Zinc-based metal-organic nanoparticles, preparation method thereof, and photoresist

Abstract

The present application discloses a zinc-based metal-organic nanoparticle with a core-shell structure, and the general formula is Zn x O y [A] 2x [B]2, where x is 2 or 3, 2x ≤ y ≤ 4x, Zn x O y is the inner core of the core-shell structure, A is the first organic ligand, B is the second organic ligand, the first organic ligand A and the second organic ligand B together constitute the outer shell of the core-shell structure, the first organic ligand A is selected from one or more of substituted or unsubstituted aliphatic groups and substituted or unsubstituted aromatic groups, and the second organic ligand B is selected from one or more of organic amines and their derivatives. The present application also discloses a preparation method of the zinc-based metal-organic nanoparticle and a photoresist.

Description

[0001] This application claims the priority of a Chinese patent application with the application number 202011547342.7 and the title "Photoresist, Preparation Method, Patterning Method and Method for Generating Printed Circuit Board", which was filed on December 24, 2020, and the entire content thereof is incorporated herein by reference. Technical Field

[0002] This application relates to the technical field of photoresists, and particularly to a zinc-based metal-organic nanoparticle, a preparation method thereof, and a photoresist. Background Art

[0003] A photoresist is a corrosion-resistant material whose solubility changes under the irradiation of light beams such as ultraviolet light, electron beam, particle beam, extreme ultraviolet (EUV), or X-ray. Photoresists are widely used in the pattern transfer during the manufacturing of semiconductor integrated circuits, liquid crystal panels, and high-end optical devices. According to Moore's Law, the semiconductor integration per unit area doubles every 18 - 24 months. With the continuous progress of semiconductor technology, the semiconductor size is continuously reduced, posing higher requirements for reducing the feature size in semiconductor processing. To meet more advanced semiconductor processes and achieve smaller feature sizes, lithography technology is also constantly evolving, from I-line, G-line, deep ultraviolet (DUV), 193nm, immersion 193nm and other lithography technologies to extreme ultraviolet lithography, electron beam lithography and other fine processing means.

[0004] Traditional photoresists have complex components, including a photoresist resin body, a photosensitizer, a leveling agent, a stabilizer, a dispersant, a thickening agent, and a solvent, etc. The production and manufacturing process is cumbersome, and the process requirements for controlling the ratio and purity are extremely high. Since traditional photoresists contain macromolecular polymers and various additives, their complex composition leads to a relatively wide size distribution of photoresist components, with components of various sizes, and the size conformation of some components can reach 10nm - 20nm, making it difficult to control the size of photoresist patterns and possibly generating numerous defects. In addition, the use of traditional photoresists is restricted by the wavelength of the light source, and different photoresists are required to match different wavelengths of light sources. Summary of the Invention

[0005] Based on this, it is necessary to propose a zinc-based metal-organic nanoparticle, a preparation method thereof, and a photoresist.

[0006] A zinc-based metal-organic nanoparticle has a core-shell structure and the general formula Zn x O y [A] 2x [B]2, where x is 2 or 3, 2x ≤ y ≤ 4x, Zn x Oy is the core of the core-shell structure, A is the first organic ligand, B is the second organic ligand, and the first organic ligand A and the second organic ligand B together form the shell of the core-shell structure. The first organic ligand A is selected from one or more of substituted or unsubstituted aliphatic groups and substituted or unsubstituted aromatic groups, and the second organic ligand B is selected from one or more of organic amines and their derivatives.

[0007] In some embodiments, the zinc-based metal-organic nanoparticles have photoactive groups.

[0008] In some embodiments, at least one of the first organic ligand A and the second organic ligand B has a photoactive group.

[0009] In some embodiments, the photoactive group is selected from one or more of carbon-carbon double bonds, acyloxy groups, acyl groups, aldehyde groups, carboxyl groups, ester groups, and amino groups.

[0010] In some embodiments, x = 3, and two Zn atoms are located at opposite ends of the Zn x O y core and are respectively connected to the N atoms in two of the second organic ligands B.

[0011] In some embodiments, x = 2, and two Zn atoms are jointly connected to the first organic ligand A through the surrounding O atoms, and the N atoms in two of the second organic ligands B are located at both ends of the Zn x O y core and are respectively connected to the two Zn atoms.

[0012] In some embodiments, the general formula of the zinc-based metal-organic nanoparticles is Zn2O8[A]4[B]2, Zn3O 12 [A]6[B]2 or Zn3O 10 [A]6[B]2.

[0013] In some embodiments, the size of the zinc-based metal-organic nanoparticles is 1 nm to 3 nm.

[0014] In some embodiments, the aliphatic group is a C1-C10 hydrocarbon group or a C3-C10 cycloalkyl group; the aromatic group has one or more aromatic rings, substituted aromatic rings, heteroaromatic rings, or substituted heteroaromatic rings, preferably a phenyl group or a substituted phenyl group.

[0015] In some embodiments, the first organic ligand A is represented by one or more of the following structures, where the dashed line represents the bond connected to the O of the Zn x O y core:

[0016]

[0017] Among them, R1 is independently selected from one or more of H, halogen, carboxyl, carbonyl, hydroxyl, amino, R, OR, NR2, SR, C(O)R, C(O)OR, C(O)NR2, CN, CF3, NO2, SO2, SOR, and SO3R. R is a substituent. In some embodiments, R is independently a C1-C10 linear alkyl group, a C2-C10 alkenyl group, a C2-C10 alkynyl group, a C3-C10 aryl group, a C3-C10 alkaryl group, or a C3-C10 cycloalkyl group; in some embodiments, R is independently a C1-C4 linear alkyl group, a C2-C4 alkenyl group, a C2-C4 alkynyl group, a phenyl group, or an alkylphenyl group.

[0018] In some embodiments, the second organic ligand B is selected from any one or more of chain amines and their derivatives and cyclic amines and their derivatives. The cyclic amines and their derivatives are selected from any one or more of imidazole and its derivatives, pyridine and its derivatives, pyrrole and its derivatives, pyrimidine and its derivatives, pyridazine and its derivatives, piperidine and its derivatives. The chain amines and their derivatives are selected from, but not limited to, any one or more of trimethylamine, triethylamine, tripropylamine, triisopropylamine, triethanolamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, and ethyldiisopropylamine.

[0019] In some embodiments, the general formula of the zinc-based metal-organic nanoparticles is Zn x O y [A1,A2] 2x [B1]2, Zn x O y [A1] 2x [B1,B2]2 or Zn x O y [A1,A2] 2x [B1,B2]2, where A1 and A2 respectively represent two different first organic ligands A, and B1 and B2 respectively represent two different second organic ligands B.

[0020] A method for preparing zinc-based metal-organic nanoparticles, comprising the following steps:

[0021] Mix a metal salt of zinc with an organic solvent to obtain a zinc metal salt solution;

[0022] Mix the zinc metal salt solution with a first organic ligand source and a second organic ligand source, and heat and stir for reaction;

[0023] Perform vacuum rotary evaporation on the reaction product to remove the organic solvent.

