A Zn-based organic coordination nanoparticle, a preparation method thereof, a photoresist composition containing the same, and applications thereof

Abstract

This invention relates to Zn-based organic coordination nanoparticles, their preparation method, photoresist compositions comprising the same, and their applications. The Zn-based organic coordination nanoparticles are obtained by mixing and stirring a zinc-containing compound, preferably zinc acetate or benzoic acid, and a nitrogen-containing organic ligand in an organic solvent, followed by post-treatment, to obtain the nanoparticles with the general chemical formula [Zn]. m X n (CH3COO) t Y p H q ] r The nanoparticles contain X, which represents benzoate, CH3COO, Y, a nitrogen-containing organic ligand, r, and m, n, p, q, n, and r, each independently selected from any integer from 1 to 20, and t selected from any integer from 0 to 20. These Zn-based organic coordination nanoparticles, used as a photoresist component, can achieve superior photolithography performance, including high resolution, high sensitivity, and low line roughness.

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 containing the same, and its applications. Background Technology

[0002] Photolithography is a core technology in chip manufacturing, accounting for more than one-third of the total cost. The photolithography process is as follows: photoresist coated on the substrate is excited by light transmitted through a mask, causing changes in solubility in the illuminated and unilluminated areas, thus etching the pattern on the mask. The pattern on the substrate is then processed into integrated circuits. With a fixed photolithography wavelength, the photoresist determines the quality of the lithography. As photolithography technology continues to develop and the linewidth of the light source decreases, extreme ultraviolet (EUV) light source exposure technology at 13.5nm has gradually become the main choice for photolithography nodes below 7nm.

[0003] Photoresist is a corrosion-resistant thin film material whose solubility changes upon irradiation with ultraviolet light, electron beams, particle beams, extreme ultraviolet (EUV), or soft X-rays. It is widely used for pattern transfer in high-end micro / nano structure manufacturing processes, including semiconductor integrated circuits, LCD panel processing, and high-end optical device manufacturing. With the continuous advancement of semiconductor technology and the development of Moore's Law, semiconductor processes are constantly shrinking, placing higher demands on minimizing feature sizes. To meet the needs of more advanced semiconductor processes and achieve smaller feature sizes, photolithography technology is also constantly evolving, from I-line, G-line, deep ultraviolet (DUV), 193nm, immersion 193nm to finer processing methods such as extreme ultraviolet lithography and electron beam lithography.

[0004] Traditional photoresists have a complex composition, including photoresist resin, photosensitizer, leveling agent, stabilizer, dispersant, thickener, and solvent. Their manufacturing process is cumbersome, requiring extremely high precision in controlling the proportions and purity. Because traditional photoresists are mostly macromolecular polymers and contain numerous functionalized additives, their 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 photoresists is greatly affected by the wavelength of the light source; different photoresists are required to match different light sources.

[0005] 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 in the exposure process during the fabrication of semiconductor devices.

[0006] However, in the existing technology, the patterns obtained by photolithography have large edge roughness and low resolution, which is not conducive to the application of photolithography technology. It is necessary to improve this. Summary of the Invention

[0007] Therefore, it is necessary to address the problems of large edge roughness and low pattern resolution obtained by traditional photoresist lithography by proposing a Zn-based organic coordination nanoparticle, its preparation method, a photoresist composition containing the nanoparticle, and its application.

[0008] In one aspect, this invention provides Zn-based organic coordination nanoparticles, which are prepared by the following method: a zinc-containing compound, benzoic acid, and a nitrogen-containing organic ligand are mixed and stirred in an organic solvent, followed by post-treatment, wherein the molar ratio of the zinc-containing compound to benzoic acid and the nitrogen-containing organic ligand is (2-10):(4-10):(2-10). Further, 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. The zinc-containing compound is such as a zinc-soluble salt, such as zinc acetate, zinc acetate dihydrate, zinc chloride, or zinc sulfate, preferably zinc acetate or zinc acetate dihydrate.

