A Zn-based organic coordination nanoparticle and its preparation method, a photoresist composition and its application

Abstract

This invention provides Zn-based organic coordination nanoparticles, their preparation method, a photoresist composition, and their applications. The Zn-based organic coordination nanoparticles are obtained by mixing and stirring a zinc-containing compound, a nitrogen-containing organic ligand, and compound A in an organic solvent, followed by post-treatment. Compound A is benzoylformic acid and its derivatives. The Zn-based organic coordination nanoparticle photoresist provided by this invention can directly obtain exposure patterns without a photoinitiator by self-initiating exposure through photon absorption by benzoylformic acid in the photoresist structure, thereby improving exposure efficiency.

Description

Technical Field

[0001] The embodiments of the present invention relate 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 key material for fabricating fine patterns in microelectronics. It typically consists of photoinitiators, photoresist resins, solvents, monomers, and other additives. Photoinitiators are compounds that absorb energy of a specific wavelength in the ultraviolet (250–420 nm) or visible (400–800 nm) region, generating free radicals, cations, etc., thereby initiating monomer polymerization or polymer decomposition. Traditional photoresists and the metal-based photoresists that have been extensively studied in recent years have always required a chemical change under the action of a photoinitiator, resulting in a change in solubility.

[0003] However, photons must first be absorbed and decomposed by the photoinitiator, and then the photoinitiator products react with the photoresist resin. To ensure the solubility of the photoinitiator in the solvent, the amount of photoinitiator added is limited, resulting in low exposure efficiency and low photoresist sensitivity, which greatly affects production efficiency. In addition, photoinitiators are chemically unstable and expensive, thus increasing the cost and difficulty of the production process. Summary of the Invention

[0004] Therefore, it is necessary to address the problems of low exposure efficiency and high cost of traditional photoresists by proposing a new Zn-based organic coordination nanoparticle, its preparation method, a photoresist composition containing it, and its applications.

[0005] In one aspect, this invention provides Zn-based organic coordination nanoparticles, which are obtained using the following preparation method:

[0006] The zinc-containing compound, nitrogen-containing organic ligand, and compound A are mixed and stirred in an organic solvent and then post-treated to obtain the product. Compound A is benzoylformic acid and its derivatives.

[0007] Optionally, the molar percentage of compound A relative to the zinc-containing compound is in the range of ≥2:1.

[0008] Optionally, compound A is a compound represented by general formula (I). R1, R2, R3, R4, and R5 are independently selected from hydrogen, alkyl, alkoxy, alkyl alcohol, haloalkanes, hydroxyl, methoxy, nitro, -F, -Cl, -Br, or -I.

[0009] Optionally, the structural formula of the compound represented by general formula (I) is:

[0010] Optionally, the nitrogen-containing organic ligand is selected from diethylamine, tetrahydropyrrole, piperidine, or diisopropylethylamine, and the zinc-containing compound is selected from zinc acetate, zinc acetate dihydrate, zinc chloride, or zinc sulfate.

[0011] In another aspect, the present invention provides a method for preparing Zn-based organic coordination nanoparticles, comprising the following steps:

[0012] A zinc-containing compound, a nitrogen-containing organic ligand, and compound A are mixed and stirred in an organic solvent to obtain a clear solution. Compound A is benzoylformic acid and its derivatives.

[0013] The clarified solution is then subjected to post-treatment, which includes: stirring at 50°C for 6-24 hours, then vacuum evaporating in a rotary evaporator for 1 hour, and then vacuum drying in a vacuum oven at 50°C for 5 hours.

[0014] Optionally, the molar percentage of compound A relative to the zinc-containing compound is in the range of ≥2:1.

[0015] Optionally, the nitrogen-containing organic ligand is selected from organic amines such as diethylamine, tetrahydropyrrole, piperidine, or diisopropylethylamine; the zinc-containing compound is selected from zinc acetate, zinc acetate dihydrate, zinc chloride, or zinc sulfate.

[0016] In another aspect, the present invention provides a photoresist composition comprising the aforementioned nanoparticles.

[0017] Optionally, the photoresist composition further includes an organic dispersion solvent 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.

[0018] Optionally, the solid content of the Zn-based coordinated nanoparticles ranges from 1 wt% to 10 wt%.