[0024] In some embodiments, the molar ratio of the metal salt of zinc, the first organic ligand source, and the second organic ligand source is 1:(0.5 - 6):(0.5 - 6).

[0025] A zinc-based metal-organic nanoparticle crystal is obtained by recrystallizing the zinc-based metal-organic nanoparticles or the product of vacuum rotary evaporation after redissolving them in the organic solvent.

[0026] A photoresist is obtained by dispersing any one or both of the zinc-based metal-organic nanoparticles and the zinc-based metal-organic nanoparticle crystals in an organic dispersion solvent.

[0027] In some embodiments, the photoresist is composed of the zinc-based metal-organic nanoparticles and an organic dispersion solvent.

[0028] This application provides a novel class of self-initiating zinc-based metal-organic nanoparticles based on a Zn x O y core and organic ligands, also known as photoresist particles. These photoresist particles can agglomerate under light irradiation without the need for photoacid generators, photoacid catalysts, photoinitiators, etc., and their solubility in the developer decreases. The photoresist particles in the unexposed area do not agglomerate and dissolve in the developer, so that the non-exposed area can be removed after development. When only these photoresist particles are contained, pattern fabrication can be carried out under various exposure conditions such as ultraviolet, deep ultraviolet, electron beam, extreme ultraviolet, etc., and at the same time, extremely high sensitivity and resolution can be obtained. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] To more clearly illustrate the technical solutions in the embodiments of the present disclosure, the following will briefly introduce the drawings required for description in the embodiments. Obviously, the following drawings are only some embodiments of the present disclosure. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0030] Figure 1 It is a schematic structural diagram of zinc-based metal-organic nanoparticles according to an embodiment of the present application.

[0031] Figure 2 It is a particle size distribution diagram of zinc-based metal-organic nanoparticles and traditional photoresist particles according to an embodiment of the present application.

[0032] Figure 3 It is a single crystal structure diagram of zinc-based metal-organic nanoparticles in Example 1 of the present application.

[0033] Figure 4 It is a chemical structure diagram of zinc-based metal-organic nanoparticles in Example 1 of the present application.

[0034] Figure 5Structural diagram of single crystal of zinc-based metal-organic nanoparticles for Example 2 of this application.

[0035] Figure 6 Chemical structure diagram of zinc-based metal-organic nanoparticles for Example 2 of this application.

[0036] Figure 7 Structural diagram of single crystal of zinc-based metal-organic nanoparticles for Example 3 of this application.

[0037] Figure 8 Chemical structure diagram of zinc-based metal-organic nanoparticles for Example 3 of this application.

[0038] Figure 9 Structural diagram of single crystal of zinc-based metal-organic nanoparticles for Example 4 of this application.

[0039] Figure 10 Chemical structure diagram of zinc-based metal-organic nanoparticles for Example 4 of this application.

[0040] Figure 11 For Example 5 of this application at 45 mJ / cm -2 Scanning electron microscope photo of the patterned photoresist layer obtained by deep ultraviolet exposure at the dose.

[0041] Figure 12 For Example 5 of this application at 75 mJ / cm -2 Scanning electron microscope photo of the patterned photoresist layer obtained by deep ultraviolet exposure at the dose.

[0042] Figure 13 For Example 5 of this application at 110 mJ / cm -2 Scanning electron microscope photo of the patterned photoresist layer obtained by deep ultraviolet exposure at the dose.

[0043] Figure 14 Scanning electron microscope photo of the patterned photoresist layer obtained by electron beam exposure at a dose of 50 μC under a mask for Example 5 of this application.

[0044] Figure 15 Scanning electron microscope photo of the patterned photoresist layer obtained by electron beam exposure at a dose of 50 μC under another mask for Example 5 of this application.

[0045] Figure 16 Scanning electron microscope photo of the patterned photoresist layer obtained by electron beam exposure at a dose of 50 μC under yet another mask for Example 5 of this application.

[0046] Figure 17 For Example 5 of this application at 7 mJ cm -2 Scanning electron microscope photo of the patterned photoresist layer obtained by extreme ultraviolet exposure at the dose.

[0047] Figure 18 Optical photograph of the patterned photoresist layer obtained by ultraviolet exposure at a wavelength of 254 nm at a dose of 300 mJ cm -2 for Example 5 of the present application under air test conditions.

[0048] Figure 19 Optical photograph of the patterned photoresist layer obtained by ultraviolet exposure at a wavelength of 254 nm at a dose of 300 mJ cm -2 for Example 5 of the present application under air test conditions. Detailed implementation manners

[0049] To facilitate the understanding of the present application, the present application will be described more comprehensively below with reference to the relevant drawings. Preferred embodiments of the present application are shown in the drawings. However, the present application can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, these embodiments are provided to make the understanding of the disclosure of the present application more thorough and comprehensive.

[0050] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field to which this application belongs. The terms used in the description of the present application herein are only for the purpose of describing specific embodiments and are not intended to limit the present application.

[0051] The scope of the term "light" used in the present application includes, but is not limited to, ultraviolet, deep ultraviolet, and extreme ultraviolet light, and also broadly encompasses electron beams, X-rays, etc.

[0052] An embodiment of the present application provides a photoresist particle. The crystal structure of the photoresist particle is a core-shell structure. The general formula of the photoresist particle is Zn x O y [A] 2x [B]2, where x is 2 or 3, 2x ≤ y ≤ 4x, Zn x O y is the inner core of the core-shell structure, A is the first organic ligand, B is the second organic ligand, and the first organic ligand A and the second organic ligand B together form the outer shell of the core-shell structure. The first organic ligand A is selected from one or more of substituted or unsubstituted aliphatic groups and substituted or unsubstituted aromatic groups. The second organic ligand B is selected from one or more of organic amines and their derivatives. The photoresist particle may have a photo-responsive group. Specifically, at least one of the first organic ligand A and the second organic ligand B may have a photo-responsive group. Under light irradiation, reactions may occur between the photo-responsive groups of different photoresist particles, causing the photoresist particles to agglomerate, thereby reducing the solubility of the exposed area in the developer.

[0053] The crystalline state of the photoresist particles refers to the state after the photoresist particles are dissolved in a solvent and then crystallized and precipitated.