[0009] Furthermore, 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; the pyridazine and its derivatives are selected from any one or more of vinylpyridazine and divinylpyridazine; the piperidine and its derivatives are selected from any one or more of piperidine, vinylpiperidine, and 3-methylpiperidine; and the amide and its derivatives are selected from any one or more of formamide, stearamide, succinamide, oxalamide, acrylamide, and nicotinamide.

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

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

[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-containing compound, benzoic acid, and nitrogen-containing organic ligands are mixed and stirred in an organic solvent, followed by post-treatment. The molar ratio of the zinc-containing compound, benzoic 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. The zinc-containing compound is a soluble salt of zinc, such as zinc acetate, zinc acetate dihydrate, zinc chloride, or zinc sulfate, preferably zinc acetate or zinc acetate dihydrate.

[0015] This invention provides Zn-based organic coordination nanoparticles with the general chemical formula [Zn m X n (CH3COO) t Y p H q H q ] r Where X is benzoic 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.

[0016] 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.

[0017] 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.

[0018] 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 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, using these Zn-based organic coordination nanoparticles as a photoresist component can achieve superior photolithographic performance, including high resolution, high sensitivity, and low line roughness. This invention discovers that introducing benzoic 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.

[0019] Furthermore, Y is selected from diethylamine, piperidine, diisopropylethylamine, and tetrahydropyrrole.

[0020] 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.

[0021] Furthermore, the size of the Zn-based organic coordination nanoparticle crystals is 1nm-4nm.

[0022] Furthermore, Zn-based organic coordination nanoparticles can have the following structure:

[0023] Zn2(C6H5COO)5(C4H 11 N)H, where C4H 11N is diethylamine, and C6H5COO is benzoate.

[0024] Zn4(C6H5COO)6(CH3COO)6(C4H9N)4H4, where C4H9N is tetrahydropyrrole;

[0025] Zn3(C6H5COO)7(CH3COO)(C5H 11 N)2H2 where C5H 11 N stands for piperidine;

[0026] Zn2(C6H5COO)5(C8H 19 N)H, where C8H 19 N is diisopropylethylamine.

[0027] This invention also provides a method for preparing Zn-based organic coordination nanoparticles, comprising 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, wherein the molar ratio of the zinc-containing compound to benzoic acid and the nitrogen-containing organic ligand is (2-10):(4-10):(2-10). The zinc-containing compound is preferably zinc acetate.

[0028] The present invention also provides a photoresist composition comprising the above-mentioned nanoparticles.

[0029] Furthermore, the above-mentioned photoresist composition also includes a photoacid and an organic dispersing solvent, wherein the photoacid preferably accounts for 5wt%-10wt% of the composition, and the nanoparticles preferably account for 3wt%-20wt% of the composition.

[0030] 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.

[0031] 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.

[0032] The present invention also provides a photolithography method, which uses the above-mentioned photoresist composition, drops the photoresist composition onto a substrate, rotates it, heats it, and then exposes it with an electron beam, mid-ultraviolet, deep ultraviolet or extreme ultraviolet light, and develops it with a developer.

[0033] The exposure dose to medium ultraviolet, deep ultraviolet, or extreme ultraviolet light is 50 mJ / cm². 2 ~500 mJ / cm 2The 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.

[0034] Furthermore, the developer is selected from any one or more mixtures of indene, indane, quinoline, 1-methylnaphthalene, toluene, o-xylene, m-xylene, ethyl acetate, butyl acetate, ethanol, n-propanol, decahydronaphthalene, tetrahydronaphthalene, isopropanol, n-butanol, n-hexane, and cyclohexane, and the developing temperature is 20℃~50℃.

[0035] 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.

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

[0037] 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.

[0038] The substrate is selected from silicon substrates, and other substrates that are insoluble in developer can also be selected according to actual needs.

[0039] 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.