[0019] In another aspect, the present invention provides a photolithography method, which employs the aforementioned photoresist composition, wherein the photoresist composition is dropped onto a substrate, rotated, heated, and then exposed to electron beam, mid-ultraviolet, deep ultraviolet or extreme ultraviolet light, and developed using a developer.

[0020] Optionally, the exposure dose under medium ultraviolet light is 5 mJ / cm. 2 ~500mJ / cm 2 .

[0021] Optionally, 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, isopropanol, ethanol, n-propanol, tetrahydronaphthalene, decahydronaphthalene, n-butanol, n-hexane, and cyclohexane, and the developing temperature is 20℃~50℃.

[0022] In another aspect, the present invention provides the use of Zn-based organic coordination nanoparticles in the field of photoresists, including electron beam, mid-ultraviolet, deep ultraviolet or extreme ultraviolet photoresists.

[0023] The Zn-based organic coordination nanoparticle photoresist provided in this invention has the following advantages: First, it can directly obtain exposure patterns by absorbing photons and self-initiating through benzoylformic acid in the photoresist structure without the need for a photoinitiator, thereby improving exposure efficiency. Second, the Zn-based organic coordination nanoparticle photoresist provided in this invention does not contain a photoinitiator, thus reducing production costs. Attached Figure Description

[0024] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of this application. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.

[0025] Figure 1 The 1H NMR spectra of the Zn-based organic coordination nanoparticles and raw materials in Example 1 of this invention are shown.

[0026] Figure 2 The infrared spectrum of the Zn-based organic coordination nanoparticle photoresist of Example 1 of the present invention is shown below.

[0027] Figure 3 This is an image of the Zn-based organic coordination nanoparticles of Example 1 of the present invention, exposed at 254 nm.

[0028] Figure 4 This is a sample image of the photoresist exposed at 254nm, which is a comparative example of the present invention. Detailed Implementation

[0029] Reference will now be made to detailed embodiments of the present invention, one or more of which are described below. Each example is provided for explanation and not for limitation of the invention. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made to the invention without departing from its scope or spirit. For example, features described or illustrated as part of one embodiment may be used in another embodiment to produce further embodiments.

[0030] Therefore, this invention is intended to cover such modifications and variations falling within the scope of the appended claims and their equivalents. Other objects, features, and aspects of the invention are disclosed in or will be apparent from the following detailed description. It will be understood by those skilled in the art that this discussion is merely a description of exemplary embodiments and is not intended to limit the broader aspects of the invention.

[0031] 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 specification of this invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0032] Unless otherwise shown or indicated in the operational embodiments, all figures used to represent the amounts, physicochemical properties, etc., of ingredients in the specification and claims are to be understood to be adjusted by the term "about" in all cases. For example, therefore, unless stated to the contrary, the numerical parameters listed in the foregoing specification and appended claims are approximations, and those skilled in the art can appropriately modify these approximations to obtain the desired characteristics by utilizing the teachings disclosed herein. The use of numerical ranges indicated by endpoints includes all numbers within that range and any range within that range; for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, etc.

[0033] Photoresist "sensitivity" refers to the minimum light energy or minimum charge (for electron beam photoresist) incident per unit area that causes the photoresist to react completely. In this invention, the unit for ultraviolet photoresist sensitivity is mJ / cm². -2 (The smaller the value, the higher the photoresist sensitivity); the unit for electron beam photoresist sensitivity is μC / cm. -2 This indicates (the smaller the value, the higher the photoresist sensitivity). Photoresist sensitivity can also be reflected by the minimum exposure dose, where exposure dose = light intensity × exposure time.

[0034] This invention provides a Zn-based organic coordination nanoparticle, which is obtained by the following preparation method:

[0035] The zinc-containing compound, nitrogen-containing organic ligand, and compound A are mixed and stirred in an organic solvent and then post-treated to obtain the product. Compound A is benzoylformic acid and its derivatives.

[0036] Benzoylcarboxylic acid derivatives refer to compounds in which one or more hydrogen atoms on the benzene ring of benzoylcarboxylic acid are replaced by one or more substituents. The substituents may be selected from, but are not limited to, halogens, carboxyl groups, carbonyl groups, hydroxyl groups, amino groups, R, OR, NR2, SR, C(O)R, C(O)OR, C(O)NR2, CN, CF3, NO2, SO2, SOR, and SO3R. R may independently be, but is not limited to, C1C. 10 Alkyl chain, C2C 10 Alkenyl, C2C 10 Alkynyl. In some embodiments, R is independently a C1C4 alkyl, C2C4 alkenyl, or C2C4 alkynyl, specifically, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, vinyl, propenyl, ethynyl, etc.

