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

Abstract

The application relates to a Zn-based organic coordination nanoparticle, a preparation method thereof, a photoresist composition and application thereof. The Zn-based organic coordination nanoparticle with a chemical general formula of [Zn m X n (CH3COO) t Y p H q ] r is prepared by mixing and stirring zinc acetate, m-toluic acid and a nitrogen-containing organic ligand in an organic solvent and then performing post-treatment, wherein X is m-toluic acid, CH3COO represents an acetate, Y is a nitrogen-containing organic ligand, r is a polymerization degree, m, n, p, q, n and r are each independently selected from any integer from 1 to 20, and t is selected from any integer from 0 to 20. The Zn-based organic coordination nanoparticle is used as a photoresist film former, and compared with existing photoresists, the prepared photoresist has high resolution, high sensitivity and low line roughness photoetching performance.

Description

Technical Field

[0001] This invention relates to the field of photoresist technology, and in particular to a Zn-based organic coordination nanoparticle and its preparation method, a photoresist composition and its application. Background Technology

[0002] Photoresist is a material used to etch patterns from a photomask onto a wafer for integrated circuit fabrication, caused by the difference in solubility between irradiated and unirradiated areas when exposed to ultraviolet light, electron beams, particle beams, extreme ultraviolet (EUV), or soft X-rays. Smaller photoresist lithography lines allow for the fabrication of more transistors per unit area, resulting in chips with superior performance. Reducing the lithography wavelength is the most effective way to lower the resolution limit of photolithography. Over the past 40 years, the light source for lithography machines has evolved from 436nm (G-line), 365nm (I-line), 248nm (KrF) to 193nm (ArF). A single 193nm exposure technology node is 65nm; however, by using immersion lenses to increase the numerical aperture, the single exposure technology node is improved by 33nm. Currently, most 5nm and 7nm chips are manufactured using immersion 193nm technology combined with multiple exposures and overlay techniques. However, this process suffers from difficulty in controlling overlay precision, low yield, and high cost. After nearly 10 years of research and development, the world's first 13.5nm extreme ultraviolet lithography machine was developed in 2014. The theoretical single-exposure technology node of 13.5nm lithography is 8nm, which theoretically can produce chips with a process technology of 1nm.

[0003] Chip fabrication is inseparable from photoresist. Traditional photoresist has a complex composition, including photoresist resin, photosensitizer, leveling agent, stabilizer, dispersant, thickener, and solvent, making the manufacturing process cumbersome and requiring extremely high precision in controlling the proportions and purity. Because traditional photoresist is mostly composed of large polymer molecules and contains numerous functionalized additives, its complex composition results in a wide size distribution, with components of various sizes, some reaching 10nm to 20nm. This makes it difficult to control the size of the photoresist pattern and can potentially introduce numerous defects. Furthermore, the application range of traditional photoresist is greatly affected by the wavelength of the light source; different photoresists are required to match different light sources.

[0004] Extreme ultraviolet (EUV) lithography has attracted attention as a fundamental technology for manufacturing next-generation semiconductor devices. EUV lithography is a patterning technique that uses EUV rays with a wavelength of approximately 13.5 nanometers as the exposure source. According to EUV lithography, it is known that extremely fine patterns (e.g., less than or equal to approximately 20 nanometers) can be formed during the exposure process in semiconductor device manufacturing. However, the patterns obtained by lithography in existing technologies have large edge roughness and low pattern resolution, which is detrimental to the application of lithography technology and necessitates improvements. Summary of the Invention

[0005] Therefore, it is necessary to address the problems of large edge roughness and low pattern resolution obtained by traditional photoresist lithography, and to propose a new Zn-based organic coordination nanoparticle, its preparation method, a photoresist composition containing it, and its application.

[0006] In one aspect, the present invention provides a Zn-based organic coordination nanoparticle, which is prepared by the following method: zinc salt, m-methylbenzoic acid and nitrogen-containing organic ligand are mixed and stirred in an organic solvent and then post-treated, wherein the molar ratio of zinc salt: m-methylbenzoic acid and 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, with zinc acetate or zinc acetate dihydrate being preferred.

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

[0009] Furthermore, the nitrogen-containing organic ligand is selected from any one or more of organic fatty 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.