[0054] This application has designed and prepared a new type of self-initiating metal oxide nanoparticles based on Zn x O y cores and organic ligands (this application also refers to them as photoresist particles or zinc-based metal-organic nanoparticles). Under the action of light, these photoresist particles agglomerate in the developer, resulting in a decrease in solubility, while the photoresist particles in the unexposed area do not agglomerate and dissolve in the developer, so that the photoresist in the non-exposed area can be removed after development. In particular, in the case of only containing photoresist particles, pattern fabrication can be carried out under various exposure wavelength conditions such as ultraviolet, deep ultraviolet, electron beam, extreme ultraviolet, etc., and at the same time, extremely high sensitivity and resolution can be obtained. The number of Zn atoms in the core Zn x O y is 2 - 3, and the outer shell is composed of two organic ligands. Zinc oxide Zn x O y cores have a high electron-donating ability and are highly sensitive to radiation of different wavelengths of rays or particles, and can cause agglomeration between the irradiated photoresist particles, thereby reducing the solubility of the exposed area in the developer. Through the synergistic effect of the Zn x O y core and the first organic ligand A and / or the second organic ligand B with photo-reactive groups, the photoresist particles themselves can be photosensitive and can thus be directly used as photoresists for pattern fabrication. In the photoresist containing these photoresist particles, it is not necessary to add photoacid generators, photoacid catalysts, photoinitiators, etc. to achieve the photosensitive effect.

[0055] If the core of the photoresist particles is approximately regarded as a sphere with an equator and two poles, in some embodiments, the content of the first organic ligand A decreases from the equator direction to the two-pole direction of the core, and the content of the second organic ligand B decreases from the two-pole direction to the equator direction of the core. Optionally, the second organic ligand B is distributed within the range extending 10° - 45° from the two poles to the equator, and the first organic ligand A is distributed within the range extending 45° - 80° from the equator to the two poles. The angles here refer to the central angles on any cross-section passing through the center of the sphere. Optionally, only the second organic ligand B is contained at the two poles, and only the first organic ligand A is contained at the equator, as Figure 1 shown.

[0056] Due to the very small volume of the core, the organic ligands basically continuously wrap around the core, and the first organic ligand A and the second organic ligand B completely wrap the core, and there is basically no blank on the outer shell.

[0057] Such as Figure 2As shown, the size of the photoresist particles is 1 nm to 3 nm. Through the characterization of single crystal structure data, it can be known that the first organic ligand A and the second organic ligand B cooperate with each other, and the photoresist particles conforming to this general formula have an exact structure. It can be seen from the material size that the photoresist of the present application can significantly reduce the edge roughness of the pattern after exposure compared with the traditional photoresist.

[0058] In the photoresist particles, that is, the zinc-based metal-organic nanoparticles, Zn x O y In each Zn atom in the core, it can be connected to the surrounding O atoms and / or N atoms in the second organic ligand B. In some embodiments, the total number n of O atoms and N atoms connected to the same Zn atom can be 4, 5 or 6, so as to form a tetrahedron (n = 4), hexahedron (n = 5) or octahedron (n = 6) unit. The Zn atom is located at the center of the tetrahedron, hexahedron or octahedron, and the O atom or N atom is located at the vertex of the tetrahedron, hexahedron or octahedron. Adjacent Zn atoms can be directly connected through O atoms, that is, a Zn-O-Zn bond is formed. At this time, the polyhedrons can share one oxygen atom. Or, adjacent Zn atoms can be jointly connected to the same first organic ligand A through O atoms to form a Zn-O-C-O-Zn group.

[0059] In some embodiments, x = 3, and three Zn atoms are arranged in sequence to form a non-cyclic structure. The two Zn atoms at both ends are directly connected to the N atoms in two second organic ligands B respectively, and the Zn atom in the center is only directly connected to the O atom. Since the N atom comes from the second organic ligand B, the second organic ligand B is also located at both poles of the core.

[0060] In some embodiments, x = 2, and the two Zn atoms are not directly connected through O atoms, but are jointly connected to the first organic ligand A through the surrounding O atoms, and are connected through a Zn-O-C-O-Zn group. The N atoms in the two second organic ligands B are located at x O y both ends of the Zn

[0061] More specifically, in some embodiments, the general formula of the photoresist particles can be Zn x O 4x [A] 2x [B]2, such as Zn2O8[A]4[B]2, Zn3O 12 [A]6[B]2; in other embodiments, the general formula of the photoresist particles can be Zn3O 10 [A]6[B]2.

[0062] The first organic ligand A is directly connected to Zn through its own C atom x O y in the core. The second organic ligand B is directly connected to the Zn atom in the core through its own N atom x O y in the core. In some embodiments, the same first organic ligand A is respectively connected to two O atoms, and then connected to two Zn atoms through the two O atoms. In the synthesis of the photoresist particles, the O atom in the Zn x O y core at least partially comes from the reactant for forming the first organic ligand A (also referred to as the first organic ligand source in this application), for example, from the oxygen-containing unsaturated bond possessed by the first organic ligand source, such as a carboxyl group or a carbonyl group, so that the first organic ligand A is located between the two poles of the core, such as the equatorial position.

[0063] The first organic ligand A is selected from a substituted or unsubstituted aliphatic group, or a substituted or unsubstituted aromatic group. The aliphatic group can be a C1-C10 hydrocarbon group or a C3-C10 cycloalkyl group. The hydrocarbon group can be a straight-chain or branched-chain alkyl group, alkenyl group or alkynyl group. In the substituted aliphatic group, the hydrogen of the hydrocarbon group or cycloalkyl group can be substituted by one or more substituents. The aromatic group can have one or more aromatic rings, substituted aromatic rings, heteroaromatic rings or substituted heteroaromatic rings, and can be a phenyl group or a substituted phenyl group in some embodiments. In the substituted aromatic group, the hydrogen on the aromatic ring, such as the benzene ring, can be substituted by one or more substituents. The substituents can be selected from, but not limited to, one or more of halogen, carboxyl group, carbonyl group, hydroxyl group, amino group, R, OR, NR2, SR, C(O)R, C(O)OR, C(O)NR2, CN, CF3, NO2, SO2, SOR, SO3R. R can independently be, but not limited to, a C1-C10 chain alkyl group, a C2-C10 chain alkenyl group, a C2-C10 chain alkynyl group, a C3-C10 aryl group, a C3-C10 alkaryl group, or a C3-C10 cycloalkyl group. In some embodiments, R is independently a C1-C4 chain alkyl group, a C2-C4 chain alkenyl group, a C2-C4 chain alkynyl group, a phenyl group or an alkylphenyl group. Specifically, for example, it can be a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a vinyl group, an allyl group, an ethynyl group, etc. The alkylphenyl group can be, for example, a methylphenyl group, an ethylphenyl group, a n-propylphenyl group, an isopropylphenyl group, etc. In some embodiments, the total number of carbon atoms in each first organic ligand A can be 1-10. In some embodiments, the first organic ligand A is derived from any one or more of benzene and its derivatives, alkanes, alkenes, carboxylic acids. The derivative can refer to the substitution of the hydrogen atom in benzene by the above substituents.

[0064] In some embodiments, the first organic ligand A is represented by one or more of the following structures, where the dashed line represents an O-linked bond to the Zn x O y kernel:

[0065]

[0066] wherein, R1 is independently selected from one or more of H, halogen, carboxyl, carbonyl, hydroxyl, amino, R, OR, NR2, SR, C(O)R, C(O)OR, C(O)NR2, CN, CF3, NO2, SO2, SOR, SO3R; the number of R1 is 1-5, and they are respectively connected to C in the benzene ring. In some embodiments, R1 is independently C1-C4 alkyl, C2-C4 alkenyl, or C2-C4 alkynyl.