[0037] In one specific embodiment, compound A is a compound of general formula (I). (I) Wherein, R1, R2, R3, R4, and R5 are independently selected from hydrogen, alkyl, alkoxy, alkyl alcohol, haloalkanes, hydroxyl, methoxy, nitro, -F, -Cl, -Br, or -I; the alkyl group can be a straight-chain alkyl group or a branched alkyl group, for example, alkyl can be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl. Alkoxy refers to the combination of alkyl and oxygen atoms, specifically, it can be ethylene oxide or propylene oxide. Alkyl alcohol refers to the combination of alkyl and hydroxyl groups, and can be a straight-chain alkyl alcohol or a branched alkyl alcohol, specifically, alkyl alcohol can be ethanol, propanol, butanol, isobutanol, pentanol, etc.

[0038] Specifically, the structural formula of compound A can be:

[0039] The nitrogen-containing organic ligand is 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 organic fatty amines are selected from any one or more of triisopropylamine, triethanolamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, and diisopropylethylamine; the pyridines and their derivatives are selected from any one or more of methylpyridine, vinylpyridine, methylpyridinidine, perhydropyridine, and α-pyridine; the pyrroles and their derivatives are selected from any one or more of tetrahydropyrrole, methylpyrrole, and vinylpyrrole; the pyridazines and their derivatives are selected from any one or more of vinylpyridazine and divinylpyridazine; the piperidines and their derivatives are selected from any one or more of piperidine, vinylpiperidine, and 3-methylpiperidine; and the amides and their derivatives are selected from any one or more of formamide, stearamide, succinamide, oxalamide, acrylamide, and nicotinamide.

[0040] In one specific embodiment, the nitrogen-containing organic ligand is selected from organic amines such as diethylamine, tetrahydropyrrole, piperidine, or diisopropylethylamine;

[0041] The zinc-containing compound is selected from zinc salts such as zinc acetate, zinc acetate dihydrate, zinc chloride, or zinc sulfate.

[0042] The molar ratio of zinc-containing compounds, benzoylcarboxylic acid, and nitrogen-containing organic ligands is 1:(1-6):(2-8).

[0043] As the amount of compound A increases, the number of -COCOOH groups increases, and the efficiency of photoresist nanoparticles in capturing photons increases. In one specific embodiment, the molar percentage of compound A relative to the zinc-containing compound is in the range of ≥2:1.

[0044] The post-processing includes: stirring at 50°C for 6-24 hours, then vacuum evaporating in a rotary evaporator for 1 hour, and then vacuum drying in a vacuum oven at 50°C for 5 hours.

[0045] The Zn-based organic coordination nanoparticles provided in this invention, through the synergistic effect between zinc atoms, benzoylformic acid and nitrogen-containing organic ligands, and the high reactivity of -COCOOH in benzoylformic acid, directly capture photons, making the photoresist particles themselves photosensitive. Thus, they can be directly used as photoresist for pattern fabrication without photoinitiators.

[0046] The Zn-based organic coordination nanoparticle photoresist provided in this invention, on the one hand, can directly obtain exposure patterns through photon self-initiation by benzoylformic acid in the photoresist structure without a photoinitiator, thereby improving exposure efficiency. On the other hand, the Zn-based organic coordination nanoparticle photoresist provided in this invention does not contain a photoinitiator, reducing production costs.

[0047] The preparation method of the above-mentioned Zn-based organic coordination nanoparticles includes the following steps:

[0048] Step S1: The zinc-containing compound, the nitrogen-containing organic ligand, and compound A are mixed and stirred in an organic solvent to obtain a clear solution, wherein compound A is benzoylformic acid and its derivatives;

[0049] The molar ratio of zinc-containing compounds, benzoylcarboxylic acid, and nitrogen-containing organic ligands is 1:(1-6):(2-8).

[0050] In one specific embodiment, the molar ratio of the zinc-containing compound, the nitrogen-containing organic ligand, and compound A is 2:3:4.

