Zn-based organic coordination nanoparticles, their preparation method, photoresist composition, and use 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 in particular to Zn-based organic coordination nanoparticles, their preparation method, photoresist compositions and their use. [Background technology]

[0002] Photoresists are materials that are irradiated with ultraviolet, electron, particle, extreme ultraviolet (EUV), or soft X-rays, which create a difference in solubility between irradiated and non-irradiated areas, allowing the pattern on a mask to be etched onto a wafer using lithography to create integrated circuits. The smaller the size of the lithography line in the photoresist, the more transistors can be fabricated per unit area, resulting in chips with superior performance. The most effective way to reduce the limiting resolution of photolithography is to shorten the wavelength of the photolithography. Over the past 40 years, the light source for lithography equipment has evolved from 436nm (G-line), 365nm (I-line), and 248nm (KrF) to 193nm (ArF). The single-exposure technology node for 193nm alone is 65nm. Increasing the numerical aperture using an immersion lens increases the single-exposure technology node by 33nm. 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 overlay accuracy, has low yields, and is expensive. After nearly 10 years of research and development, the world's first 13.5nm wavelength extreme ultraviolet lithography equipment was developed in 2014. The theoretical technology node for a single exposure of 13.5nm photolithography is 8nm, which theoretically makes it possible to manufacture 1nm process chips.

[0003] Photoresists are essential for chip manufacturing. Conventional photoresists have complex components, including the photoresist resin itself, photosensitizers, leveling agents, stabilizers, dispersants, thickeners, and solvents. This makes production processes complicated and places strict demands on control of formulation and purity. Conventional photoresists are mostly high-molecular-weight polymers containing numerous functional additives. Their complex composition results in a wide size distribution of photoresists, with components of various sizes, some of which reach sizes ranging from 10 to 20 nm. This makes it difficult to control the size of photoresist patterns and can lead to numerous defects. Furthermore, the range of use of conventional photoresists is significantly affected by the wavelength of the light source, requiring different photoresists for different light sources.

[0004] Extreme ultraviolet (EUV) lithography is attracting attention as a fundamental technology for the manufacturing of next-generation semiconductor devices. EUV lithography is a patterning technology that uses EUV light with a wavelength of approximately 13.5 nm as the exposure light source. As can be seen from EUV lithography, extremely fine patterns (e.g., approximately 20 nm or less) can be formed in the exposure process during the manufacturing of semiconductor devices. However, conventional technologies are not suitable for the application of photolithography because the patterns obtained by photolithography have high edge roughness and low pattern resolution, and this needs to be improved. Summary of the Invention [Problem to be solved by the invention]

[0005] Based on this, it is necessary to provide new Zn-based organic coordination nanoparticles, a method for preparing the same, a photoresist composition containing the nanoparticles, and the use thereof to address the problems of large edge roughness and low pattern resolution obtained by conventional photoresist lithography. [Means for solving the problem]

[0006] According to a first aspect of the present invention, there is provided Zn-based organic coordination nanoparticles produced by the following method. Specifically, 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 post-treating the mixture. The molar ratio of the zinc salt, m-methylbenzoic acid, and nitrogen-containing organic ligand is (2-10):(4-10):(2-10).

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

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

[0009] Furthermore, the nitrogen-containing organic ligand is any one or more selected from organic aliphatic amines and derivatives thereof, pyridine and derivatives thereof, pyrrole and derivatives thereof, pyrimidine and derivatives thereof, pyridazine and derivatives thereof, piperidine and derivatives thereof, and amide and derivatives thereof.

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

[0011] Further work-up involves stirring at 45-80°C for 5-24 h, followed by rotary evaporation at 40-60°C for 20-80 min, followed by vacuuming in a vacuum oven at 45-75°C for 5 h.

[0012] Furthermore, the organic solvent is 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 photoresist is as follows. Nanoparticles are obtained by mixing and stirring a zinc salt, m-methylbenzoic acid, and a nitrogen-containing organic ligand in an organic solvent, followed by post-treatment. 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 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, and amides and their derivatives.

