Coordination compound and application thereof as photoresist component

Abstract

The invention belongs to the field of photosensitive materials, and particularly relates to a coordination compound and application thereof as a photoresist component. The coordination compound provided by the invention has a trinuclear zirconium cluster structure, and compared with a traditional polymer, the coordination compound provided by the invention has a smaller molecular size and can obtain better photoetching resolution; meanwhile, according to the coordination compound disclosed by the invention, by introducing the cyclopentadienyl ring or the derivative thereof into the cluster structure, the corrosion resistance can be effectively improved, so that the resolution ratio and the characteristic size of a photoetching pattern are improved, and huge application potential is shown.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of photosensitive material, and particularly relates to a novel zirconium cluster coordination compound and application thereof as a photoresist component. BACKGROUND

[0002] Photoresist is a core material in the photolithography process, also known as photoresist, which is a kind of etching-resistant material that changes solubility under the irradiation of light sources such as ultraviolet light, X-ray and electron beam, and then becomes soluble or insoluble in the developing solution, playing a role in transferring patterns, and can be widely applied to the field of fine pattern processing of display, integrated circuit and optoelectronic device. With the development of Moore's law, the feature size of technology nodes has entered 22 nm and below. At present, the industry has relied on 193 nm immersion lithography technology to obtain finer features on resist materials through multiple lithography procedures, resulting in a substantial increase in the cost of photolithography processing. Latest research shows that extreme ultraviolet (EUV) lithography technology has the advantages of high resolution, easy processing, high throughput and less design limitations, and it is expected to obtain high-resolution lithography patterns with smaller features in one exposure step, and is expected to become an ideal solution to obtain finer and higher-resolution lithography patterns.

[0003] In recent years, it has been found that transition metals have high absorption cross-section at EUV wavelengths, which makes hybrid photoresists containing transition metals exhibit significant advantages in advanced lithography technology. Compared with traditional polymer-based chemical amplification photoresists (CARs), such materials not only enable the dramatic reduction of device size, but also have better etching selectivity. In particular, hybrid nanomaterials composed of inorganic "core" and organic "shell", such as methyl acrylic acid (MAA) modified zirconium oxide (ZrO2) nanoparticles, have shown excellent EUV sensitivity. However, traditional nanoparticles are prone to uneven size and shape distribution during preparation, which directly affects the resolution and roughness of the lithography pattern. SUMMARY

[0004] In view of the problems existing in the prior art, the present application first develops a novel trinuclear metal coordination compound (hereinafter referred to as zirconium cluster coordination compound) by introducing a metallocycle or its derivative, and uses the trinuclear metal coordination compound as a component of photoresist. The trinuclear metal coordination compound of the present application is a metal-organic coordination compound, and its size and atomic composition are controllable, which has potential advantages in making high-resolution patterns, and is expected to become the most promising photoresist material in the next generation of high-resolution lithography.

[0005] Specifically, the present application provides a coordination compound, characterized in that the chemical formula of the coordination compound is {[(Cp nZr)3(μ2-OH)3(μ3-O)L3] + Cl -},

[0006] wherein Cp n is a structure of formula I In formula I, R1, R2, R3, R4, R5are each independently selected from the group consisting of a hydrogen atom, an unsubstituted or substituted C1-C10 alkyl group, and an unsubstituted or substituted C2-C10 alkenyl group;

[0007] Zr is a zirconium atom;

[0008] L is a ligand formed by removing a hydrogen atom from a carboxyl group of an organic carboxylic acid, the chemical formula of the organic carboxylic acid being Y-COOH, wherein Y is an organic group.

[0009] In one or more embodiments, the substituents on R1, R2, R3, R4, R5are selected from the group consisting of a halogen atom and a trifluoromethyl group.

[0010] In one or more embodiments, Cp n is a structure of formula II

[0011] In one or more embodiments, Cp n is a structure of formula II In formula II, R6is an unsubstituted or substituted C1-C10 alkyl group or an unsubstituted or substituted C2-C10 alkenyl group.

[0012] In one or more embodiments, Cp n is a structure of formula II In formula II, the substituents on R6are selected from the group consisting of a halogen atom and a trifluoromethyl group.

[0013] In one or more embodiments, Cp n is a structure of formula II In formula II, R6is an unsubstituted or substituted C1-C10 alkyl group or an unsubstituted or substituted C2-C10 alkenyl group.

[0014] In one or more embodiments, Y is an unsubstituted or substituted C1-C10 alkyl group, an unsubstituted or substituted C2-C10 alkenyl group, an unsubstituted or substituted C2-C10 alkynyl group, an unsubstituted or substituted C3-C8 cycloalkyl group, an unsubstituted or substituted C5-C10 cycloalkenyl group, a methylenecyclobutane group, a methylenecyclopentane group, a methylenecyclohexane group, an adamantyl group, a C6-C10 aryl group, a biphenyl group, or a structure of formula III In formula III, * indicates the position connected to -COOH, and R is a halogen atom, a trifluoromethyl group, a methyl group, a tert-butyl group, a methoxy group, or a phenyl group.