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

[0011] Further post-treatment includes: stirring at 45℃-80℃ for 5-24 hours, then rotary evaporating at 40℃-60℃ for 20-80 minutes, and then vacuum drying in a vacuum oven at 45℃-75℃ for 5 hours.

[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 preparation method of the Zn-based organic coordination nanoparticles for the above photoresist is as follows:

[0014] The zinc salt, m-methylbenzoic acid, and nitrogen-containing organic ligands are mixed and stirred in an organic solvent and then post-treated. The molar ratio of zinc salt, m-methylbenzoic acid, and nitrogen-containing organic ligands is (2-10):(4-10):(2-10). The nitrogen-containing organic ligands are selected from any one or more of organic fatty 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.

[0015] The zinc salt can be selected from zinc acetate, zinc acetate dihydrate, zinc chloride, and zinc sulfate, with zinc acetate or zinc acetate dihydrate being preferred.

[0016] Furthermore, the zinc salt is zinc acetate.

[0017] A second aspect of the present invention also provides Zn-based organic coordination nanoparticles, having the general chemical formula [Zn m X n (CH3COO) t Y p H q ] r Where X is m-methylbenzoic acid, CH3COO represents acetate, Y is a nitrogen-containing organic ligand, r is the degree of polymerization, m, n, p, q, n, and r are each independently selected from any integer from 1 to 20, and t is selected from any integer from 0 to 20.

[0018] Y is further selected from any one or more of organic fatty 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.

[0019] The organic fatty amines are selected from any one or more of triisopropylamine, triethanolamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, and diisopropylethylamine; pyridine and its derivatives are selected from any one or more of methylpyridine, vinylpyridine, methylpyridinane, perhydropyridine, and α-pyridine; pyrrole and its derivatives are selected from any one or more of tetrahydropyrrole, methylpyrrole, and vinylpyrrole; pyridazine and its derivatives are selected from any one or more of vinylpyridazine and divinylpyridazine; piperidine and its derivatives are selected from any one or more of piperidine, vinylpiperidine, and 3-methylpiperidine; and amides and their derivatives are selected from any one or more of formamide, stearamide, succinamide, oxalamide, acrylamide, and nicotinamide.

[0020] This invention discovers that introducing m-methylbenzoic acid ligands into Zn-based organic coordination nanoparticles can effectively reduce the crystallinity of the complex, improve the solubility of the material in organic reagents, and facilitate storage and application.

[0021] Furthermore, Y is selected from diethylamine, piperidine, diisopropylethylamine, and tetrahydropyrrole.

[0022] Furthermore, m, n, p, q, n, and r are each independent integers between 1 and 10, such as 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.

[0023] Furthermore, the size of the Zn-based organic coordination nanoparticle crystals is 1nm-4nm.

[0024] Furthermore, Zn-based organic coordination nanoparticles can have the following structure:

[0025] Zn2(CH3C6H4COO)5(C4H 11 N)H, where C4H 11 N is diethylamine, and CH3C6H4COO is m-methylbenzoate.

[0026] Zn4(CH3C6H4COO)6(CH3COO)6(C4H9N)4H4, where C4H9N is tetrahydropyrrole;

[0027] Zn3(CH3C6H4COO)7(CH3COO)(C5H 11 N)2H2 where C5H 11 N stands for piperidine;

[0028] Zn2(CH3C6H4COO)5(C8H 19 N)H, where C8H 19 N is diisopropylethylamine.

[0029] The present invention also provides a method for preparing Zn-based organic coordination nanoparticles, comprising the following steps: zinc acetate, m-methylbenzoic acid and nitrogen-containing organic ligands are mixed and stirred in an organic solvent and then post-treated to obtain the nanoparticles, wherein the molar ratio of zinc acetate: m-methylbenzoic acid and nitrogen-containing organic ligands is (2-10):(4-10):(2-10).

[0030] The present invention also provides a photoresist composition comprising the above-mentioned nanoparticles.

[0031] Furthermore, the above-mentioned photoresist composition also includes a photoacid and an organic dispersing solvent, wherein the photoacid preferably accounts for 5 wt%-10 wt% of the composition, and the nanoparticles preferably account for 3 wt%-20 wt% of the composition.