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

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

[0016] According to a second aspect of the present invention, there is further provided a Zn-based organic coordination nanoparticle, the chemical formula of which is [Zn m X n (CH3COO) t Y p H q ] r In the 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 an integer selected from 1 to 20, and t is an integer selected from 0 to 20.

[0017] Y is one or more selected from organic aliphatic amines and derivatives thereof, pyridine and derivatives thereof, pyrrole and derivatives thereof, pyrimidine and derivatives thereof, pyridazine and derivatives thereof, piperidine and derivatives thereof, amide and derivatives thereof, etc.

[0018] The organic aliphatic 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, and the like. 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, stearic acid amide, succinic acid amide, oxamide, acrylamide, and nicotinamide.

[0019] In this study, we found that the introduction of m-methylbenzoic acid ligands into Zn-based organic coordination nanoparticles effectively reduced the crystallinity of the complexes, improved the solubility of the materials in organic reagents, and facilitated their storage and application.

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

[0021] Furthermore, m, n, p, q, n, and r are each independently an integer selected from 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.

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

[0023] Furthermore, the Zn-based organic coordination nanoparticles may have the following structure: Zn2(CH3C6H4COO)5(C4H 11N)H (in the formula, 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 (in the formula, C5H 11 N is piperidine); Zn2(CH3C6H4COO)5(C8H 19 N)H (in the formula, C8H 19 N is diisopropylethylamine).

[0024] The present invention further provides a method for preparing Zn-based organic coordination nanoparticles, which comprises mixing zinc acetate, m-methylbenzoic acid, and a nitrogen-containing organic ligand in an organic solvent, stirring the mixture, and then post-treating to obtain Zn-based organic coordination nanoparticles, wherein the molar ratio of zinc acetate, m-methylbenzoic acid, and the nitrogen-containing organic ligand is (2-10):(4-10):(2-10).

[0025] The present invention further provides a photoresist composition comprising the above-described nanoparticles.

[0026] Furthermore, the photoresist composition further comprises a photoacid generator and an organic dispersion solvent, the photoacid generator preferably being 5 wt%-10 wt% of the composition, and the nanoparticles preferably being 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, perfluorooctanesulfonic acid tert-butylphenyliodonium salt, triphenylsulfonium perfluorobutanesulfonate, triphenylsulfonium perfluorobutyl, and triphenylsulfonium trifluorosulfonate.

[0028] The organic dispersion solvent is one or more selected from the group consisting of 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 using the photoresist composition, comprising applying the photoresist composition to a substrate, spinning the composition, heating the composition, exposing the composition to an electron beam, mid-ultraviolet radiation, deep-ultraviolet radiation, or extreme-ultraviolet radiation, and developing the composition with a developer.

[0030] The exposure conditions are any one selected from the group consisting of mid-ultraviolet rays, deep ultraviolet rays, electron beams, and extreme ultraviolet rays, and the photoresist composition of the present invention can be applied to any of these exposure conditions.

[0031] The substrate is selected from a silicon plate, and other substrates that are insoluble in the developer can be used according to actual needs.

[0032] Regarding the mask, a transmission mask is used for a light source of long wavelengths of deep ultraviolet or longer, and a reflection mask is used for an extreme ultraviolet light source, and the electron beam is exposed according to a pattern set by software.

[0033] Furthermore, the exposure dose of mid-ultraviolet, deep-ultraviolet or extreme-ultraviolet rays is 50 mJ / cm 2 ~500mJ / cm 2 The electron beam exposure dose was 50 μC / cm 2 ~500μC / cm 2The exposure dose must be controlled within an appropriate range. Too little exposure and too low energy are unfavorable for the polymerization of photoresist particles in the exposed areas, leading to the formation of solubility differences between the exposed and unexposed areas, resulting in poor development. Nanoparticles containing organic ligands are more likely to polymerize than bare metal nanoparticles. Too much exposure may cause the organic ligands to fall off from the metal oxide and become fragments, preventing the photoresist particles from undergoing organic ligand exchange reactions and reducing the degree of polymerization in the exposed areas.