[0051] Furthermore, to ensure effective photolithography, the molar percentage of compound A to the zinc-containing compound must be greater than or equal to 1:1. If the molar percentage of benzoylformic acid and its derivatives to the zinc-containing compound is too small, the exposure sensitivity will be greatly reduced, or even impossible to obtain an exposure pattern.

[0052] The zinc-containing compound is selected from zinc acetate, zinc acetate dihydrate, zinc chloride, or zinc sulfate.

[0053] The nitrogen-containing organic ligand is selected from diethylamine, tetrahydropyrrole, piperidine, or diisopropylethylamine.

[0054] Step S2 involves post-processing the clarified solution, which includes stirring at 50°C for 6-24 hours, then vacuum evaporating it for 1 hour using a rotary evaporator, and finally vacuum drying it at 50°C for 5 hours in a vacuum oven.

[0055] The purpose of vacuum rotary evaporation is to remove the organic solvent quickly, making it difficult for the crystal nuclei of zinc-based organometallic nanoparticles to grow, thereby forming single crystals, that is, monodisperse zinc-based organometallic nanoparticles. Of course, in other embodiments, other methods can also be used to remove the organic solvent.

[0056] The temperature for vacuum rotary evaporation is 20℃ to 80℃. For example, it can be selected from 20℃, 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃, etc.

[0057] The present invention also provides a photoresist composition comprising the aforementioned nanoparticles.

[0058] Furthermore, the photoresist composition also includes an organic dispersion solvent 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.

[0059] Too much photoresist may prevent dissolution; too little photoresist may prevent film formation. Therefore, in one specific embodiment, the solid content of Zn-based nanoparticles in the photoresist composition should be controlled within the range of 1 wt% to 10 wt%.

[0060] The present invention also provides a photolithography method comprising the aforementioned photoresist composition, wherein the photoresist composition is dropped onto a substrate, rotated, heated, and then exposed to electron beam, mid-ultraviolet, deep ultraviolet or extreme ultraviolet light, and developed using a developer.

[0061] 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.

[0062] 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; however, excessive exposure dose may cause line adhesion, preventing the acquisition of independent exposure patterns. Therefore, in one specific embodiment, the exposure dose under mid-ultraviolet conditions can be 5 mJ / cm². 2 ~500mJ / cm 2 Specifically, it could be 5mJ / cm 2 15mJ / cm 2 100mJ / cm 2 200mJ / cm 2 wait.

[0063] The substrate is selected from silicon substrates. Other substrates that are insoluble in developer can also be selected according to actual needs.

[0064] 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.

[0065] 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, isopropanol, n-propanol, tetrahydronaphthalene, decahydronaphthalene, n-butanol, n-hexane, and cyclohexane. The developing temperature is 20℃ to 50℃, such as 25℃, 30℃, 40℃, etc.

[0066] The thickness of the pre-formed film cannot be too thick or too thin. If it is too thick, the lithography lines are prone to collapse; if it is too thin, the lines are easily washed away. Therefore, in one specific embodiment, the thickness of the pre-formed film after removing the organic dispersion solvent can be 10nm to 100nm. Specifically, the thickness of the pre-formed film can be 10nm to 20nm, 20nm to 30nm, 30nm to 40nm, 40nm to 50nm, 50nm to 60nm, 60nm to 70nm, 70nm to 80nm, 80nm to 90nm, or 90nm to 100nm.

[0067] Furthermore, the aforementioned Zn-based organic coordination nanoparticles are used in the field of photoresists, including electron beam, mid-ultraviolet, deep ultraviolet, or extreme ultraviolet photoresists.

[0068] The following detailed explanation is provided with reference to specific embodiments:

[0069] Example 1

[0070] Weigh appropriate amounts of zinc acetate dihydrate, benzoylformic acid, and diethylamine, wherein the molar percentages of zinc acetate dihydrate, benzoylformic acid, and diethylamine are 2:4:3. Disperse these components in a 150 mL round-bottom flask with a certain amount of ethyl acetate. Stir and heat at 50 °C for 6–24 h to obtain the reaction product. Cool the reaction product and then remove the solvent ethyl acetate by rotary evaporation at 50 °C for 1 h. Finally, vacuum dry at 50 °C for 5 h to obtain the Zn-based coordinated nanoparticle photoresist.

