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

Abstract

The embodiment of the invention provides Zn-based organic coordination nanoparticles and a preparation method thereof, a photoresist composition and application thereof, the Zn-based organic coordination nanoparticles are obtained by mixing and stirring a zinc-containing compound, a nitrogen-containing organic ligand and a compound A in an organic solvent and then performing post-treatment, and the compound A is benzoylformic acid and a derivative thereof. According to the Zn-based organic coordination nanoparticle photoresist provided by the embodiment of the invention, under the condition of no photoinitiator, benzoylformic acid in the photoresist structure absorbs photons for self-initiation, and an exposure pattern is directly obtained, so that the exposure efficiency is improved.

Description

Technical Field

[0001] The embodiments of the present invention relate to the field of photoresist technology, and in particular to Zn-based organic coordination nanoparticles and a preparation method thereof, a photoresist composition and an application thereof. Background Art

[0002] Photoresist is a key material for fine pattern processing in microelectronics technology. It is usually composed of photoinitiators, photoresist resins, solvents, monomers and other additives. Among them, photoinitiators are a class of compounds that can absorb energy of a certain wavelength in the ultraviolet region (250-420nm) or visible light region (400-800nm) to produce free radicals, cations, etc., thereby initiating monomer polymerization or polymer decomposition. Traditional photoresists and metal-based photoresists that have been widely studied in recent years have always needed to undergo chemical changes under the action of photoinitiators, thereby producing changes in solubility.

[0003] However, photons need to be absorbed by the photoinitiator first and then decomposed. Then the photoinitiator product reacts with the photoresist resin. In order to ensure the solubility of the photoinitiator in the solvent, the amount of photoinitiator added is limited, so the exposure efficiency is low and the sensitivity of the photoresist is low, which greatly affects the production efficiency. In addition, the chemical properties of the photoinitiator are unstable and expensive, which increases the cost and difficulty of the production process. Summary of the invention

[0004] Based on this, it is necessary to propose a new Zn-based organic coordination nanoparticle and a preparation method thereof, a photoresist composition containing the same and its application to address the problems of low exposure efficiency and high cost of traditional photoresists.

[0005] In one aspect, the present invention provides a Zn-based organic coordination nanoparticle, which is obtained by the following preparation method:

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

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

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

[0009] Optionally, the structural formula of the compound represented by the 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] The zinc-containing compound, the nitrogen-containing organic ligand and the compound A are mixed and stirred in an organic solvent to obtain a clear solution, wherein the compound A is benzoylformic acid and its derivatives;

[0013] The clear solution is post-treated, and the post-treatment includes: stirring at 50° C. for 6 h to 24 h, then vacuum evaporating for 1 h using a rotary evaporator, and then vacuum drying in a vacuum oven at 50° C. for 5 h.

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

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

[0016] Another aspect of the present invention provides a photoresist composition comprising the aforementioned nanoparticles.

[0017] Optionally, the photoresist composition further comprises an organic dispersing solvent, and the organic dispersing 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.

[0018] Optionally, the solid content of the Zn-based organic-coordinated nanoparticles is in the range of 1 wt% to 10 wt%.

[0019] Another aspect of the present invention provides a photolithography method, which uses the above-mentioned photoresist composition, drops the photoresist composition onto a substrate, rotates, heats, and then exposes it with an electron beam, mid-ultraviolet, deep ultraviolet or extreme ultraviolet, and develops it with a developer.

[0020] Optional, exposure dose under mid-UV is 5mJ / cm 2 ~500mJ / cm 2 .

[0021] Optionally, the developer is selected from any one or more of indene, indane, quinoline, 1-methylnaphthalene, toluene, o-xylene, m-xylene, ethyl acetate, butyl acetate, isopropanol, ethanol, n-propanol, tetralin, decalin, n-butanol, n-hexane and cyclohexane, and the developing temperature is 20°C to 50°C.