[0032] Furthermore, the photoacid is selected from any one or more of N-hydroxynaphthalimide trifluoromethanesulfonic acid, 1,4-aminonaphthalenesulfonic acid, 2-amino-5,7-naphthalenedisulfonic acid, tert-butylphenyliodonium salt perfluorooctanesulfonic acid, triphenylsulfonium perfluorobutanesulfonic acid, triphenylsulfonium perfluorobutyl and triphenylsulfonium trifluorosulfonic acid.

[0033] Furthermore, the organic dispersion solvent is selected from any one or more of ethyl acetate, butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol methyl ether acetate, 1-ethoxy-2-propanol, methanol, ethanol, and propanol. Ethyl acetate is preferred as the solvent.

[0034] The present invention also provides a photolithography method, characterized in that the above-mentioned photoresist composition is used, the photoresist composition is dropped onto a substrate, rotated, heated, and then exposed with an electron beam, mid-ultraviolet, deep ultraviolet or extreme ultraviolet, and developed with a developer.

[0035] The exposure conditions are selected from any one of mid-ultraviolet, deep ultraviolet, electron beam, and extreme ultraviolet. The photoresist composition of the present invention can be used under any exposure condition.

[0036] The substrate is selected from silicon substrates. Other substrates that are insoluble in developer can also be selected according to actual needs.

[0037] Regarding masks, deep ultraviolet and longer wavelength light sources are used as transmission masks, while extreme ultraviolet light is used as a reflection mask. The electron beam is exposed according to the pattern set in the software.

[0038] Furthermore, the exposure dose for mid-ultraviolet, deep ultraviolet, or extreme ultraviolet light is 50 mJ / cm². 2 ~500mJ / cm 2 The electron beam exposure dose was 50 μC / cm. 2 ~500μC / cm 2 The exposure dose should be controlled within a suitable range. Too low an exposure dose results in insufficient energy, which is detrimental to the polymerization of photoresist particles in the exposed area, hindering the formation of a solubility difference between the exposed and unexposed areas, leading to poor development. Compared to bare metal nanoparticles, nanoparticles containing organic ligands polymerize more easily. Excessive exposure dose may cause the organic ligands to detach directly from the metal oxide, forming fragments. This prevents the photoresist particles from undergoing the organic ligand exchange reaction, reducing the degree of polymerization in the exposed area.

[0039] Furthermore, the developer is selected from any one or more mixtures of decahydronaphthalene, tetrahydronaphthalene, indene, indene, quinoline, 1-methylnaphthalene, toluene, o-xylene, m-xylene, ethyl acetate, butyl acetate, ethanol, n-propanol, isopropanol, n-butanol, n-hexane, and cyclohexane, and the developing temperature is room temperature or 20°C to 50°C.

[0040] The thickness of the pre-formed film after removing the organic dispersion solvent can be 10 nm to 100 nm. Specifically, the thickness of the pre-formed film can be 10 nm to 20 nm, 20 nm to 30 nm, 30 nm to 40 nm, 40 nm to 50 nm, 50 nm to 60 nm, 60 nm to 70 nm, 70 nm to 80 nm, 80 nm to 90 nm, or 90 nm to 100 nm.

[0041] Furthermore, the aforementioned nanoparticles are used in the field of photoresists, including electron beam, mid-ultraviolet, deep ultraviolet, or extreme ultraviolet photoresists.

[0042] The Zn-based organic coordination nanoparticles obtained in this invention possess a unique structure. Under illumination, they can interact with photoacid-generating agents (photoacidifiers), causing a change in material polarity and aggregation. This results in a change in the solubility of the Zn-based organic coordination nanoparticles before and after illumination. Due to these properties, using these Zn-based organic coordination nanoparticles as a photoresist component can create a difference in the solubility of the photosensitive and light-shielding portions of the photoresist in the developer. The photosensitive portion aggregates and its solubility in the developer decreases, while the light-shielding portion does not aggregate and dissolves in the developer. This allows for the removal of unexposed areas after development, thereby obtaining a pattern of the desired shape. In particular, due to the unique structure of these Zn-based organic coordination nanoparticles, compared to traditional polymer-based photoresists and molecular glass photoresists, the nanoparticles synthesized in this invention have a size of only about 2 nm. Using these Zn-based organic coordination nanoparticles as a photoresist component can achieve superior photolithography performance, including high resolution, high sensitivity, and low line roughness. Furthermore, the presence of m-methylbenzoic acid can effectively reduce the crystallinity of the complex, improve the solubility of the material in organic reagents, and facilitate storage and application. Attached Figure Description

[0043] Figure 1 This is a dynamic light scattering diagram of the Zn-based organic coordination nanoparticles of Example 1 of the present invention;

[0044] Figure 2A The 1H NMR spectra of the Zn-based organic coordination nanoparticles and raw materials in Example 1 of this invention are shown.