[0071] The raw materials used and the obtained photoresist were characterized by 1H NMR spectroscopy, and the test results are as follows: Figure 1 As shown. Among them, zinc acetate: 1 ¹H NMR (400MHz, DMSO-d6) δ 1.82 (s, 6H). Diethylamine: 1 ¹H NMR (400 MHz, DMSO-d6) δ 2.50 (q, J = 7.1 Hz, 4H), 0.98 (t, J = 7.1 Hz, 6H). Benzoylcarboxylic acid: ¹H NMR (400 MHz, DMSO-d6) δ 7.99–7.92 (m, 2H), 7.83–7.74 (m, 1H), 7.68–7.57 (m, 2H). Ethyl acetate: 1 ¹H NMR (400MHz, DMSO-d⁶) δ 4.03 (q, J = 7.1Hz, 2H), 1.99 (s, 3H), 1.18 (t, J = 7.1Hz, 3H). Photoresist: ¹H NMR (400MHz, DMSO-d⁶) δ 7.97-7.87 (m, 2H), 7.67-7.58 (m, 1H), 7.55-7.44 (m, 2H), 2.89 (q, J = 7.3Hz, 3H), 1.83 (s, 3H), 1.14 (t, J = 7.3Hz, 5H).

[0072] The NMR spectra show that after the photoresist was synthesized, 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 2.89, respectively; the methyl peak in zinc acetate shifted from 1.82 to 1.83; and the peaks in benzoylformic acid shifted from 7.96, 7.78, and 7.63 to 7.92, 7.61, and 7.50. The other peaks in the photoresist NMR are those of the solvent ethyl acetate.

[0073] The photoresist of Example 1 was characterized by infrared spectroscopy, such as... Figure 2 As shown. By Figure 2 Therefore, 1737cm -1 This is the carbonyl peak of benzoylformic acid, at 1595 cm⁻¹. -1 1445cm -1 The peak at this point represents the vibrational peak of the benzene ring skeleton.

[0074] Example 2

[0075] Weigh appropriate amounts of the photoresist from Example 1 and an organic solvent (propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, or propylene glycol monoethyl ether) and prepare a photoresist solution of a certain concentration (solid content 5 wt%) in a certain proportion. After dissolving, filter to remove impurities from the prepared photolithography solution. Add 5 drops of photoresist solution to the substrate, set the rotation speed to 2000 r / min, and rotate for 1 min. Then heat at 80°C on a hot plate for 1 min. Expose using a medium ultraviolet lithography machine and an electron beam lithography machine, respectively. After exposure, remove the substrate and develop it with trimethylbenzene for 1-10 s. After development, dry the substrate (with nitrogen) and observe the photolithography imaging results. Figure 3 This is a mid-ultraviolet (254nm) exposure image with a dose of 120mJ / cm. 2 The use of low-dose exposure to obtain photolithographic patterns demonstrates that the Zn-based coordinated nanophotoresist prepared in this application has high sensitivity.

[0076] Comparative Example 1

[0077] In Example 1, benzoylcarboxylic acid was replaced with benzoic acid. Appropriate amounts of zinc acetate dihydrate, benzoic acid, and diethylamine were weighed and dispersed in a 150 mL round-bottom flask with a certain amount of ethyl acetate. The mixture was stirred and heated at 65°C for 6-24 hours to obtain the reaction product. The reaction product was cooled and then removed by rotary evaporation at 65°C for 1 hour. The product was then vacuum dried at 65°C for 5 hours. 10% photoinitiator was added during the preparation of the photoresist solution. Exposure was performed using a mid-ultraviolet (254 nm) exposure machine with an exposure dose of 150 mJ / cm². -2 The exposed image is as follows Figure 4 As shown.

[0078] Based on Examples 1-2, it can be concluded that the Zn-based nanoparticle photoresists prepared in the embodiments of the present invention can form photolithographic images without the need for photoinitiators. Furthermore, the use of low-dose exposure to obtain photolithographic patterns demonstrates that the Zn-based coordinated nanophotoresists prepared in this application have high sensitivity.

[0079] As can be seen from Example 1 and Comparative Example 1, the photoresist in Comparative Example 1 with added initiator can only obtain exposure patterns under UV exposure at 254nm, while the photoresist of the present invention can be directly exposed without adding a photoinitiator. This indicates that the Zn-based nanoparticle photoresist prepared in the embodiments of the present invention can directly obtain exposure patterns through photon self-initiation by benzoylformic acid in the photoresist structure without a photoinitiator, thereby improving the exposure efficiency.