[0022] Another aspect of the present invention provides a use of Zn-based organic coordination nanoparticles for use 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 by the embodiment of the present invention, on the one hand, can directly obtain an exposure pattern by self-initiating by benzoylformic acid in the photoresist structure absorbing photons in the absence of a photoinitiator, thereby improving the exposure efficiency; on the other hand, the Zn-based organic coordination nanoparticle photoresist provided by the present invention does not contain a photoinitiator, thereby reducing the cost in the production process. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on the provided drawings without paying any creative work.

[0025] Figure 1 The nuclear magnetic hydrogen spectrum of the Zn-based organic coordination nanoparticles and raw materials of Example 1 of the present invention;

[0026] Figure 2 This is an infrared spectrum of the Zn-based organic coordination nanoparticle photoresist of Example 1 of the present invention;

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

[0028] Figure 4 The photoresist of the comparative example of the present invention is exposed at 254nm. DETAILED DESCRIPTION

[0029] References to embodiments of the present invention will now be provided in detail, one or more examples of which are described below. Each example is provided as an explanation rather than a limitation of the present invention. In fact, it will be apparent to those skilled in the art that various modifications and variations may be made to the present invention without departing from the scope or spirit of the present invention. For example, a feature illustrated or described as part of one embodiment may be used in another embodiment to produce a further embodiment.

[0030] Therefore, it is intended that the present invention covers such modifications and variations that fall within the scope of the appended claims and their equivalents. Other objects, features and aspects of the present invention are disclosed in or are obvious from the following detailed description. Those of ordinary skill in the art will appreciate that this discussion is only a description of exemplary embodiments and is not intended to limit the broader aspects of the present invention.

[0031] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art of the present invention. The terms used herein in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more related listed items.

[0032] Except as shown in the operating examples or otherwise indicated, all numbers used in the specification and claims to indicate the amount of ingredients, physicochemical properties, etc. are understood to be adjusted by the term "about" in all cases. For example, therefore, unless otherwise indicated, the numerical parameters listed in the above specification and the appended claims are approximate values, and those skilled in the art can use the teachings disclosed herein to seek to obtain the desired properties and appropriately change these approximate values. The use of numerical ranges expressed as endpoints includes all numbers within the range and any range within the 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 beams) incident on a unit area that causes the photoresist to react completely. In the present invention, the unit of ultraviolet photoresist sensitivity is mJ cm -2 The smaller the value, the higher the sensitivity of the photoresist. The unit of electron beam photoresist sensitivity is μC cm -2 The smaller the value, the higher the sensitivity of the photoresist. The sensitivity of the photoresist can also be reflected by the minimum exposure dose, which is exposure dose = light intensity × exposure time.

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

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

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

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

[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; pyridine and its derivatives are selected from any one or more of methylpyridine, vinylpyridine, methylpyridine, perhydropyridine, α-pyridine, etc.; 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; amides and their derivatives are selected from any one or more of formamide, stearamide, succinamide, oxalamide, acrylamide, and nicotinamide.

[0040] In a 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 the zinc-containing compound: benzoylformic acid and the nitrogen-containing organic ligand is in the range of 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 a specific embodiment, the molar percentage range of the compound A relative to the zinc-containing compound is ≥2:1.

[0044] The post-treatment comprises: stirring at 50° C. for 6 h to 24 h, then vacuum evaporating the mixture using a rotary evaporator for 1 h, and then vacuum drying the mixture in a vacuum oven at 50° C. for 5 h.

[0045] The Zn-based organic coordination nanoparticles provided in the embodiment of the present invention directly capture photons through the synergistic effect between zinc atoms, benzoylformic acid and nitrogen-containing organic ligands, and the -COCOOH in benzoylformic acid has high reactivity, so that the photoresist particles themselves can be photosensitized, and thus can be directly used as photoresist for graphic manufacturing without a photoinitiator.

[0046] The Zn-based organic coordination nanoparticle photoresist provided by the embodiment of the present invention can, on the one hand, directly obtain an exposure pattern by self-initiating by absorbing photons by benzoylformic acid in the photoresist structure without a photoinitiator, thereby improving the exposure efficiency. On the other hand, the Zn-based organic coordination nanoparticle photoresist provided by the present invention does not contain a photoinitiator, thereby reducing the cost in the production process.