[0040] 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 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, using these Zn-based organic coordination nanoparticles as a photoresist component can achieve superior photolithographic performance, including high resolution, high sensitivity, and low line roughness. Furthermore, due to the coexistence of benzoic acid and nitrogen-containing ligands mentioned in this application, its stability is improved to a certain extent compared to benzoic acid and triethylamine ligands, making it easier to store and use. Attached Figure Description

[0041] Figure 1 This is a dynamic light scattering diagram of the Zn-based organic coordination nanoparticles of Example 1 of the present invention;

[0042] Figure 2A The 1H NMR spectra of the Zn-based organic coordination nanoparticles and raw materials in Example 1 of this invention are shown.

[0043] Figure 2B This is a single-crystal image of the Zn-based organic coordination nanoparticles of Example 1 of the present invention;

[0044] Figure 3 This is a dynamic light scattering diagram of the Zn-based organic coordination nanoparticles of Example 2 of the present invention;

[0045] Figure 4 This is a single-crystal image of the Zn-based organic coordination nanoparticles of Example 2 of the present invention;

[0046] Figure 5 This is a dynamic light scattering diagram of the Zn-based organic coordination nanoparticles of Example 3 of the present invention;

[0047] Figure 6A The 1H NMR spectra of the Zn-based organic coordination nanoparticles and raw materials in Example 3 of this invention are shown.

[0048] Figure 6B This is a single-crystal image of the Zn-based organic coordination nanoparticles of Example 3 of the present invention;

[0049] Figure 7 This is a dynamic light scattering diagram of the Zn-based organic coordination nanoparticles of Example 4 of the present invention;

[0050] Figure 8A The 1H NMR spectra of the Zn-based organic coordination nanoparticles and raw materials in Example 4 of this invention are shown.

[0051] Figure 8B This is a single-crystal image of the Zn-based organic coordination nanoparticles of Example 4 of the present invention;

[0052] Figure 9A and Figure 9B The image shows the Zn-based organic coordination nanoparticles of Example 1 of this invention exposed at 254 nm using an electron beam (E-beam).

[0053] Figure 10A and Figure 10B The image shows the Zn-based organic coordination nanoparticles of Example 2 of this invention exposed at 254 nm using an electron beam (E-beam).

[0054] Figure 11A and Figure 11B The image shows the Zn-based organic coordination nanoparticles of Example 3 of the present invention exposed at 254 nm and with an electron beam (E-beam).

[0055] Figure 12A and Figure 12B The image shows the Zn-based organic coordination nanoparticles of Example 4 of this invention exposed at 254 nm using an electron beam (E-beam).

[0056] Figure 13 The difference in exposure performance between the initial synthesis and two months after the synthesis in Example 1 of this invention;

[0057] Figure 14 This invention compares the exposure performance of Example 1 immediately after synthesis and after two months of storage. Detailed Implementation

[0058] 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.

[0059] 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.

[0060] Example 1

[0061] 0.02 mol zinc acetate, 0.04 mol benzoic acid, 0.03 mol diisopropylethylamine (an organic amine), and 45 mL ethyl acetate 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. Analysis showed that the nanoparticles obtained in Example 1 contained Zn2(C6H5COO)5(C8H... 19 N)H, the nanoparticles 1 H NMR (400 MHz, DMSO- d 6) 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).

[0062] The raw materials used, as well as the particle size, 1H NMR spectrum, and single-crystal image of the obtained nanoparticles, were characterized, specifically as follows: Figure 1 As shown in Figure 2. 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 2.96, 2.42, and 0.94 to 3.26, 2.74, and 1.08, respectively; the methyl peak in zinc acetate shifted from 1.82 to 1.85; and the benzene ring peak in benzoic acid also shifted from 7.51, 7.63, and 7.95 to 7.40, 7.46, and 7.93.