[0080] In summary, the nanoparticles and corresponding compositions prepared in the embodiments of the present invention have demonstrated good photolithography performance under medium ultraviolet and electron beam conditions. They can directly obtain exposure patterns by absorbing photons through benzoylformic acid in the photoresist structure without photoinitiators, thereby improving exposure efficiency. On the other hand, the Zn-based organic coordination nanoparticle photoresist provided by the present invention does not contain photoinitiators, which reduces the cost in the production process.

[0081] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0082] The embodiments described above are merely illustrative of several implementations of this application, and while their descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent application. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the protection scope of this application. Therefore, the protection scope of this patent application should be determined by the appended claims.

Claims

1. A Zn-based organic coordination nanoparticle, characterized in that, It is obtained by the following preparation method: The zinc-containing compound, nitrogen-containing organic ligand, and compound A are mixed and stirred in an organic solvent and then post-treated to obtain the product. Compound A is benzoylformic acid and its derivatives. Wherein, compound A is a compound represented by general formula (I). (I), wherein R1, R2, R3, R4, and R5 are each independently selected from hydrogen, alkyl, alkoxy, alkyl alcohol, hydroxyl, nitro, -F, -Cl, -Br, or -I; The nitrogen-containing organic ligand is selected from diethylamine, tetrahydropyrrole, piperidine, or diisopropylethylamine, and the zinc-containing compound is selected from zinc acetate, zinc acetate dihydrate, zinc chloride, or zinc sulfate.

2. The Zn-based organic coordination nanoparticles as described in claim 1, characterized in that, The molar percentage of compound A relative to the zinc-containing compound is in the range of ≥2:

1.

3. The Zn-based organic coordination nanoparticles as described in claim 1, characterized in that, The structural formula of the compound represented by general formula (I) is: .

4. A method for preparing Zn-based organic coordination nanoparticles, characterized in that, The steps include: mixing and stirring a zinc-containing compound, a nitrogen-containing organic ligand, and compound A in an organic solvent to obtain a clear solution, wherein compound A is benzoylformic acid and its derivatives; The clarified solution is post-treated, which includes: stirring at 50°C for 6-24 hours, then vacuum evaporating in a rotary evaporator for 1 hour, and then vacuum drying in a vacuum oven at 50°C for 5 hours. Wherein, compound A is a compound represented by general formula (I). (I), wherein R1, R2, R3, R4, and R5 are each independently selected from hydrogen, alkyl, alkoxy, alkyl alcohol, hydroxyl, nitro, -F, -Cl, -Br, or -I; The nitrogen-containing organic ligand is selected from diethylamine, tetrahydropyrrole, piperidine, or diisopropylethylamine, and the zinc-containing compound is selected from zinc acetate, zinc acetate dihydrate, zinc chloride, or zinc sulfate.

5. The method for preparing Zn-based organic coordination nanoparticles as described in claim 4, characterized in that, The molar percentage of compound A relative to the zinc-containing compound is in the range of ≥2:

1.

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

7. The photoresist composition according to claim 6, characterized in that, It also includes an organic dispersion solvent, which 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. The photoresist composition according to claim 7, characterized in that, The solid content of the Zn-based coordinated nanoparticles ranges from 1 wt% to 10 wt%.

9. A photolithography method, characterized in that, Using the photoresist composition according to any one of claims 6-8, 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.

10. The photolithography method according to claim 9, characterized in that, The exposure dose under medium ultraviolet light is 5 mJ / cm 2 ~500mJ / cm 2 .

11. The photolithography method according to claim 9, 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, isopropanol, tetrahydronaphthalene, decahydronaphthalene, n-butanol, n-hexane, and cyclohexane, and the developing temperature is 20℃~50℃.

12. An application of a nanoparticle, characterized in that, The nanoparticles are Zn-based organic coordination nanoparticles as described in any one of claims 1-3, and the nanoparticles are used in the field of photoresist.

13. The use of the nanoparticles according to claim 12, characterized in that, The photoresist is an electron beam, mid-ultraviolet, deep ultraviolet, or extreme ultraviolet photoresist.

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