[0047] The method for preparing the above-mentioned Zn-based organic coordination nanoparticles comprises the following steps:

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

[0049] The molar ratio of the zinc-containing compound: benzoylformic acid and the nitrogen-containing organic ligand is in the range of 1:(1-6):(2-8).

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

[0051] Furthermore, to ensure the photolithography effect, the molar percentage range of the compound A to the zinc-containing compound is greater than or equal to 1: 1. If the molar percentage range of benzoylformic acid and its derivatives to the zinc-containing compound is too small, the exposure sensitivity will be greatly reduced or even the exposure pattern cannot be obtained.

[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, post-treating the clarified solution, wherein the post-treating comprises: stirring at 50° C. for 6 h to 24 h, then vacuum evaporating with a rotary evaporator for 1 h, and then vacuum drying in a vacuum oven at 50° C. for 5 h.

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

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

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

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

[0059] Too much photoresist may not be dissolved; too little photoresist may not form a film. Therefore, in a specific embodiment, the solid content of Zn-based nanoparticles in the photoresist composition should be controlled within a range of 1 wt% to 10 wt%.

[0060] The present invention also provides a photolithography method, comprising the above-mentioned photoresist composition, dropping the photoresist composition onto a substrate, rotating, heating, then exposing with electron beam, mid-ultraviolet, deep ultraviolet or extreme ultraviolet, and developing with a developer.

[0061] The exposure condition is selected from any one of mid-ultraviolet, deep ultraviolet, electron beam, and extreme ultraviolet. The photoresist composition of the present invention can be used in any exposure condition.

[0062] The exposure dose should be controlled within an appropriate range. If the exposure dose is too small, the energy is too low, which is not conducive to the polymerization of the photoresist particles in the exposure area, and is not conducive to the formation of the difference in solubility between the exposure area and the non-exposure area, resulting in poor development effect. Compared with bare metal nanoparticles, the polymerization of nanoparticles containing organic ligands is easier to proceed. If the exposure dose is too large, it may cause line adhesion and it is impossible to obtain an independent exposure pattern. Therefore, in a specific embodiment, the exposure dose under medium ultraviolet conditions can be 5mJ / cm 2 ~500mJ / cm 2 , specifically, it can be 5mJ / cm 2 , 15mJ / cm 2 , 100mJ / cm 2 , 200mJ / cm 2 wait.

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

[0064] Regarding masks, deep ultraviolet and longer wavelength light sources are transmissive masks, extreme ultraviolet is a reflective mask, and the electron beam exposes according to the pattern set by the software.

[0065] 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, isopropanol, n-propanol, tetralin, decalin, n-butanol, n-hexane and cyclohexane, and the developing temperature is 20°C to 50°C, such as 25°C, 30°C, 40°C, etc.

[0066] The thickness of the pre-film layer cannot be too thick or too thin. If it is too thick, the lines of the lithography machine will collapse easily, and if it is too thin, the lines will be easily washed away. Therefore, in a specific embodiment, the thickness of the pre-film layer after removing the organic dispersion solvent can be 10nm to 100nm. Specifically, the thickness of the pre-film layer 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, 90nm to 100nm.

[0067] Furthermore, the above-mentioned 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 is described in detail with reference to specific embodiments:

[0069] Example 1

[0070] Weigh appropriate amounts of zinc acetate dihydrate, benzoylformic acid and diethylamine, wherein the molar percentage of zinc acetate dihydrate, benzoylformic acid and diethylamine is 2:4:3, disperse them in a 150mL round-bottom flask with a certain amount of ethyl acetate, and stir and heat at 50°C for 6-24h to obtain a reaction product. Cool the reaction product, and then use a rotary evaporator at 50°C for 1h to remove the solvent ethyl acetate. Then vacuum dry at 50°C for 5h to obtain a Zn-based coordinated nanoparticle photoresist.