[0034] Furthermore, the developer is any one or a mixture of a plurality of types selected from decalin, tetralin, indene, indane, 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-film layer after removing the organic dispersion solvent may be 10 nm to 100 nm. Specifically, the thickness of the pre-film 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] Further applications of the nanoparticles include use in photoresists, including e-beam, mid-UV, deep UV or extreme UV photoresists. [Effects of the Invention]

[0037] The Zn-based organic coordination nanoparticles obtained in this invention have a unique structure. When exposed to light, they interact with a photoacid generator (photoacid generator), which changes the polarity of the material, causing aggregation and changing the solubility of the Zn-based organic coordination nanoparticles before and after irradiation. These properties allow the use of Zn-based organic coordination nanoparticles as a photoresist component to produce a difference in the solubility of the exposed and shaded portions of the photoresist in the developer. The exposed portions aggregate and become less soluble in the developer, while the shaded portions remain soluble in the developer. This allows the unexposed areas to be removed after development, resulting in a pattern of the desired shape. In particular, the unique structure of these Zn-based organic coordination nanoparticles allows the nanoparticles synthesized in this invention to be only approximately 2 nm in size, compared to conventional polymer photoresists and molecular glass photoresists. Using the Zn-based organic coordination nanoparticles of this invention as a photoresist component can achieve superior photolithography performance, including high resolution, high sensitivity, and low line roughness. 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 drawings]

