Zn-based organic coordination nanoparticles, their preparation method, photoresist composition containing the same, and use 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 technical field of photoresists, and in particular to Zn-based organic coordination nanoparticles, a method for preparing the same, a photoresist composition 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 manufacturing. The photolithography process is as follows: photoresist coated on a substrate is excited by light passing through a mask, causing a change in the solubility of the irradiated and unirradiated areas, resulting in negative or positive etching of the mask pattern. Through subsequent processes, the pattern on the substrate is transformed into an integrated circuit. Given the wavelength of photolithography, the photoresist determines the quality of the photolithography. With the continued development of photolithography technology, the linewidth of the light source continues to decrease, and 13.5nm extreme ultraviolet light source exposure technology is gradually becoming the primary choice for photolithography below 7nm.

[0003] Photoresists are corrosion-resistant thin-film materials whose solubility changes when exposed to ultraviolet light, electron beams, particle beams, extreme ultraviolet (EUV), or soft X-rays. They are widely used for pattern transfer in the manufacturing of high-end micro- and nanostructures, including semiconductor integrated circuits, LCD panel processing, and high-end optical devices. With the continuous advancement of semiconductor technology and the development of Moore's Law, semiconductor manufacturing processes are becoming increasingly miniaturized, resulting in higher demands for smaller feature sizes. To accommodate more advanced semiconductor manufacturing processes and achieve smaller feature sizes, photolithography technology has evolved, from I-line, G-line, deep ultraviolet (DUV), 193 nm, and immersion 193 nm to microfabrication methods such as extreme ultraviolet lithography and electron beam lithography.

[0004] Conventional photoresists have complex components, including the photoresist resin itself, photosensitizers, leveling agents, stabilizers, dispersants, thickeners, and solvents, making their production process complicated and placing strict requirements 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.

[0005] Extreme ultraviolet (EUV) lithography is attracting attention as a fundamental technology for manufacturing 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 semiconductor device manufacturing.

[0006] However, in the conventional techniques, the edge roughness of the patterns obtained by photolithography is large and the pattern resolution is low, so that the techniques are not suitable for application of photolithography, and this needs to be improved. Summary of the Invention [Problem to be solved by the invention]

[0007] Based on this, it is necessary to provide Zn-based organic coordination nanoparticles, a method for preparing the same, a photoresist composition containing the nanoparticles, and a use thereof to address the problems of large edge roughness and low pattern resolution obtained by conventional photoresist lithography. [Means for solving the problem]

[0008] According to a first aspect of the present invention, Zn-based organic coordination nanoparticles are provided by the following method. Specifically, the nanoparticles are obtained by mixing and stirring a zinc-containing compound, benzoic acid, and a nitrogen-containing organic ligand in an organic solvent, followed by post-treatment. 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 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. Examples of zinc-containing compounds, such as soluble zinc salts, include zinc acetate, zinc acetate dihydrate, zinc chloride, and zinc sulfate, with zinc acetate or zinc acetate dihydrate being preferred.

[0009] Furthermore, 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, 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, stearic acid amide, succinic acid amide, oxamide, acrylamide, and nicotinamide.

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

[0011] Further work-up involves stirring at 45-80°C for 5-24 hours, followed by rotary evaporation at 40-60°C for 20-80 minutes, followed by vacuuming in a vacuum oven at 45-75°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 photoresist is as follows. The nanoparticles are obtained by mixing and stirring a zinc-containing compound, benzoic acid, and a nitrogen-containing organic ligand in an organic solvent, followed by post-treatment. 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, and amides and their derivatives. Examples of zinc-containing compounds, such as soluble zinc salts, include zinc acetate, zinc acetate dihydrate, zinc chloride, and zinc sulfate, with zinc acetate or zinc acetate dihydrate being preferred.

[0014] According to the present invention, there is provided a Zn-based organic coordination nanoparticle, the chemical formula of which is [Zn m X n (CH3COO) t Y p H q ] r where X is benzoic 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.

[0015] Y may further be 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 amides and derivatives thereof.

[0016] 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.

[0017] The Zn-based organic coordination nanoparticles obtained in the present invention have a unique structure. When exposed to light, they interact with a photoacid generator (photoacid generator) under photoirradiation conditions, causing a change in the polarity of the material, resulting in 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 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 to obtain a desired pattern. In particular, the unique structure of the Zn-based organic coordination nanoparticles allows for superior photolithography performance, including high resolution, high sensitivity, and low line roughness, compared to conventional polymer photoresists and molecular glass photoresists. Furthermore, the present invention has been found to effectively reduce the crystallinity of the complexes by incorporating benzoic acid ligands into the Zn-based organic coordination nanoparticles, improving the solubility of the material in organic reagents and facilitating storage and application.

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

[0019] Furthermore, 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.