[0063] Example 2

[0064] The organic amine in Example 1 was selected as diethylamine, and all other aspects were the same as in Example 1. Analysis revealed that the obtained nanoparticles contained Zn2(C6H5COO)5(C4H 11 N)H, the raw materials used and the particle size and single-crystal diagram of the obtained nanoparticles were characterized, specifically as follows: Figure 3-4 As shown.

[0065] Example 3

[0066] The organic amine in Example 1 was selected as piperidine, and all other parameters were the same as in Example 1. Analysis revealed that the obtained nanoparticles contained Zn3(C6H5COO)7(CH3COO)(C5H 11 The raw materials used in the N)2H2 nanoparticles, as well as their particle size, 1H NMR spectrum, and single-crystal image, were characterized. Specifically, as follows... Figure 5 As shown in Figure -6. Based on the MRI results: 1 H NMR (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 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, 1.60, and 2.99, respectively; the methyl peak in zinc acetate shifted from 1.82 to 1.86; and the benzene ring peak in benzoic acid also shifted from 7.51, 7.63, and 7.95 to 7.40, 7.45, and 7.94.

[0067] Example 4

[0068] The organic amine in Example 1 was selected as tetrahydropyrrole, and other parameters were the same as in Example 1. Analysis revealed that the obtained nanoparticles contained Zn4(C6H5COO)6(CH3COO)6(C4H9N)4H. The raw materials used, as well as the particle size, 1H NMR spectrum, and single-crystal image of the obtained nanoparticles, were characterized, as detailed below. Figure 7 As shown in Figure -8. Based on the MRI results: 1 H NMR (600 MHz, DMSO- d 6) 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). Each monomer undergoes coordination, resulting in peak shifts. The peaks in the tetrahydropyrrole structure shifted from 1.54 and 2.66 to 1.77 and 3.06, respectively; the methyl peak in zinc acetate shifted from 1.82 to 1.86; and the benzene ring peak in benzoic acid also shifted from 7.51, 7.63, and 7.95 to 7.38, 7.44, and 7.93.

[0069] Example 5

[0070] 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, triphenylsulfonate perfluorobutane sulfonic acid, accounting for 10% of the composition by mass, was added as a photoacid. The mixture was stirred for 5 minutes until it was completely dissolved, resulting in a photoresist mixed solution.

[0071] 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.

[0072] The pattern obtained from the test is as follows Figure 9A and Figure 9B As shown. Figure 9A The composition in Example 5 is shown under medium ultraviolet (150 mJ / cm2) and electron beam (200 μC / cm2) conditions. 2 ,50 nm) Figure 9B Under these conditions, a clear exposure pattern was obtained.

[0073] Examples 6-8

[0074] The nanoparticles obtained in Examples 2-4 were subjected to photolithography tests according to the corresponding compositions obtained in Example 5, and the resulting patterns are as follows. Figure 10A-12B As shown. Figure 10A and Figure 10B The composition of Example 6 was tested under medium ultraviolet light (150 mJ / cm). 2 Under these conditions and with an electron beam (150 μC / cm²), 2 Exposure pattern under conditions of 50 nm. Figure 11A and Figure 11B They were respectively in the mid-ultraviolet (150 mJ / cm) 2 Under these conditions and with an electron beam (200 μC / cm²), 2 Exposure pattern of the composition of Example 7 under conditions of 50 nm. Figure 12A and Figure 12B They were respectively in the mid-ultraviolet (150 mJ / cm) 2 Under these conditions and with an electron beam (150 μC / cm²), 2 Exposure pattern of the composition of Example 8 under conditions of 50 nm.

[0075] Comparative Example 1

[0076] For the preparation method in Example 1, the organic amine was replaced with triethylamine to obtain nanoparticles. Everything else was the same as in Example 1. Further, the corresponding photoresist composition was obtained according to Example 5.

[0077] Example 10

[0078] For Example 5 and Comparative Example 1, exposure was performed under EUV (exposure conditions 90 mJ / cm). 2 And obtain it after 2 months. Figure 13-14The exposed image.