[0038] [Figure 1] FIG. 2 is a dynamic light scattering diagram of the Zn-based organic coordination nanoparticles of Example 1 of the present invention. [Figure 2A] 1 shows the nuclear magnetic resonance hydrogen spectra of the Zn-based organic coordination nanoparticles and the raw material of Example 1 of the present invention. [Figure 2B] 1 is an infrared spectrum of the Zn-based organic coordination nanoparticles of Example 1 of the present invention. [Figure 3] FIG. 2 is a dynamic light scattering diagram of the Zn-based organic coordination nanoparticles of Example 2 of the present invention. [Figure 4A] 1 shows the nuclear magnetic resonance hydrogen spectra of the Zn-based organic coordination nanoparticles and the raw material of Example 2 of the present invention. [Figure 4B] 1 is an infrared spectrum of the Zn-based organic coordination nanoparticles of Example 2 of the present invention. [Figure 5] FIG. 1 is a dynamic light scattering diagram of the Zn-based organic coordination nanoparticles of Example 3 of the present invention. [Figure 6A] 1 shows the nuclear magnetic resonance hydrogen spectra of the Zn-based organic coordination nanoparticles and the raw material of Example 3 of the present invention. [Figure 6B] 1 is an infrared spectrum of the Zn-based organic coordination nanoparticles of Example 3 of the present invention. [Figure 7] FIG. 1 is a dynamic light scattering diagram of the Zn-based organic coordination nanoparticles of Example 4 of the present invention. [Figure 8A] 1 shows the nuclear magnetic resonance hydrogen spectra of the Zn-based organic coordination nanoparticles and the raw material of Example 4 of the present invention. [Figure 8B] 1 is an infrared spectrum of the Zn-based organic coordination nanoparticles of Example 4 of the present invention. [Figure 9] 9A and 9B are exposure patterns of the Zn-based organic coordination nanoparticles of Example 1 of the present invention by deep ultraviolet photolithography and electron beam photolithography at 254 nm. [Figure 10] 10A and 10B are exposure patterns of the Zn-based organic coordination nanoparticles of Example 2 of the present invention by deep ultraviolet photolithography and electron beam photolithography at 254 nm. [Figure 11] 11A and 11B are exposure patterns of the Zn-based organic coordination nanoparticles of Example 3 of the present invention by deep ultraviolet photolithography and electron beam photolithography at 254 nm. [Figure 12] 12A and 12B are exposure patterns of the Zn-based organic coordination nanoparticles of Example 4 of the present invention by deep ultraviolet photolithography and electron beam photolithography at 254 nm. [Figure 13] 1 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] 1 shows the difference in extreme ultraviolet exposure performance immediately after synthesis and after standing for two months in Comparative Example 1 of the present invention. [Figure 15] 1 shows the difference in exposure performance immediately after synthesis and after standing for 2 months in Comparative Example 2 of the present invention. DETAILED DESCRIPTION OF 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. The mixture was then subjected to rotary evaporation at 50°C for 30 minutes and then vacuumed 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(CH8H 19 N)H was contained in this nanoparticle. 1 H NMR (600 MHz, DMSO-d6) showed δ 7.77-7.75 (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 particle size, nuclear magnetic resonance (NMR) spectrum, and infrared spectrum of the raw materials used and the resulting nanoparticles were characterized. Specifically, these are shown in Figures 1, 2A, and 2B. Nuclear magnetic detection results 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 zinc acetate methyl peak 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 in Figure 2B, the peaks at 1630 cm -1 , 1558cm -1 and 1370 cm -1 The peak at 820 cm corresponds to the COO symmetric and asymmetric stretching of the carboxy group. -1 -650cm -1 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 and 1500 cm -1 -1450cm -1 It was observed at 621cm -1The peak is due to the stretching vibration 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 The raw materials used and the resulting nanoparticles were characterized by particle size and nuclear magnetic resonance hydrogen spectrum. Specifically, these are shown in Figures 3, 4A, and 4B. From the results of nuclear magnetic detection, 1 HNMR (400 MHz, DMSO-d6) showed δ 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, the coordination of each monomer resulted 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, the peaks at 1630 cm -1 , 1558cm -1 and 1370 cm -1 The peak at 820 cm corresponds to the COO symmetric and asymmetric stretching of the carboxy group. -1 -650cm -1 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 and 1500 cm -1 -1450cm -1 It was observed at 621cm -1 The peak is due to the stretching vibration 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 changed to piperidine. Analysis revealed that the obtained nanoparticles contained Zn(CHCHCOO)(CHCOO)(CH 11 The raw materials used and the particle size of the obtained nanoparticles were characterized by nuclear magnetic resonance hydrogen spectrum. Specifically, the results are shown in Figures 5, 6A, and 6B. From the results of nuclear magnetic detection, 1 HNMR (400 MHz, DMSO-d6) showed δ 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), 1.53 (s). After the synthesis of the photoresist nanoparticles in Example 3, each monomer coordinated, resulting in a peak shift. 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 zinc acetate methyl peak shifted from 1.82 to 1.85. The m-methylbenzoic acid methyl peak 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, the peaks at 1630 cm -1 , 1558cm -1 and 1370 cm -1 The peak at 820 cm corresponds to the COO symmetric and asymmetric stretching of the carboxy group. -1 -650cm -1 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 and 1500 cm -1 -1450cm -1 It was observed at 621cm -1 The peak is due to the stretching vibration 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 changed to tetrahydropyrrole. Analysis revealed that the obtained nanoparticles contained Zn(CHCHCOO)(CHCOO)(CHN)H. The raw materials used and the particle size and nuclear magnetic resonance hydrogen spectrum of the obtained nanoparticles were characterized. Specifically, these are shown in Figures 7, 8A, and 8B. The results of nuclear magnetic detection showed that 1 HNMR (600 MHz, DMSO-d6) showed δ 7.75 (dd), 7.72 (ddd), 7.32-7.24 (m), 3.03 (d), 2.34 (s), 1.85 (s), and 1.75 (q). Coordination of each monomer resulted 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 shifted from 7.39, 7.44, and 7.76 to 7.27, 7.72, and 7.75. As can be seen in Figure 8B, the peaks at 1630 cm -1 , 1558cm -1 and 1370 cm -1 The peak at 820 cm corresponds to the COO symmetric and asymmetric stretching of the carboxy group. -1 -650cm -1 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 and 1500 cm -1 -1450cm -1 It was observed at 621cm -1 The peak is due to the stretching vibration of the Zn-O bond.