[0045] Figure 2B The infrared spectrum of the Zn-based organic coordination nanoparticles of Example 1 of this invention;

[0046] Figure 3 This is a dynamic light scattering diagram of the Zn-based organic coordination nanoparticles of Example 2 of the present invention;

[0047] Figure 4A The 1H NMR spectra of the Zn-based organic coordination nanoparticles and raw materials in Example 2 of this invention are shown.

[0048] Figure 4BThe infrared spectrum of the Zn-based organic coordination nanoparticles of Example 2 of this invention;

[0049] Figure 5 This is a dynamic light scattering diagram of the Zn-based organic coordination nanoparticles of Example 3 of the present invention;

[0050] Figure 6A The 1H NMR spectra of the Zn-based organic coordination nanoparticles and raw materials in Example 3 of this invention are shown.

[0051] Figure 6B The infrared spectrum of the Zn-based organic coordination nanoparticles of Example 3 of this invention;

[0052] Figure 7 This is a dynamic light scattering diagram of the Zn-based organic coordination nanoparticles of Example 4 of the present invention;

[0053] Figure 8A The 1H NMR spectra of the Zn-based organic coordination nanoparticles and raw materials in Example 4 of this invention are shown.

[0054] Figure 8B The infrared spectrum of the Zn-based organic coordination nanoparticles of Example 4 of this invention;

[0055] Figure 9A and Figure 9B The images show the Zn-based organic coordination nanoparticles of Example 1 of this invention exposed by deep ultraviolet lithography and electron beam lithography at 254 nm.

[0056] Figure 10A and Figure 10B The images show the Zn-based organic coordination nanoparticles of Example 2 of this invention exposed by deep ultraviolet lithography and electron beam lithography at 254 nm.

[0057] Figure 11A and Figure 11B The images show the Zn-based organic coordination nanoparticles of Example 3 of this invention exposed by deep ultraviolet lithography and electron beam lithography at 254 nm.

[0058] Figure 12A and Figure 12B The images are taken from the Zn-based organic coordination nanoparticles of Example 4 of the present invention under deep ultraviolet lithography and electron beam lithography at 254 nm.

[0059] Figure 13 The difference in extreme ultraviolet exposure performance of Example 1 of the present invention immediately after synthesis and after two months of storage;

[0060] Figure 14 The difference in extreme ultraviolet exposure performance of Comparative Example 1 of this invention immediately after synthesis and after two months of storage;

[0061] Figure 15The difference in exposure performance between Comparative Example 2 of this invention immediately after synthesis and after two months of storage. Detailed Implementation

[0062] To facilitate understanding of the present invention, a more complete description will be given below with reference to the accompanying drawings. Preferred embodiments of the invention are shown in the drawings. However, the invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a thorough and complete understanding of the disclosure of the invention.

[0063] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0064] Example 1

[0065] 0.02 mol zinc acetate, 0.04 mol m-methylbenzoic acid, 0.03 mol organic amine diisopropylethylamine, and 45 mL ethyl acetate solvent were mixed and stirred until homogeneous. The mixture was stirred at 65°C for 8 hours. Then, it was rotary evaporated at 50°C for 30 minutes, followed by vacuum drying at 65°C for 5 hours to obtain the synthesized product of Example 1. Analysis showed that the nanoparticles obtained in Example 1 contained Zn2(CH3C6H4COO)5(C8H... 19 N)H, the nanoparticles 1 ¹H NMR (600MHz, DMSO-d⁶) 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), 1.08(d). The raw materials used and the particle size, ¹H NMR spectrum, and IR spectrum of the obtained nanoparticles were characterized, as detailed below. Figure 1 , Figure 2A and Figure 2B As shown. According to the NMR detection results: after synthesizing the photoresist nanoparticles of Example 1, each monomer underwent coordination, resulting in peak shifts. The peaks in the diisopropylethylamine structure shifted from 0.94, 2.42, and 2.96 to 1.08, 2.73, and 3.24, respectively; the methyl peak in zinc acetate shifted from 1.82 to 1.87; the methyl peak in 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 7.29, 7.73, and 7.76. Figure 2B It can be known that 1630cm -1 1558cm -1 and 1370cm -1The peak at 820 cm⁻¹ corresponds to the symmetric and asymmetric stretching of the COO group of the carboxyl group. -1 -650cm -1 This is the CH bending vibration peak of the aromatic ring of m-methylbenzoic acid. At 1600 cm⁻¹ -1 and 1500cm -1 -1450cm -1 Vibrational signals were observed in the benzene ring skeleton. 621 cm -1 The peak at that point is attributed to the stretching vibration of the Zn-O bond.