[0079] The images show that the nanoparticles of Example 1, when first synthesized, exhibited good contrast with no bridging in the lines. After two months, the lines became relatively clear with fewer bridging and still maintained good contrast. In contrast, the nanoparticles of Comparative Example 1, when first synthesized, showed slightly poor contrast with bridging in the lines. After two months, the lines became severely adhered and fractured, resulting in relatively poor contrast. Therefore, the nanoparticles in this application demonstrate better stability than those of Comparative Example 1.

[0080] In summary, this invention has obtained four effective nanoparticles and corresponding compositions, verified their particle size distribution and good photolithography performance at 254 nm and under electron beam exposure conditions, which can achieve superior photolithography performance such as high resolution, high sensitivity, and low line roughness, and proved that benzoic acid as a ligand can improve the stability of nanoparticles in photolithography.

Claims

1. A Zn-based organic coordination nanoparticle, characterized in that, The general chemical formula is [Zn] m X n (CH3COO) t Y p H q H q ] r Where X is benzoate, CH3COO represents acetate, Y is a nitrogen-containing organic ligand, r is the degree of polymerization, m, n, p, q, 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 nitrogen-containing organic ligands are selected from diethylamine, tetrahydropyrrole, piperidine, and diisopropylethylamine.

2. The nanoparticles according to claim 1, characterized in that, The Zn-based organic coordination nanoparticles have the structural formula Zn2(C6H5COO)5(C4H 11 N)H, where C4H 11 N is diethylamine, and C6H5COO is benzoate; or Zn4(C6H5COO)6(CH3COO)6(C4H9N)4H4, where C4H9N is tetrahydropyrrole; or Zn3(C6H5COO)7(CH3COO)(C5H 11 N)2H2, where C5H 11 N represents piperidine; or Zn2(C6H5COO)5(C8H 19 N)H, where C8H 19 N is diisopropylethylamine.

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

4. A method for preparing Zn-based organic coordination nanoparticles, characterized in that, The Zn-based organic coordination nanoparticles according to any one of claims 1-3 are obtained by mixing and stirring a zinc-containing compound, benzoic acid, and a nitrogen-containing organic ligand in an organic solvent and then performing 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 post-treatment includes stirring at 45℃-80℃ for 5h-24h, then rotary evaporating at 40℃-60℃ for 20min-80min, and then vacuum drying at 45℃-75℃ for 5h in a vacuum oven.

5. The method for preparing nanoparticles as described in claim 4, characterized in that, The zinc-containing compound is zinc acetate.

6. A photoresist composition, characterized in that, Including the nanoparticles described in any one of claims 1-3.

7. The photoresist composition according to claim 6, 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.

8. The photoresist composition according to claim 7, 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.

9. The photoresist composition according to claim 7, 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.

10. A photolithography method, characterized in that, Using the photoresist composition according to any one of claims 6-9, the photoresist composition is dropped onto a substrate, rotated, heated, and then exposed with an electron beam, mid-ultraviolet, deep ultraviolet, or extreme ultraviolet light, and developed with a developer.

11. The photolithography method according to claim 10, 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 .

12. The photolithography method according to claim 10, characterized in that, The developer is selected from any one or more of indene, indane, quinoline, 1-methylnaphthalene, toluene, o-xylene, m-xylene, ethyl acetate, butyl acetate, ethanol, n-propanol, tetrahydronaphthalene, decahydronaphthalene, isopropanol, n-butanol, n-hexane, and cyclohexane, and the developing temperature is 20℃~50℃.

13. An application of a nanoparticle, characterized in that, The nanoparticles are those described in any one of claims 1-3, and the nanoparticles are used in the field of photoresist.

14. The use of the nanoparticles as described in claim 13, characterized in that, The photoresist is an electron beam, mid-ultraviolet, deep ultraviolet, or extreme ultraviolet photoresist.

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