[0067] In some embodiments, the first organic ligand A is selected from one or more of the following structures:

[0068]

[0069] In some embodiments, the second organic ligand B is selected from organic amines and their derivatives, including but not limited to any one or more of chain amines and their derivatives and cyclic amines and their derivatives. The derivatives may refer to substituted chain amines or substituted cyclic amines formed by substituting one or more substituents for hydrogen atoms in the organic amines. The substituents may be selected from, but not limited to, one or more of 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 H, C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl, C3-C10 aryl, C3-C10 alkaryl, or C3-C10 cycloalkyl. In some embodiments, R is independently C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, phenyl, or alkylphenyl. Specifically, for example, it may be methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, vinyl, propenyl, ethynyl, etc. The alkylphenyl may be, for example, methylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, etc.

[0070] In some embodiments, the cyclic amine and its derivatives may be selected from, but not limited to, any one or more of imidazole and its derivatives, pyridine and its derivatives, pyrrole and its derivatives, pyrimidine and its derivatives, pyridazine and its derivatives, piperidine and its derivatives. The chain amine and its derivatives may be selected from, but not limited to, any one or more of trimethylamine, triethylamine, tripropylamine, triisopropylamine, triethanolamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, ethyldiisopropylamine. Imidazole and its derivatives may be, but not limited to, any one or more of methylimidazole, vinylimidazole. Pyridine and its derivatives may be, but not limited to, any one or more of methylpyridine, vinylpyridine, methylpyrrolidine, perhydropyridine. Pyrrole and its derivatives may be, but not limited to, any one or more of methylpyrrole, vinylpyrrole. Pyridazine and its derivatives may be, but not limited to, any one or more of vinylpyridazine, divinylpyridazine. Piperidine and its derivatives may be, but not limited to, vinylpiperidine, etc. In some embodiments, the second organic ligand B has an N-containing unsaturated structure, so that the electron-donating ability can be increased, further making it easier for the photoactive reactive group to obtain electrons, having a high reactivity, and then promoting the reaction between the photoactive reactive groups.

[0071] In some embodiments, at least one of the first organic ligand A and the second organic ligand B may have a photoactive reactive group. Under light irradiation, reactions can occur between the photoactive reactive groups of different photoresist particles, for example, generating a linking group to connect the photoresist particles through this linking group. Since the zinc oxide Zn x O y core has a high electron-donating ability, making it easier for the photoactive reactive group to obtain electrons and having a high reactivity, so that the photoresist particle itself can be photosensitive without the need to add photoacid generators, photoacid catalysts, photoinitiators, etc. The reactions between the photoactive reactive groups may be, for example, but not limited to, one or more of addition reactions and condensation reactions. The addition reaction may be, for example, one or more of radical addition reactions, nucleophilic addition reactions, and electrophilic addition reactions. The photoactive reactive group may be one or more of a carbon-carbon double bond, a carbonyl group (such as acyloxy, acyl, aldehyde group, ester group, etc.), a carboxyl group, and an amino group.

[0072] In one embodiment, at least one of the first organic ligand A and the second organic ligand B has a carbon-carbon double bond. Under light irradiation, a radical addition reaction can occur between the carbon-carbon double bonds of different photoresist particles to generate a linking group -C-C-.

[0073] In another embodiment, both the first organic ligand A and the second organic ligand B have photo-responsive groups. The photo-responsive group of the first organic ligand A is an aldehyde group (-CHO), and the second organic ligand B is an amino group (such as -NH-, -NH2-). The above two photo-responsive groups of different photoresist particles can react under light irradiation to form a linking group -C-N-.

[0074] In some embodiments, the first organic ligand A has an aromatic ring structure, and the second organic ligand B is selected from cyclic amines and their derivatives, especially selected from imidazoles and their derivatives. The aromatic ring structure of the first organic ligand A (such as a phenyl group) and the cyclic amine structure of the second organic ligand B (such as an imidazole group) have a high electron-donating ability, making the photo-responsive groups more likely to obtain electrons, thereby promoting the reaction between the photo-responsive groups.

[0075] In the photoresist particles, the first organic ligand A and the second organic ligand B can be one or more organic ligands respectively. For example, when they are respectively selected from one or two organic ligands, the general formula of the photoresist particles can be Zn x O y [A1,A2] 2x [B1]2, Zn x O y [A1] 2x [B1,B2]2, Zn x O y [A1,A2] 2x [B1,B2]2. A1 and A2 respectively represent two different first organic ligands A, such as two different substituted or unsubstituted aliphatic groups or aromatic groups. B1 and B2 respectively represent two different second organic ligands B, such as two different organic amines.

[0076] The embodiment of the present application also provides a preparation method of a photoresist particle, that is, a zinc-based metal-organic nanoparticle, including the following steps:

[0077] Mix a metal salt of zinc with an organic solvent to obtain a zinc metal salt solution;

[0078] Mix the zinc metal salt solution with a first organic ligand source and a second organic ligand source, and heat and stir for reaction;

[0079] Perform vacuum rotary evaporation on the reaction product to remove the organic solvent;

[0080] Wherein, the molar ratio of the metal salt of zinc, the first organic ligand source, and the second organic ligand source is 1:(0.5 - 6):(0.5 - 6).

[0081] The first organic ligand source is a reactant for forming the first organic ligand A, including the group that is the first organic ligand A, i.e., the substituted or unsubstituted aliphatic group or the substituted or unsubstituted aromatic group. It also includes an oxygen-containing unsaturated bond capable of reacting with the metal salt of zinc, such as a carboxyl group or a carbonyl group. The second organic ligand participates in the reaction through its own nitrogen atom and connects to the Zn atom in the core. Therefore, the second organic ligand can directly serve as the second organic ligand source.

[0082] In the preparation method of this application, the molar ratio of the metal salt of zinc, the first organic ligand source, and the second organic ligand source plays a crucial role in obtaining the photoresist particles with the above specific structure. The molar ratio of the metal salt of zinc, the first organic ligand source, and the second organic ligand source is 1:(0.5 - 6):(0.5 - 6). After the reaction and before removing the organic solvent, the resulting solution is clear and transparent, and the generated photoresist particles do not precipitate out in the form of a precipitate but are uniformly dispersed in the organic solvent. If the addition amount of the first organic ligand source or the second organic ligand source is too much or too little, only a white precipitate that cannot be dissolved in the organic solvent will be formed or the photoresist particles with the specific structure cannot be obtained.

[0083] In some embodiments, the temperature of the heating and stirring is 50°C to 120°C, and the time is 10 h to 40 h; optionally, the temperature of the heating and stirring is 50°C to 80°C, and the time is 15 h to 28 h. If the temperature is too low, the reaction rate is too slow; if the temperature is too high, the reaction is unstable, and a white precipitate that cannot be dissolved in the organic solvent will be formed instead of the photoresist particles with the specific structure.