[0043] Example 5 The nanoparticles of Example 1 were dissolved in propylene glycol methyl ether acetate to adjust the mass ratio of the nanoparticles in the composition to 5%, and then a 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, yielding a photoresist mixed solution.

[0044] The photoresist mixture was filtered twice using a filter head. The silicon wafer was then placed on a spin coater, the photoresist was dropped onto the silicon wafer, and the spin speed was set to 2000 r / min for 1 minute. The wafer was then heated on a heating plate at 80°C for 1 minute. This allowed for exposure to electron beams or mid-UV, deep-UV, or extreme-UV light. After exposure, the silicon wafer was developed in decalin for 10-40 seconds and dried by blowing nitrogen.

[0045] The patterns obtained in the test are shown in Figures 9A and 9B. Figure 9A shows the pattern obtained by irradiating the synthesized product of Example 1 with mid-ultraviolet light (150 mJ / cm 2 ) conditions and electron beam (150 μC / cm 2 ) (Figure 9B) shows a clear exposure pattern obtained under these conditions.

[0046] Examples 6-9 Photolithography tests were carried out on the nanoparticles obtained in Examples 2 to 4. The patterns obtained are shown in Figures 10A to 12B. Figures 10A and 10B show the patterns obtained by irradiating the nanoparticles with mid-ultraviolet light (150 mJ / cm). 2 ) conditions and electron beam (150 μC / cm 2 11A and 11B show the exposure patterns of the nanoparticle photoresist synthesized in Example 2 under mid-ultraviolet (150 mJ / cm , 50 nm) conditions, respectively. 2 ) conditions and electron beam (270 μC / cm 2 12A and 12B show the exposure patterns of the nanoparticle photoresist synthesized in Example 3 under mid-ultraviolet (150 mJ / cm , 50 nm) conditions, respectively. 2 ) conditions and electron beam (120 μC / cm 2 1 shows the exposure pattern of the nanoparticle photoresist synthesized in Example 4 under conditions of 100 nm (50 nm).

[0047] Comparative Example 1 The manufacturing method was the same as in Example 1, except that nanoparticles were obtained by changing m-methylbenzoic acid in Example 1 to benzoic acid.

[0048] Comparative Example 2 The procedure was the same as in Example 1, except that nanoparticles were obtained by changing the organic amine in the production method of Example 1 to triethylamine.

[0049] Example 10 For Example 1, Comparative Example 1, and Comparative Example 2, exposure under EUV (exposure condition 200 mJ / cm 2 ) and obtained the exposure patterns shown in Figures 13-15 after two months. As can be seen from the patterns, the nanoparticles of Example 1 had good contrast and no bridging in the lines immediately after synthesis, and after two months, had good contrast and essentially no bridging in the lines.

[0050] For the nanoparticles of Comparative Example 1, immediately after synthesis, there were essentially no line bridges and the contrast was good, but after two months, there were line bridges and the contrast was slightly worse. For the nanoparticles of Comparative Example 2, immediately after synthesis, there were line bridges and the contrast was slightly worse, but after two months, the line bridges became severe and the contrast was further worse. As can be seen from the above, the nanoparticles of the present invention have higher stability than Comparative Examples 1 and 2.

[0051] From the above, it has been demonstrated that the present invention provides four types of effective nanoparticles with good particle size distribution and lithographic performance under deep ultraviolet lithography and electron beam lithography conditions at a wavelength of 254 nm, enabling the realization of superior photolithographic performance such as high resolution, high sensitivity, and low line roughness. It has also been demonstrated that m-methylbenzoic acid, as a ligand, can improve the stability of the nanoparticles during photolithography.

Claims

1. The chemical formula is [Zn ｍ X ｎ (CH ３ COO) ｔ Y ｐ H ｑ ] ｒ Zn-based organic coordination nanoparticles, In the formula, X is m-methylbenzoate ion, CH ３ COO represents an acetate ion; Y represents a nitrogen-containing organic ligand; r represents a degree of polymerization; m, n, p, q, n, and r each independently represent an integer selected from 1 to 20; and t represents an integer selected from 0 to 20.