[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 (in the formula, C4H 11 N is diethylamine and C6H5COO is the benzoate ion); Zn4(C6H5COO)6(CH3COO)6(C4H9N)4H4 (where C4H9N is tetrahydropyrrole); Zn3(C6H5COO)7(CH3COO)(C5H 11 N)2H2 (in the formula, C5H 11 N is piperidine); Zn2(C6H5COO)5(C8H 19 N)H (in the formula, C8H 19 N is diisopropylethylamine).

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

[0023] The present invention further provides a photoresist composition comprising the nanoparticles.

[0024] 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.

[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, perfluorooctanesulfonic acid tert-butylphenyliodonium salt, triphenylsulfonium perfluorobutanesulfonate, and triphenylsulfonium perfluorobutylate triphenylsulfonium trifluorosulfonate.

[0026] 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.

[0027] 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.

[0028] The exposure dose of mid-UV, deep UV or extreme UV is 50mJ / cm 2 ~500mJ / cm 2 The electron beam exposure dose was 50 μC / cm 2 ~500μC / cm 2 The 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.

[0029] Furthermore, the developer is any one or a mixture of two or more selected from indene, indane, 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-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.

[0031] Further applications of the nanoparticles include use in photoresists, including e-beam, mid-UV, deep UV or extreme UV photoresists.

[0032] 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.

[0033] The substrate is selected from a silicon plate, and other substrates that are insoluble in developer may be used according to actual needs.

[0034] 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. [Effects of the Invention]

[0035] The Zn-based organic coordination nanoparticles obtained by the present 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. Due to these properties, using Zn-based organic coordination nanoparticles as a photoresist component results in 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 desired pattern. In particular, the unique structure of the Zn-based organic coordination nanoparticles allows the use of the Zn-based organic coordination nanoparticles of the present invention as a photoresist component to achieve superior photolithography performance, including high resolution, high sensitivity, and low line roughness, compared to conventional polymer photoresists and molecular glass photoresists. Furthermore, the combined presence of benzoic acid and a nitrogen-containing ligand in the present invention provides a certain degree of improved stability compared to benzoic acid and triethylamine ligands, making storage and application easier. [Brief explanation of the drawings]

[0036] [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 shows a single crystal pattern of 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 4] 1 shows a single crystal pattern of 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 shows a single crystal pattern of 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 shows a single crystal pattern of Zn-based organic coordination nanoparticles of Example 4 of the present invention. [Figure 9A] 1 shows an exposure pattern of the Zn-based organic coordination nanoparticles of Example 1 of the present invention at 254 nm. [Figure 9B] 1 shows an exposure pattern of Zn-based organic coordination nanoparticles of Example 1 of the present invention with an electron beam (E-beam). [Figure 10A] 1 shows an exposure pattern of Zn-based organic coordination nanoparticles of Example 2 of the present invention at 254 nm. [Figure 10B] 1 shows an exposure pattern of Zn-based organic coordination nanoparticles of Example 2 of the present invention with an electron beam (E-beam). [Figure 11A] 1 shows an exposure pattern of Zn-based organic coordination nanoparticles of Example 3 of the present invention at 254 nm. [Figure 11B] 1 shows an exposure pattern of Zn-based organic coordination nanoparticles of Example 3 of the present invention with an electron beam (E-beam). [Figure 12A] 1 shows an exposure pattern of Zn-based organic coordination nanoparticles of Example 4 of the present invention at 254 nm. [Figure 12B] 1 shows an exposure pattern of Zn-based organic coordination nanoparticles of Example 4 of the present invention with an electron beam (E-beam). [Figure 13] 1 shows the difference in exposure performance between immediately after synthesis and after being left for 2 months in Example 1 of the present invention. [Figure 14] 1 shows the difference in exposure performance between immediately after synthesis and after being left for 2 months in Comparative Example 1 of the present invention. DETAILED DESCRIPTION OF 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, the mixture was subjected to rotary evaporation at 50°C for 30 minutes using a rotary evaporator, and then vacuumed 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 contained in this nanoparticle. 1 HNMR (400 MHz, DMSO-d6) δ 7.97-7.89 (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), 1.08 (d).

[0038] The raw materials used and the resulting nanoparticles were characterized for particle size, nuclear magnetic resonance hydrogen spectrum, and single crystal pattern. 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 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 peaks of the benzene ring 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 was the same as in Example 1, except that the organic amine in Example 1 was changed to diethylamine. Analysis revealed that the nanoparticles obtained contained Zn2(C6H5COO)5(C4H 11 The raw materials used and the particle size and single crystal pattern of the resulting nanoparticles were characterized. Specifically, the results are shown in Figures 3-4.

[0040] Example 3 The procedure was the same as in Example 1, except that the organic amine in Example 1 was changed to piperidine. Analysis revealed that the nanoparticles obtained contained Zn(C6H5COO)7(CH3COO)(C5H 11 The raw materials used and the particle size of the obtained nanoparticles were characterized by nuclear magnetic resonance hydrogen spectrum and single crystal pattern. Specifically, the results are shown in Figures 5, 6A, and 6B. From the results of nuclear magnetic detection, 1 HNMR (400 MHz, DMSO-d6) δ 7.98-7.91 (m), 7.49-7.43 (m), 7.42-7.35 (m), 2.99 (d), 1.86 (s), 1.60 (dq), 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 peaks of the benzene ring of benzoic acid also shifted from 7.51, 7.63, and 7.95 to 7.40, 7.45, and 7.94.