[0084] In some embodiments, 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. Optionally, the temperature of the vacuum rotary evaporation is 20°C to 40°C. If the temperature is too low, the reaction rate is too slow; if the temperature is too high, the properties of the photoresist particles are unstable under vacuum, and the groups are easily damaged. The temperature of the vacuum rotary evaporation is usually lower than the temperature of the heating and stirring.

[0085] In some embodiments, the pressure of the vacuum rotary evaporation is 5 mbar to 40 mbar. For example, it can be 5 mbar, 10 mbar, 15 mbar, 20 mbar, 25 mbar, 30 mbar, 35 mbar, 40 mbar, etc.

[0086] The purpose of the vacuum rotary evaporation is to quickly remove the organic solvent, making it difficult for the crystal nuclei of the zinc-based metal-organic nanoparticles to grow, thereby forming single crystals, that is, zinc-based metal-organic nanoparticles in a monodisperse state.

[0087] The organic solvent is not particularly limited. For example, it can be selected from, but not limited to, 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.

[0088] The embodiment of the present application also provides a photoresist particle crystal, which is obtained by crystallizing the photoresist particles of any of the above embodiments in an organic solvent. During the crystallization process, the solvent can be slowly removed to allow the crystal nuclei of the zinc-based metal-organic nanoparticles to grow. In one embodiment, the photoresist particles obtained by the vacuum rotary evaporation can be redissolved in an organic solvent, and then left standing to completely volatilize the organic solvent to obtain the photoresist particle crystal. In another embodiment, the reaction product before vacuum rotary evaporation can be directly left standing to completely volatilize the organic solvent to obtain the photoresist particle crystal. The photoresist particle crystal is observed using a double microfocus single crystal X-ray diffractometer and analyzed by the single crystal analysis software Olex2 to obtain the single crystal structure and size characteristics of the photoresist particles.

[0089] The embodiment of the present application also provides a photoresist, which is obtained by dispersing any one or two of the photoresist particles or photoresist particle crystals of any of the above embodiments in an organic dispersion solvent. The dispersion in the organic dispersion solvent is, for example, to dissolve the photoresist particles in the organic solvent to form a clear and transparent solution.

[0090] In some embodiments, the organic dispersion solvent can be 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.

[0091] The embodiment of the present application also provides a patterning method for a photoresist, including the following steps:

[0092] Coat the photoresist on the surface of the substrate, remove the organic dispersion solvent in the photoresist, and form a preformed film layer on the surface of the substrate;

[0093] Irradiate the preformed film layer on the substrate with a light source through a mask for an exposure operation, so that a photoresist particle aggregate is formed in the exposed area of the preformed film layer; and

[0094] Apply a developer to the exposed preformed film layer, so that the unexposed area covered by the mask on the preformed film layer is dissolved in the developer, while the exposed area of the preformed film layer remains on the substrate due to the formation of photoresist particle aggregates, thereby forming a patterned photoresist layer.

[0095] During the photoresist patterning process of the present application, a photoacid generator, a catalyst, and a photoinitiator do not need to be added to perform graphic manufacturing.

[0096] The embodiment of the present application also provides a photoresist combination product, including the photoresist of any one of the above embodiments and a developer. The photoresist combination product is used to form a patterned photoresist layer.

[0097] In some embodiments, the light source used for exposure is selected from any one of ultraviolet, deep ultraviolet, electron beam, and extreme ultraviolet light sources. The wavelength of extreme ultraviolet light is 10 nm - 14 nm. The wavelength of ultraviolet light can be, for example, 254 nm or 365 nm. The photoresist of the present application can be used for the exposure light source used in any existing lithography technology, and no photoacid generator, catalyst, or initiator is required.

[0098] In some embodiments, the substrate is selected from a silicon substrate or other substrates that are insoluble in the developer according to actual requirements.

[0099] In some embodiments, regarding the mask, when the exposure uses a deep ultraviolet and longer wavelength light source, the mask used is a transmissive mask; when the exposure uses an extreme ultraviolet light source, the mask used is a reflective mask; when the exposure light source is an electron beam source, a mask may or may not be set, and the electron beam exposes the preformed film layer according to the pattern set by the software.

[0100] In some embodiments, the light source used for the exposure operation is an ultraviolet, deep ultraviolet, or extreme ultraviolet light source, and the exposure dose of the exposure operation is 4 mJ / cm 2 ~1000 mJ / cm 2 . In some other embodiments, the light source used for the exposure operation is an electron beam source, and the dose is 10 μC / cm 2 ~10 mC / cm 2 . The exposure dose should be controlled within a suitable range. If the exposure dose is too small, the energy is too low, which is not conducive to the polymerization of photoresist particles in the exposure area, is not conducive to forming the solubility difference between the exposure area and the non-exposure area, and the development effect is poor. If the exposure dose is too large, the photoresist in the non-exposure area may react, resulting in a reduction in pattern accuracy.

[0101] In some embodiments, the developer is mainly used to dissolve non-agglomerated photoresist particles. The photoresist particles in the exposed area form aggregates, which are insoluble in the developer or have low solubility in the developer in the exposed area. Even if partially dissolved, the exposed area can still be covered by aggregates. The developer and the organic solvent in the photoresist can be the same or different. Optionally, the solubility of the photoresist particles in the developer is less than that in the organic solvent of the photoresist, to prevent the photoresist particles from being dissolved in the developer due to insufficient polymerization degree after exposure, resulting in dissolution or partial dissolution of the exposed area and reducing the accuracy of the exposed pattern. In some embodiments, the developer can be selected from any one or more of decalin, tetralin, indene, indan, quinoline, 1-methylnaphthalene, toluene, o-xylene, m-xylene, p-xylene, ethyl acetate, butyl acetate, ethanol, n-propanol, isopropanol, n-butanol, n-hexane, and cyclohexane. In some embodiments, the development temperature can be room temperature, for example, 20°C to 30°C.

[0102] In one embodiment, the thickness of the preformed film layer after removing the organic dispersion solvent can be 10 nm to 500 nm. Specifically, the thickness of the preformed film layer can be 10 nm to 50 nm, 50 nm to 100 nm, 100 nm to 150 nm, 150 nm to 200 nm, 200 nm to 250 nm, 250 nm to 300 nm, 300 nm to 350 nm, 350 nm to 400 nm, 400 nm to 450 nm, or 450 nm to 500 nm.

[0103] The embodiments of the present application also provide a method for generating a printed circuit board, including the following steps:

[0104] Preparing a pre-patterned sheet having a patterned photoresist layer on a silicon substrate according to the patterned method of the photoresist as described above; and

[0105] Etching the pre-patterned sheet by dry or wet etching.