[0071] The raw materials and photoresist were characterized by nuclear magnetic hydrogen spectrum, and the test results are as follows: Figure 1 As shown. Among them, zinc acetate: 1 H NMR (400MHz, DMSO-d6) δ1.82 (s, 6H). Diethylamine: 1 H NMR (400 MHz, DMSO-d6) δ2.50 (q, J = 7.1 Hz, 4H), 0.98 (t, J = 7.1 Hz, 6H). Benzoylformic acid: 1H NMR (400 MHz, DMSO-d6) δ7.99-7.92 (m, 2H), 7.83-7.74 (m, 1H), 7.68-7.57 (m, 2H). Ethyl acetate: 1 H NMR (400 MHz, DMSO-d6) δ4.03 (q, J = 7.1 Hz, 2H), 1.99 (s, 3H), 1.18 (t, J = 7.1 Hz, 3H). Photoresist: 1H NMR (400 MHz, DMSO-d6) δ7.97-7.87 (m, 2H), 7.67-7.58 (m, 1H), 7.55-7.44 (m, 2H), 2.89 (q, J = 7.3 Hz, 3H), 1.83 (s, 3H), 1.14 (t, J = 7.3 Hz, 5H).

[0072] It can be seen from the NMR spectrum that after the photoresist is synthesized, each monomer is coordinated and peak shifts occur. The peaks in the diethylamine structure shift from 0.98 and 2.50 to 1.14 and 2.89 respectively; the peak of the methyl group in zinc acetate shifts from 1.82 to 1.83; the peak in benzoylformic acid shifts from 7.96, 7.78, 7.63 to 7.92, 7.61, 7.50. The other peaks in the photoresist NMR are the peaks of the solvent ethyl acetate.

[0073] The photoresist of Example 1 was characterized by infrared spectroscopy. Figure 2 As shown. Figure 2 Available, 1737cm -1 is the carbonyl peak of benzoylformic acid, 1595 cm -1 、1445cm -1 It is the vibration peak of the benzene ring skeleton.

[0074] Example 2

[0075] Weigh an appropriate amount of the photoresist of Example 1 and an organic solvent (propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether or propylene glycol monoethyl ether) in a certain proportion to prepare a photoresist solution of a certain concentration (solution solid content 5wt%), and filter after dissolving to remove impurities in the prepared photolithography solution. Add 5 drops of photoresist solution to the substrate, set the rotation speed to 2000r / min, and rotate for 1min. Then heat on a hot plate at 80°C for 1min. Then expose using a medium ultraviolet exposure machine and an electron beam exposure machine respectively. After exposure, take out the substrate and develop it with mesitylene for 1-10s. After development (nitrogen), blow dry the substrate and observe the photolithography imaging results. Among them, Figure 3 This is a mid-UV (254nm) exposure image with a dose of 120mJ / cm 2 ; The photolithographic pattern was obtained by adopting small-dose exposure, indicating that the Zn-based coordinated nano-photoresist prepared in this application has high sensitivity.

[0076] Comparative Example 1

[0077] Replace the benzoylformic acid in Example 1 with benzoic acid, weigh appropriate amounts of zinc acetate dihydrate, benzoic acid and diethylamine, disperse them in a 150 mL round-bottom flask with a certain amount of ethyl acetate, and stir and heat at 65°C for 6-24 hours to obtain a reaction product. Cool the reaction product, and then use a rotary evaporator to evaporate at 65°C for 1 hour to remove the solvent ethyl acetate. Then vacuum dry at 65°C for 5 hours, and add 10% of photoinitiator during the preparation of the photoresist solution. Use a medium ultraviolet (254nm) exposure machine for exposure, and the exposure dose is 150mJ cm -2 , the exposure picture is as follows Figure 4 shown.

[0078] In combination with 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, photolithographic patterns are obtained by using small-dose exposure, indicating that the Zn-based nanoparticle photoresists prepared in the present application have high sensitivity.

[0079] Combining Example 1 and Comparative Example 1, it can be seen that the photoresist with added initiator in Comparative Example 1 can obtain exposure patterns only under 254nm ultraviolet exposure, while the photoresist of the present invention can be directly exposed without adding photoinitiator. This shows that the Zn-based nanoparticle photoresist prepared in the embodiment of the present invention can directly obtain exposure patterns without photoinitiator through self-initiation of benzoylformic acid absorbing photons in the photoresist structure, thereby improving exposure efficiency.