[0066] Example 2

[0067] The organic amine in Example 1 was selected as diethylamine, and all other steps were the same as in Example 1, resulting in the synthetic product of Example 2. Analysis revealed that the obtained nanoparticles contained Zn2(CH3C6H4COO)5(C4H 11 The raw materials used, as well as the particle size and 1H NMR spectrum of the obtained nanoparticles, were characterized, specifically as follows: Figure 3 , Figure 4A and Figure 4B As shown. Based on the MRI results: 1 ¹H NMR (400MHz, DMSO-d⁶) δ 7.74(d), 7.71(dt), 7.30–7.22(m), 2.86(q), 2.33(s), 1.83(s), 1.14(t). After synthesizing the photoresist nanoparticles of Example 2, each monomer underwent coordination, 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 in zinc acetate shifted from 1.82 to 1.83; the methyl peak in 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. Figure 4B It can be known that 1630cm -1 1558cm -1 and 1370cm -1 The peak at 820 cm⁻¹ corresponds to the symmetric and asymmetric stretching of the COO group of the carboxyl group. -1 -650cm -1 This is the CH bending vibration peak of the aromatic ring of m-methylbenzoic acid. At 1600 cm⁻¹ -1 and 1500cm -1 -1450cm -1 Vibrational signals were observed in the benzene ring skeleton. 621 cm -1 The peak at that point is attributed to the stretching vibration of the Zn-O bond.

[0068] Example 3

[0069] The organic amine in Example 1 was replaced with piperidine, and all other steps were the same as in Example 1, resulting in the synthetic product of Example 3. Analysis revealed that the obtained nanoparticles contained Zn3(CH3C6H4COO)7(CH3COO)(C5H 11 The raw materials used in the N)2H2 nanoparticles and their particle size and 1H NMR spectra were characterized, specifically as follows: Figure 5 , Figure 6A and Figure 6B As shown. Based on the MRI results: 1 ¹H NMR (400MHz, DMSO-d⁶) δ 7.77–7.74 (m), 7.75–7.70 (m), 7.29–7.23 (m), 2.96 (t, J=5.5Hz), 2.33 (s), 1.85 (s), 1.63–1.54 (m), 1.53 (s). After synthesizing the photoresist nanoparticles of Example 3, each monomer underwent coordination, 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 in zinc acetate shifted from 1.82 to 1.85; the methyl peak in 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 7.26, 7.73, and 7.75. Figure 6B It can be known that 1630cm -1 1558cm -1 and 1370cm -1 The peak at 820 cm⁻¹ corresponds to the symmetric and asymmetric stretching of the COO group of the carboxyl group. -1 -650cm -1 This is the CH bending vibration peak of the aromatic ring of m-methylbenzoic acid. At 1600 cm⁻¹ -1 and 1500cm -1 -1450cm -1 Vibrational signals were observed in the benzene ring skeleton. 621 cm -1 The peak at that point is attributed to the stretching vibration of the Zn-O bond.