2. 2. The nanoparticles according to claim 1, wherein Y is one or more selected from the group consisting of organic aliphatic amines and derivatives thereof, pyridine and derivatives thereof, pyrrole and derivatives thereof, pyrimidine and derivatives thereof, pyridazine and derivatives thereof, piperidine and derivatives thereof, and amides and derivatives thereof.

3. 2. Nanoparticles according to claim 1, characterized in that Y is selected from the group consisting of diethylamine, piperidine, diisopropylethylamine and tetrahydropyrrole.

4. The nanoparticles according to any one of claims 1 to 3, characterized in that m, n, p, q, n, and r are each independently an integer of 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.

5. The nanoparticles according to any one of claims 1 to 3, characterized in that the crystal size of the Zn-based organic coordination nanoparticles is 1 nm to 4 nm.

6. The structural formula of the Zn-based organic coordination nanoparticles is: 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, or Zn ４ (CH ３ C ６ H ４ COO) ６ (CH ３ COO) ６ (C ４ H ９ N) ４ H ４ wherein 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 wherein C ５ H １１ N is piperidine, or Zn ２ (CH ３ C ６ H ４ COO) ５ (C ８ H １９ N) H, wherein C ８ H １９ Nanoparticles according to any one of claims 1 to 3, characterized in that N is diisopropylethylamine.

7. A method for producing nanoparticles according to any one of claims 1 to 6, comprising: A method for producing the nanoparticles, comprising mixing and stirring zinc acetate, m-methylbenzoic acid, and a nitrogen-containing organic ligand in an organic solvent, followed by post-treatment, wherein the molar ratio of zinc acetate, m-methylbenzoic acid, and the nitrogen-containing organic ligand is (2-10):(4-10):(2-10).

8. A photoresist composition comprising the nanoparticles of any one of claims 1 to 6.

9. 9. The photoresist composition of claim 8, further comprising a photoacid generator and an organic dispersion solvent, wherein the photoacid generator accounts for 5 wt % to 10 wt % of the photoresist composition, and the nanoparticles account for 3 wt % to 20 wt % of the photoresist composition.

10. 10. The photoresist composition of claim 9, wherein the photoacid generator is one or more selected from the group consisting of N-hydroxynaphthalimide trifluoromethanesulfonic acid, 1,4-aminonaphthalenesulfonic acid, 2-amino-5,7-naphthalenedisulfonic acid, perfluorooctanesulfonic acid tert-butylphenyliodonium salt, triphenylsulfonium perfluorobutanesulfonate, triphenylsulfonium perfluorobutyl, and triphenylsulfonium trifluorosulfonate.

11. 10. The photoresist composition of claim 9, wherein the organic dispersion solvent is one or more selected from the group consisting of ethyl acetate, butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol methyl ether acetate, 1-ethoxy-2-propanol, methanol, ethanol, and propanol.

12. A photolithography method using the photoresist composition according to any one of claims 9 to 11, comprising dropping the photoresist composition onto a substrate, rotating the photoresist composition, heating the photoresist composition, exposing the photoresist composition to an electron beam, a medium ultraviolet ray, a deep ultraviolet ray, or an extreme ultraviolet ray, and developing the photoresist composition with a developer.

13. The exposure dose of mid-ultraviolet, deep-ultraviolet, or extreme-ultraviolet is 50 mJ / cm ２ ~500 mJ / cm ２ and the electron beam exposure dose was 50 μC / cm ２ ~500μC / cm ２ 13. The photolithography method of claim 12, wherein:

14. The photolithography method according to claim 12, wherein the developer is any one or a mixture of a plurality of compounds selected from decalin, tetralin, indene, indane, 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.

15. Use of nanoparticles according to any one of claims 1 to 6, characterized in that they are used in the field of photoresists, including electron beam, mid-UV, deep UV or extreme UV photoresists.

Images