[0080] In summary, the nanoparticles prepared in the embodiments of the present invention and the corresponding compositions have been verified to have good lithography performance under mid-ultraviolet and electron beam conditions. In the absence of a photoinitiator, the exposure pattern can be directly obtained by self-initiating through the absorption of photons by benzoylformic acid in the photoresist structure, thereby improving the exposure efficiency. On the other hand, the Zn-based organic coordination nanoparticle photoresist provided by the present invention does not contain a photoinitiator, thereby reducing the cost in the production process.

[0081] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described 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 above-mentioned embodiments only express several embodiments of the present application, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the patent application. It should be pointed out that, for a person of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present application, and these all belong to the protection scope of the present application. Therefore, the protection scope of the patent application shall be subject to the attached claims.

Claims

1. A Zn-based organic coordination nanoparticle, characterized in that: The following preparation method is used to obtain: The zinc-containing compound, the nitrogen-containing organic ligand and the A compound are mixed and stirred in an organic solvent and then post-treated to obtain the compound, wherein the A compound is benzoylformic acid and its derivatives.

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

1.

3. The Zn-based organic coordination nanoparticles according to claim 2, characterized in that: The compound A is a compound represented by the general formula (I), Among them, R1, R2, R3, R4, and R5 are each independently selected from hydrogen, alkyl, alkoxy, alkyl alcohol, halogenated hydrocarbon, hydroxy, methoxy, nitro, -F, -Cl, -Br or -I.

4. The Zn-based organic coordination nanoparticles according to claim 3, characterized in that: The structural formula of the compound represented by the general formula (I) is 5. The Zn-based organic coordination nanoparticles according to any one of claims 1 to 4, characterized in that: 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.

6. A method for preparing Zn-based organic coordination nanoparticles, characterized in that: The steps include: The zinc-containing compound, the nitrogen-containing organic ligand and the compound A are mixed and stirred in an organic solvent to obtain a clear solution, wherein the compound A is benzoylformic acid and its derivatives; The clear solution is post-treated, and the post-treatment includes: stirring at 50° C. for 6 h to 24 h, then vacuum evaporating for 1 h using a rotary evaporator, and then vacuum drying in a vacuum oven at 50° C. for 5 h.

7. The method for preparing Zn-based organic coordination nanoparticles according to claim 6, characterized in that: The molar percentage range of the compound A relative to the zinc-containing compound is ≥2:

1.

8. The method for preparing Zn-based organic coordination nanoparticles according to claim 6, characterized in that: The nitrogen-containing organic ligand is selected from diethylamine, tetrahydropyrrole, piperidine or diisopropylethylamine; The zinc-containing compound is selected from zinc acetate, zinc acetate dihydrate, zinc chloride or zinc sulfate.

9. A photoresist composition, characterized in that: The invention comprises the Zn-based organic coordination nanoparticles as described in any one of claims 1 to 5.

10. The photoresist composition according to claim 9, characterized in that It also includes an organic dispersing 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.

11. The photoresist composition according to claim 10, characterized in that The solid content of the Zn-based organic-coordinated nanoparticles is in the range of 1 wt % to 10 wt %.

12. A photolithography method, characterized in that: The photoresist composition according to any one of claims 9 to 11 is added dropwise to a substrate, rotated, heated, exposed to electron beam, mid-ultraviolet, deep ultraviolet or extreme ultraviolet light, and developed with a developer.

13. The photolithography method according to claim 12, characterized in that: The exposure dose under medium UV is 5mJ / cm 2 ~500mJ / cm 2 .

14. The photolithography method according to claim 12, characterized in that: 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, isopropanol, tetralin, decalin, n-butanol, n-hexane and cyclohexane, and the developing temperature is 20°C to 50°C.

15. The use of Zn-based organic coordination nanoparticles according to any one of claims 1 to 5, characterized in that: Used in the field of photoresists, including electron beam, mid-UV, deep UV or extreme UV photoresists.

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