[0070] Example 4

[0071] The organic amine in Example 1 was selected as tetrahydropyrrole, and other parameters remained the same as in Example 1, resulting in the synthetic product of Example 4. Analysis revealed that the obtained nanoparticles contained Zn4(CH3C6H4COO)6(CH3COO)6(C4H9N)4H. The raw materials used, as well as the particle size and 1H NMR spectrum of the obtained nanoparticles, were characterized, as detailed below. Figure 7 , Figure 8A and Figure 8B As shown. Based on the MRI results: 1¹H NMR (600MHz, DMSO-d⁶) δ 7.75 (dd), 7.72 (ddd), 7.32–7.24 (m), 3.03 (d), 2.34 (s), 1.85 (s), 1.75 (q). Each monomer underwent coordination, 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 in zinc acetate shifted from 1.82 to 1.85; the methyl peak in 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. Figure 8B It can be known that 1630cm -1 1558cm -1 and 1370cm -1 The peak at 820 cm⁻¹ corresponds to the symmetric and asymmetric stretching of the COO group of the carboxyl group. -1 -650cm -1 This is the CH bending vibration peak of the aromatic ring of m-methylbenzoic acid. At 1600 cm⁻¹ -1 and 1500cm -1 -1450cm -1 Vibrational signals were observed in the benzene ring skeleton. 621 cm -1 The peak at that point is attributed to the stretching vibration of the Zn-O bond.

[0072] Example 5

[0073] The nanoparticles in Example 1 were dissolved using propylene glycol methyl ether acetate, with the nanoparticles accounting for 5% of the composition by mass. Then, the photoacid N-hydroxynaphthalimide trifluoromethanesulfonic acid was added, accounting for 10% of the composition by mass. The mixture was stirred for 5 minutes until it was completely dissolved, resulting in a photoresist mixed solution.

[0074] Filter the photoresist mixture twice using a filter head. Then, place the silicon wafer on a spin coater and drop the photoresist onto the wafer. Set the spin speed to 2000 rpm and spin for 1 minute. Next, heat on a hot plate at 80°C for 1 minute. Electron beam, mid-ultraviolet, deep ultraviolet, or extreme ultraviolet exposures are then possible. After exposure, develop the silicon wafer with decahydronaphthalene for 10-40 seconds. Finally, dry it with nitrogen gas.

[0075] The pattern obtained from the test is as follows Figure 9A and Figure 9B As shown. Figure 9A The synthesized product of Example 1 is shown to exhibit performance in the mid-ultraviolet (150 mJ / cm) region. 2 Under these conditions and with an electron beam (150 μC / cm²), 2 ()( Figure 9B Under these conditions, a clear exposure pattern was obtained.

[0076] Examples 6-9

[0077] Photolithography tests were performed on the nanoparticles obtained in Examples 2-4, and the resulting patterns are shown below. Figure 10A-12B As shown. Figure 10A and Figure 10B They were respectively in the mid-ultraviolet (150mJ / cm) 2 Under these conditions and with an electron beam (150 μC / cm²), 2 Exposure pattern of nanoparticle photoresist synthesized in Example 2 under conditions of 50 nm. Figure 11A and Figure 11B They were respectively in the mid-ultraviolet (150mJ / cm) 2 Under these conditions and with an electron beam (270 μC / cm²), 2 Exposure pattern of nanoparticle photoresist synthesized in Example 3 under conditions of 50 nm. Figure 12A and Figure 12B They were respectively in the mid-ultraviolet (150mJ / cm) 2 Under these conditions and with an electron beam (120 μC / cm²), 2 Exposure pattern of nanoparticle photoresist synthesized in Example 4 under conditions of 50 nm.

[0078] Comparative Example 1

[0079] For the preparation method in Example 1, m-methylbenzoic acid was replaced with benzoic acid to obtain nanoparticles. Everything else was the same as in Example 1.

[0080] Comparative Example 2

[0081] In Example 1, the organic amine was replaced with triethylamine to obtain nanoparticles, and everything else was the same as in Example 1.

[0082] Example 10

[0083] Example 1, Comparative Examples 1 and 2 were exposed to EUV (exposure conditions 200 mJ / cm²). 2 ), and obtain it after 2 months. Figure 13-15 The exposure pattern shows that the nanoparticles of Example 1, when first synthesized, exhibited good contrast with no bridging in the lines, and after two months, the lines showed almost no bridging while maintaining good contrast.

[0084] When the nanoparticles of Comparative Example 1 were first synthesized, the lines showed almost no bridging and good contrast. After two months, bridging appeared, and the contrast was slightly worse. When the nanoparticles of Comparative Example 2 were first synthesized, the lines showed bridging and slightly worse contrast. After two months, the lines showed severe adhesion and breakage, resulting in even worse contrast. Therefore, the nanoparticles in this application exhibit better stability than those of Comparative Examples 1 and 2.