[0041] Example 4 This example was the same as Example 1, except that the organic amine in Example 1 was changed to 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 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, 1HNMR (600 MHz, DMSO-d6) δ 7.96-7.90 (m), 7.48-7.41 (m), 7.41-7.32 (m), 3.18-2.94 (m), 1.86 (d), 1.80-1.70 (m). Individual coordination of each monomer resulted in peak shifts. The peaks in the tetrahydropyrrole structure shifted from 1.54 and 2.66 to 1.77 and 3.06, respectively. The zinc acetate methyl peak shifted from 1.82 to 1.86. The peaks of the benzoic acid benzene ring also shifted from 7.51, 7.63, and 7.95 to 7.38, 7.44, and 7.93.

[0042] 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 a photoacid generator, triphenylsulfonium perfluorobutanesulfonate, was further 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.

[0043] 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.

[0044] The patterns obtained in the test are shown in Figures 9A and 9B. Figure 9A shows the light emitted from the composition of Example 5 when exposed to mid-ultraviolet light (150 mJ / cm 2 ) conditions and electron beam (200 μC / cm 2 , 50 nm) (Figure 9B).

[0045] Examples 6-8 The nanoparticles obtained in Examples 2-4 were subjected to photolithography tests to obtain corresponding compositions with reference to Example 5. The obtained patterns are shown in Figures 10A-12B. Figures 10A and 10B show the patterns of the composition of Example 6 exposed to mid-ultraviolet light (150 mJ / cm). 2 ) conditions and electron beam (150 μC / cm 2 11A and 11B are exposure patterns under mid-ultraviolet (150 mJ / cm 2 , 50 nm) conditions. 2 ) conditions and electron beam (200 μC / cm 2 12A and 12B show the exposure patterns of the composition of Example 7 under mid-ultraviolet (150 mJ / cm 2 , 50 nm) conditions. 2 ) conditions and electron beam (150 μC / cm 2 1 shows the exposure pattern of the composition of Example 8 under conditions of 100 nm to 50 nm.

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

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

[0048] As can be seen from the patterns, the nanoparticles of Example 1 had no bridging in the lines and good contrast immediately after synthesis, and after two months, the lines were relatively clear, the bridging was relatively small, and the contrast was relatively good, whereas the nanoparticles of Comparative Example 1 had bridging in the lines and slightly poorer contrast immediately after synthesis, and after two months, the bridging in 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 Comparative Example 1.

[0049] From the above, it has been demonstrated that the present invention provides four types of effective nanoparticles and corresponding compositions, which have good particle size distribution and lithography performance at a wavelength of 254 nm and under electron beam exposure conditions, and can achieve better photolithography performance such as high resolution, high sensitivity, and low line roughness.It has also been demonstrated that benzoic 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 a benzoate ion, and 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. The nanoparticles according to claim 1, characterized in that the nitrogen-containing organic ligand 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 amide and derivatives thereof.

3. 2. The nanoparticles according to claim 1, wherein the nitrogen-containing organic ligand is selected from the group consisting of diethylamine, tetrahydropyrrole, piperidine, and diisopropylethylamine.

4. The structural formula of the Zn-based organic coordination nanoparticles 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, or Zn ４ (C ６ H ５ 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 (C ６ H ５ COO) ７ (CH ３ COO) (C ５ H １１ N) ２ H ２ wherein C ５ H １１ N is piperidine, or Zn ２ (C ６ H ５ 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.

5. The nanoparticles according to claim 4, wherein the crystal size of the Zn-based organic coordination nanoparticles is 1 nm to 4 nm.

6. 6. A method for producing nanoparticles according to any one of claims 1 to 5, comprising: The method for producing nanoparticles includes mixing and stirring a zinc-containing compound, benzoic acid, and a nitrogen-containing organic ligand in an organic solvent, followed by post-treatment to obtain the nanoparticles, wherein the molar ratio of the zinc-containing compound, benzoic acid, and nitrogen-containing organic ligand is (2-10):(4-10):(2-10), and preferably the post-treatment comprises stirring at 45°C-80°C for 5 hours to 24 hours, followed by rotary evaporation at 40°C-60°C for 20 minutes to 80 minutes using a rotary evaporator, and then vacuuming in a vacuum oven at 45°C-75°C for 5 hours.

7. The method for producing nanoparticles according to claim 6, wherein the zinc-containing compound is zinc acetate.

8. A photoresist composition comprising the nanoparticles of any one of claims 1 to 5.

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 8 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 the group consisting of indene, indane, 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.

15. Use of nanoparticles according to any one of claims 1 to 5, characterized in that they are used in the field of photoresists, including e-beam, mid-UV, deep UV or extreme UV photoresists.

Images