[0106] Example 1:

[0107] ① Add 4.88 g (20 mmol) of benzoic acid and 1.92 g (20.4 mmol) of N-vinylimidazole to a flask and mix. Add 15 mL of ethyl acetate and mix and dissolve for 2 min.

[0108] ② Add 4.38 g (20 mmol) of zinc acetate dihydrate to the flask, add 30 mL of ethyl acetate, and drop the mixed solution obtained in ① into the flask, and stir at 65°C for 24 h.

[0109] ③ After the reaction is completed, use a rotary evaporator to perform rotary evaporation at 30 °C for 20 min, control the pressure to be 30 mbar, and obtain an aggregate of photoresist particles. Redissolve the product in ethyl acetate, and let it stand until ethyl acetate completely volatilizes to obtain crystals. Observe the crystal of the photoresist particles using a dual microfocus single crystal X-ray diffractometer, and analyze the obtained crystal through the single crystal analysis software Olex2, and obtain a single crystal structure diagram as Figure 3 shown. The obtained photoresist particles, that is, the chemical formula of the zinc-based metal-organic nanoparticles is Zn3O 12 [C7H5]6[C5N2H6]2. The particle size is less than 2 nm, as Figure 4 shown.

[0110] Example 2:

[0111] ① Add 4.88 g (20 mmol) of benzoic acid and 1.67 g (20.4 mmol) of N-methylimidazole to a flask and mix them, add 15 mL of ethyl acetate, and mix and dissolve for 2 min.

[0112] ② Add 4.38 g (20 mmol) of zinc acetate dihydrate to the flask, add 30 mL of ethyl acetate, and dropwise add the mixed solution obtained in ① to the flask, and stir at 65 °C for 24 h.

[0113] ③ After the reaction is completed, use a rotary evaporator to perform rotary evaporation at 30 °C for 20 min, control the pressure to be 30 mbar, and obtain an aggregate of photoresist particles. Redissolve the product in ethyl acetate, and let it stand until ethyl acetate completely volatilizes to obtain crystals. Observe the crystal of the photoresist particles using a dual microfocus single crystal X-ray diffractometer, and analyze the obtained crystal through the single crystal analysis software Olex2, and obtain a single crystal structure diagram as Figure 5 shown. The obtained photoresist particles, that is, the chemical formula of the zinc-based metal-organic nanoparticles is Zn3O 12 [C7H5]6[C4N2H6]2. The particle size is less than 2 nm, as Figure 6 shown.

[0114] Example 3:

[0115] ① Add 2.44 g (10 mmol) of benzoic acid and 1.67 g (20.4 mmol) of N-methylimidazole to a flask and mix them, add 15 mL of ethyl acetate, and mix and dissolve for 2 min.

[0116] ② Add 4.38 g (20 mmol) of zinc acetate dihydrate to the flask, add 30 mL of ethyl acetate, and dropwise add the mixed solution obtained in ① to the flask, and stir at 65 °C for 24 h.

[0117] ③ After the reaction is completed, use a rotary evaporator to perform rotary evaporation at 30 °C for 20 min, control the pressure to 30 mbar, and obtain an aggregate of photoresist particles. Redissolve the product in ethyl acetate, let it stand until the ethyl acetate completely volatilizes, and obtain crystals. Observe the crystal of the photoresist particles using a dual microfocus single crystal X-ray diffractometer, and analyze the obtained crystal through the single crystal analysis software Olex2 to obtain a single crystal structure diagram as Figure 7 shown. The obtained photoresist particles, that is, the chemical formula of the zinc-based metal-organic nanoparticles is Zn3O 10 [C7H5]4[C2H3O]2[C4N2H6]2. The particle size is less than 2 nm, as Figure 8 shown.

[0118] Example 4:

[0119] ① Add 5.44 g (20 mmol) of m-toluic acid and 1.92 g (20.4 mmol) of N-vinylimidazole to a flask and mix them. Add 15 mL of ethyl acetate and mix and dissolve for 2 min.

[0120] ② Add 4.38 g (20 mmol) of zinc acetate dihydrate to the flask, add 30 mL of ethyl acetate, and dropwise add the mixed solution obtained in ① to the flask, and stir at 65 °C for 2 h.

[0121] ③ After the reaction is completed, use a rotary evaporator to perform rotary evaporation at 30 °C for 20 min, control the pressure to 30 mbar, and obtain an aggregate of photoresist particles. Redissolve the product in ethyl acetate, let it stand until the ethyl acetate completely volatilizes, and obtain crystals. Observe the crystal of the photoresist particles using a dual microfocus single crystal X-ray diffractometer, and analyze the obtained crystal through the single crystal analysis software Olex2 to obtain a single crystal structure diagram as Figure 9 shown. The obtained photoresist particles, that is, the chemical formula of the zinc-based metal-organic nanoparticles is Zn2O8[C8H7]4[C4N2H6]2. The particle size is less than 2 nm, as Figure 10 shown.

[0122] Example 5:

[0123] ① Add 2.72 g (20 mmol) of m-toluic acid, 2.44 g (20 mmol) of benzoic acid, and 1.92 g (20.4 mmol) of N-vinylimidazole to a flask and mix them. Add 15 mL of ethyl acetate and mix and dissolve for 2 min.

[0124] ② Add 4.38 g (20 mmol) of zinc acetate dihydrate to the flask, add 30 mL of ethyl acetate, and dropwise add the mixed solution obtained in ① to the flask, and stir at 65 °C for 24 h.

[0125] ③ After the reaction was completed, rotary evaporation was carried out at 30 °C for 20 min using a rotary evaporator, and the pressure was controlled at 30 mbar to obtain an aggregate of photoresist particles. The product was redissolved in ethyl acetate, and after standing for the complete volatilization of ethyl acetate, crystals were obtained. The crystals of the photoresist particles were observed using a double microfocus single crystal X-ray diffractometer, and the crystals obtained were analyzed by the single crystal analysis software Olex2. It was found that a mixture of two kinds of photoresist particles was obtained. The single crystal structure diagrams of the two kinds of photoresist particles are respectively as Figure 3 and Figure 9 shown.

[0126] Preparation of the patterned photoresist layer:

[0127] Take 1 g of the photoresist particles in Example 5, dissolve them in 19 g of propylene glycol monomethyl ether acetate, disperse them evenly and then coat. Coating was carried out on a 2-inch silicon wafer at a rotation speed of 2000 rpm for 1 min, and then baked at 80 °C for 1 min to form a photoresist layer on the silicon wafer, that is, the preformed film layer.

[0128] Multiple samples of the same preformed film layer were exposed under a 248 nm deep ultraviolet light source with different exposure doses through a patterned mask, and then the exposed preformed film layer was developed with a developer. The developer used was decalin, and the exposure doses used were 45 mJ / cm -2 , 75 mJ / cm -2 , 110 mJ / cm -2 . The patterned photoresist layer obtained is as Figures 11 to 13 shown, where the line widths of the linear patterns are 429.9 nm, 468.9 nm, and 513.6 nm respectively. It can be seen that with the increase of the exposure dose, the line widths of the linear patterns formed through the same mask increase to a certain extent, but generally they are all around 0.4 μm to 0.5 μm.

