in that it is the same as the method described above.

10. The photolithography method according to claim 8, characterized in that the developer is a mixture of one or more selected from decalin, tetralin, indene, indan, quinoline, 1-methylnaphthalene, toluene, o-xylene, m-xylene, ethyl acetate, butyl acetate, ethanol, n-propanol, isopropanol, n-butanol, n-hexane, and cyclohexane, and the development temperature is room temperature or 20°C to 50°C.

11. The use of the nanoparticles according to claim 1 or 2, 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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