[0085] In summary, this invention yielded four effective nanoparticles, verifying their particle size distribution and excellent photolithography performance under deep ultraviolet lithography at a wavelength of 254 nm and electron beam lithography. These nanoparticles can achieve superior photolithography performance such as high resolution, high sensitivity, and low line roughness. Furthermore, it was demonstrated that m-methylbenzoic acid, as a ligand, can improve the photolithographic stability of the nanoparticles.

Claims

1. A Zn-based organic coordination nanoparticle, characterized in that, Its general chemical formula is [Zn m X n (CH3COO) t Y p H q ] r Where X is m-methylbenzoate, CH3COO represents acetate, Y is a nitrogen-containing organic ligand selected from diethylamine, piperidine, diisopropylethylamine, tetrahydropyrrole, r is the degree of polymerization, m, n, p, q, and r are each independently selected from any integer from 1 to 20, t is selected from any integer from 0 to 20, q=p, r=1; The Zn-based organic coordination nanoparticles have the structural formula Zn2(CH3C6H4COO)5(C4H 11 N)H, where C4H 11 N is diethylamine, and CH3C6H4COO is m-methylbenzoyl; or Zn4(CH3C6H4COO)6(CH3COO)6(C4H9N)4H4, where C4H9N is tetrahydropyrrole; or Zn3(CH3C6H4COO)7(CH3COO)(C5H 11 N)2H2, where C5H 11 N represents piperidine; or Zn2(CH3C6H4COO)5(C8H 19 N)H, where C8H 19 N is diisopropylethylamine.

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

3. The method for preparing nanoparticles according to claim 1 or 2, characterized in that, The mixture of zinc acetate, m-methylbenzoic acid and nitrogen-containing organic ligands in an organic solvent is subjected to post-treatment. The molar ratio of zinc acetate to m-methylbenzoic acid and nitrogen-containing organic ligands is (2-10):(4-10):(2-10).

4. A photoresist composition, characterized in that, Includes the nanoparticles described in claim 1 or 2.

5. The photoresist composition according to claim 4, characterized in that, It also includes a photoacid and an organic dispersing solvent, wherein the photoacid accounts for 5 wt%-10 wt% of the composition and the nanoparticles account for 3 wt%-20 wt% of the composition.

6. The photoresist composition according to claim 5, characterized in that, The photoacid is selected from any one or more of N-hydroxynaphthalimide trifluoromethanesulfonic acid, 1,4-aminonaphthalenesulfonic acid, 2-amino-5,7-naphthalenedisulfonic acid, tert-butylphenyliodonium salt perfluorooctanesulfonic acid, triphenylsulfonium perfluorobutanesulfonic acid, triphenylsulfonium perfluorobutyl and triphenylsulfonium trifluorosulfonic acid.

7. The photoresist composition according to claim 5, characterized in that, The organic dispersion solvent is selected from any one or more of ethyl acetate, butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol methyl ether acetate, 1-ethoxy-2-propanol, methanol, ethanol, and propanol.

8. A photolithography method, characterized in that, Using the photoresist composition according to any one of claims 4-7, the photoresist composition is dropped onto a substrate, rotated, heated, and then exposed with an electron beam, medium ultraviolet, deep ultraviolet or extreme ultraviolet, and developed with a developer.

9. The photolithography method according to claim 8, characterized in that, The exposure dose to medium ultraviolet, deep ultraviolet, or extreme ultraviolet light is 50 mJ / cm². 2 ~500 mJ / cm 2 The electron beam exposure dose was 50 μC / cm. 2 ~500μC / cm 2 .

10. The photolithography method according to claim 8, characterized in that, The developer is selected from any one or more of the following: decahydronaphthalene, tetrahydronaphthalene, indene, indane, quinoline, 1-methylnaphthalene, toluene, o-xylene, m-xylene, ethyl acetate, butyl acetate, ethanol, n-propanol, isopropanol, n-butanol, n-hexane, and cyclohexane. The developing 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, Used in the field of photoresists, including electron beam, mid-ultraviolet, deep ultraviolet or extreme ultraviolet photoresists.

Images