[0129] Multiple samples of the same preformed film layer were exposed under the same electron beam source through different patterned masks, and the exposure dose was 50 μC for all. Then, the exposed preformed film layer was developed with decalin as the developer. The patterned photoresist layer obtained is as Figures 14 to 16 shown, where the line widths of the linear patterns are 100 nm, 40 nm, and 25 nm, and the ratio of line to space (L / S) of the dense lines is 1:1.

[0130] Multiple samples of the same preformed film layer were exposed under the same extreme ultraviolet exposure conditions through different patterned masks, and the exposure dose was 7 mJ / cm -2 for all. Then, the exposed preformed film layer was developed with decalin as the developer. The obtained patterned photoresist layer is as Figure 17As shown. Among them, the periods of the patterns (i.e., the sum of the widths of one line and one blank bar) are 100 nm (P100), 70 nm (P70), 50 nm (P50), and 44 nm (P44), respectively.

[0131] The preformed film layer sample was exposed through different patterned masks under an ultraviolet light source with an exposure dose of 300 mJ / cm -2 , a wavelength of 254 nm, and then the exposed preformed film layer was developed using tetralin as a developer to obtain a patterned photoresist layer as Figures 18 to 19 shown. Figure 19 The line width of the linear pattern in the middle is 8.87 μm. The exposure was carried out under air test conditions, and oxygen has an inhibitory effect on the reaction, so the exposure dose is relatively high.

[0132] It can be seen that under ultraviolet, deep ultraviolet, extreme ultraviolet, and electron beam exposures, photolithographic images can be formed without the need for initiators or catalysts.

[0133] Comparative Example 1

[0134] ① 1.22 g (5 mmol) of benzoic acid and 1.92 g (20.4 mmol) of N-vinylimidazole were added to a flask and mixed. At the same time, 15 mL of ethyl acetate was added and mixed and dissolved for 2 min.

[0135] ② 4.38 g (20 mmol) of zinc acetate dihydrate was added to the flask, 30 mL of ethyl acetate was added, and the mixed solution obtained in ① was added dropwise to the flask, and stirred at 65 °C for 24 h.

[0136] ③ After the reaction was completed, rotary evaporation was carried out at 30 °C for 20 min using a rotary evaporator, and the pressure was controlled at 30 mbar.

[0137] Since the content of benzoic acid in Comparative Example 1 was too small, a white precipitate was produced in the solution after the second-step reaction, and the photoresist particles could not be obtained.

[0138] Comparative Example 2

[0139] ① 48.8 g (200 mmol) of benzoic acid and 1.92 g (20.4 mmol) of N-vinylimidazole were added to a flask and mixed. At the same time, 15 mL of ethyl acetate was added and mixed and dissolved for 2 min.

[0140] ② 4.38 g (20 mmol) of zinc acetate dihydrate was added to the flask, 30 mL of ethyl acetate was added, and the mixed solution obtained in ① was added dropwise to the flask, and stirred at 65 °C for 24 h.

[0141] ③ After the reaction was completed, rotary evaporation was carried out at 30 °C for 20 min using a rotary evaporator, and the pressure was controlled at 30 mbar.

[0142] Due to the excessive benzoic acid content in Comparative Example 2, white precipitates were formed in the solution after the second-step reaction, and the described photoresist particles could not be obtained.

[0143] Comparative Example 3

[0144] ① Add 4.88 g (20 mmol) of benzoic acid and 0.48 g (5.1 mmol) of N-vinylimidazole to a flask and mix. At the same time, add 15 mL of ethyl acetate and mix and dissolve for 2 min.

[0145] ② Add 4.38 g (20 mmol) of zinc acetate dihydrate to the flask, add 30 mL of ethyl acetate, and dropwise add the mixed solution obtained in ① to the flask, and stir at 65 °C for 24 h.

[0146] ③ After the reaction is completed, use a rotary evaporator to perform rotary evaporation at 30 °C for 20 min, and control the pressure to be 30 mbar.

[0147] Due to the too low content of N-vinylimidazole in Comparative Example 3, white precipitates were formed in the solution after the second-step reaction, and the described photoresist particles could not be obtained.

[0148] The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity of description, 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, it should be considered as the scope described in this specification.

[0149] The above-described embodiments only represent several embodiments of the present application, and their descriptions are relatively specific and detailed, but they should not be construed as limiting the scope of the patent application. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present application, several modifications and improvements can still be made, and these all belong to the protection scope of the present application. Therefore, the protection scope of the patent of the present application should be subject to the appended claims.

Claims

1. A zinc-based metal-organic nanoparticle, characterized in that, The zinc-based metal-organic nanoparticles have a core-shell structure, and the general formula of the zinc-based metal-organic nanoparticles is Zn x O y [A] 2x [B]2, where x is 2 or 3, 2x ≤ y ≤ 4x, Zn x O y is the inner core of the core-shell structure, A is the first organic ligand, B is the second organic ligand, the first organic ligand A and the second organic ligand B together form the outer shell of the core-shell structure, the first organic ligand A is selected from one or more of substituted or unsubstituted aliphatic groups, substituted or unsubstituted aromatic groups, and the second organic ligand B is selected from one or more of organic amines and their derivatives.

2. The zinc-based metal-organic nanoparticles according to claim 1, characterized in that, The zinc-based metal-organic nanoparticles have photoactive reactive groups.

3. The zinc-based metal-organic nanoparticles according to claim 2, wherein At least one of the first organic ligand A and the second organic ligand B has a photoactive reactive group.

4. The zinc-based metal-organic nanoparticles according to claim 3, characterized in that, The photoactive reactive group is selected from one or more of a carbon-carbon double bond, an acyloxy group, an acyl group, an aldehyde group, an ester group, a carboxyl group, and an amino group.

5. The zinc-based metal-organic nanoparticles according to claim 4, wherein x = 3, and two Zn atoms are located at opposite ends of the Zn x O y core and are respectively connected to the N atoms in two of the second organic ligands B.

6. The zinc-based metal-organic nanoparticles according to claim 4, wherein x = 2. Two Zn atoms are jointly connected to the first organic ligand A through the surrounding O atoms. The N atoms in the two second organic ligands B are located at both ends of the Zn x O y core and are respectively connected to the two Zn atoms.

7. The zinc-based metal-organic nanoparticles according to claim 4, wherein, The general formula of the zinc-based metal-organic nanoparticles is Zn2O8[A]4[B]2, Zn3O 12 [A]6[B]2 or Zn3O 10 [A]6[B]2.

8. The zinc-based metal-organic nanoparticles according to claim 7, wherein, The size of the zinc-based metal-organic nanoparticles is 1 nm to 3 nm.

9. The zinc-based metal-organic nanoparticles according to claim 8, wherein, The aliphatic group is a C1-C10 chain hydrocarbon group or a C3-C10 cycloalkane group, and the chain hydrocarbon group is a straight-chain or branched-chain alkyl group, alkenyl group, or alkynyl group; The aromatic group has one or more aromatic rings, substituted aromatic rings, heteroaromatic rings, or substituted heteroaromatic rings, the aromatic ring is a phenyl group, or the substituted aromatic ring is a substituted phenyl group.

10. The zinc-based metal-organic nanoparticles according to claim 9, characterized in that, In the substituted aliphatic group, the hydrogen of the chain hydrocarbon group or the cycloalkane group is substituted by one or more substituents; in the substituted aromatic group, the hydrogen on the aromatic ring is substituted by one or more substituents; The substituent is selected from one or more of a halogen, a carboxyl group, a carbonyl group, a hydroxyl group, an amino group, R, OR, NR2, SR, C(O)R, C(O)OR, C(O)NR2, CN, CF3, NO2, SO2, SOR, and SO3R, where R is independently a C1-C10 chain alkyl group, a C2-C10 chain alkenyl group, a C2-C10 chain alkynyl group, a C3-C10 aryl group, a C3-C10 alkaryl group, or a C3-C10 cycloalkyl group.

11. The zinc-based metal-organic nanoparticles according to claim 10, wherein R is independently a C1-C4 chain alkyl group, a C2-C4 chain alkenyl group, a C2-C4 chain alkynyl group, a phenyl group, or an alkylphenyl group.

12. The zinc-based metal-organic nanoparticles according to claim 11, wherein The first organic ligand A is represented by one or more of the following structures, where the dashed line represents an O-linked bond to the Zn x O y O-linked bond of the core: Wherein, R1 is independently selected from one or more of H, a halogen, a carboxyl group, a carbonyl group, a hydroxyl group, an amino group, R, OR, NR2, SR, C(O)R, C(O)OR, C(O)NR2, CN, CF3, NO2, SO2, SOR, and SO3R; wherein, R is independently a C1-C10 chain alkyl group, a C2-C10 chain alkenyl group, a C2-C10 chain alkynyl group, a C3-C10 aryl group, a C3-C10 alkaryl group, or a C3-C10 cycloalkyl group; The number of R1 is 1-5, and they are respectively connected to the C in the benzene ring; R1 is independently a C1-C4 chain alkyl group, a C2-C4 chain alkenyl group, or a C2-C4 chain alkynyl group; The first organic ligand A is selected from one or more of the following structures:

13. The zinc-based metal-organic nanoparticles according to claim 12, characterized in that, R is independently a C1-C4 chain alkyl group, a C2-C4 chain alkenyl group, a C2-C4 chain alkynyl group, a phenyl group, or an alkylphenyl group.

14. The zinc-based metal-organic nanoparticles according to claim 13, characterized in that, The second organic ligand B is selected from any one or more of chain amines and their derivatives and cyclic amines and their derivatives. The cyclic amines and their derivatives are selected from any one or more of imidazole and its derivatives, pyridine and its derivatives, pyrrole and its derivatives, pyrimidine and its derivatives, pyridazine and its derivatives, and piperidine and its derivatives. The chain amines and their derivatives are selected from, but not limited to, any one or more of trimethylamine, triethylamine, tripropylamine, triisopropylamine, triethanolamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, and ethyldiisopropylamine; The imidazole and its derivatives are selected from any one or more of methylimidazole and vinylimidazole; the pyridine and its derivatives are selected from any one or more of methylpyridine, vinylpyridine, methylpiperidine, and perhydropyridine; the pyrrole and its derivatives are selected from any one or more of 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 vinylpiperidine.

15. The zinc-based metal-organic nanoparticles according to claim 14, characterized in that, The derivative of the organic amine is obtained by substituting one or more substituents for the hydrogen atoms on the chain amine and / or the cyclic amine; The substituents are selected from one or more of halogen, carboxyl, carbonyl, hydroxyl, amino, R, OR, NR2, SR, C(O)R, C(O)OR, C(O)NR2, CN, CF3, NO2, SO2, SOR, SO3R, where R is independently H, C1-C10 chain alkyl, C2-C10 chain alkenyl, C2-C10 chain alkynyl, C3-C10 aryl, C3-C10 alkaryl, or C3-C10 cycloalkyl.

16. The zinc-based metal-organic nanoparticles according to claim 15, wherein, R is independently C1-C4 chain alkyl, C2-C4 chain alkenyl, C2-C4 chain alkynyl, phenyl, or alkylphenyl.

17. The zinc-based metal-organic nanoparticles according to claim 16, wherein, The general formula of the zinc-based metal-organic nanoparticles is Zn x O y [A1, A2] 2x [B1]2, Zn x O y [A1] 2x [B1, B2]2 or Zn x O y [A1, A2] 2x [B1, B2]2, where A1 and A2 respectively represent two different first organic ligands A, and B1 and B2 respectively represent two different second organic ligands B.

18. The preparation method of the zinc-based metal-organic nanoparticles according to any one of claims 1 to 17, characterized in that, Comprising the following steps: Mixing a metal salt of zinc with an organic solvent to obtain a zinc metal salt solution; Mixing the zinc metal salt solution with a first organic ligand source and a second organic ligand source, heating and stirring for reaction; Performing vacuum rotary evaporation on the reaction product to remove the organic solvent.

19. The preparation method of the zinc-based metal-organic nanoparticles according to claim 18, wherein, The molar ratio of the metal salt of zinc, the first organic ligand source, and the second organic ligand source is 1:(0.5-6):(0.5-6).

20. The preparation method of the zinc-based metal-organic nanoparticles according to claim 19, wherein, The temperature of the heating and stirring is 50°C to 120°C, and the time is 10 h to 40 h; The temperature of the vacuum rotary evaporation is 20°C to 80°C; The pressure of the vacuum rotary evaporation is 5 mbar to 40 mbar.

21. The preparation method of the zinc-based metal-organic nanoparticles according to claim 20, wherein, The temperature of the heating and stirring is 50°C to 80°C, and the time is 15 h to 28 h; The temperature of the vacuum rotary evaporation is 20°C to 40°C.

22. A zinc-based metal-organic nanoparticle crystal, characterized in that, It is obtained by crystallizing the zinc-based metal-organic nanoparticles described in any one of claims 1 to 17 after dissolving them in an organic solvent, or by crystallizing the product of the vacuum rotary evaporation in the preparation method of the zinc-based metal-organic nanoparticles described in any one of claims 18 to 21 after redissolving it in an organic solvent.

23. A photoresist, characterized in that, It is obtained by dispersing any one or two of the zinc-based metal-organic nanoparticles described in any one of claims 1 to 17 and the zinc-based metal-organic nanoparticle crystals described in claim 22 in an organic dispersion solvent.

24. The photoresist according to claim 23, wherein 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.

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