[0015] ​In one or more embodiments, the substituent on Y is selected from a halogen atom, a hydroxyl group, a trifluoromethyl group, a C1-C10 alkyl group, a C2-C10 alkenyl group, a C2-C10 alkynyl group, a C5-C10 cycloalkyl group, a C5-C10 cycloalkenyl group, a C5-C10 cycloalkynyl group, a C6-C10 aryl group, and a biphenyl group.

[0016] In one or more embodiments, the structure of formula III is a structure of formula III-1, formula III-2, or formula III-3 as follows:

[0017]

[0018] In formula III-1, R is F, Br, or a methyl group;

[0019] In formula III-2, R is a trifluoromethyl group, F, a methyl group, a tert-butyl group, a methoxy group, or a phenyl group;

[0020] In formula III-3, R is F, Cl, Br, a methyl group, or a methoxy group.

[0021] In one or more embodiments, the structure of the complexing compound is a structure of formula A, formula B, or formula C:

[0022]

[0023] In one or more embodiments, the complexing compound is selected from the following compounds:

[0024]

[0025]

[0026]

[0027]

[0028] Another aspect of the present application provides a method for preparing the complexing compound described in any of the embodiments herein, the method comprising the following steps:

[0029] S1: dissolving a zirconium source and an organic carboxylic acid in a mixture of a first organic solvent and water, and obtaining a crude product after stirring and filtration;

[0030] S2: re-dispersing the obtained crude product in a second organic solvent, heating at 30-100°C for 1-3h, and obtaining the pure complexing compound after post-cooling, standing, filtration, rinsing, and drying.

[0031] In one or more embodiments, in step S1, the zirconium source is bis(cyclopentadienyl)zirconium dichloride, bis(pentamethylcyclopentadienyl)zirconium dichloride, and bis(n-butylcyclopentadienyl)zirconium dichloride.

[0032] In one or more embodiments, in step S1, the molar ratio of the zirconium source to the carboxyl group in the organic carboxylic acid is 1:1-1:6.

[0033] In one or more embodiments, in step S1, in the mixed system, the volume ratio of the first organic solvent to water is 1:1-6:1.

[0034] In one or more embodiments, in step S1, the first organic solvent is one or more selected from dichloromethane, chloroform, N,N-dimethylformamide, tetrahydrofuran, dioxane, toluene, chlorobenzene, acetone, ethyl acetate, acetonitrile, methanol, ethanol and n-hexane.

[0035] In one or more embodiments, in step S1, the stirring temperature is 20-100°C and the stirring time is 1-24 hours.

[0036] In one or more embodiments, in step S1, the intermediate product is washed with water and a third organic solvent when filtering, the third organic solvent being one or more selected from n-hexane, petroleum ether, diethyl ether, tetrahydrofuran, dioxane, dichloromethane, chloroform, acetone, ethyl acetate, acetonitrile, methanol and ethanol.

[0037] In one or more embodiments, in step S2, the second organic solvent is one or more selected from n-hexane, cyclohexane, dichloromethane, chloroform, N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, toluene, acetone, ethyl acetate, acetonitrile, methanol and ethanol.

[0038] Another aspect of the present application also provides a photoresist composition comprising the complexing compound described in any one of the embodiments herein; preferably, the photoresist composition further comprises a fourth organic solvent, the fourth organic solvent preferably being one or more selected from tetrahydrofuran, acetonitrile, dioxane, chloroform, 4-methyl-2-pentanol, methyl isobutyl ketone, cyclohexanone, acetone, 2-heptanone, N,N-dimethylformamide, dichloroethane, propylene glycol, ethyl acetate, cyclohexane, isopentyl acetate, propyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, isobutyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, propylene glycol methyl ether acetate, 1-ethoxy-2-propanol, methanol, ethanol, n-propanol, isopropanol and n-butanol.

[0039] In one or more embodiments, the complex compound is present in the photoresist composition in an amount of preferably 0.05 wt% to 5 wt%.

[0040] Another aspect of the present application also provides a use of the complex compound described in any one of the embodiments herein in ultraviolet lithography, KrF lithography, ArF lithography, extreme ultraviolet lithography, nanoimprint lithography, electron beam lithography, or X-ray lithography. BRIEF DESCRIPTION OF DRAWINGS

[0041] Figure 1 Structure schematic of the zirconium cluster complex Zr-Cp-MCA of Synthesis Example 8;

[0042] Figure 2 Scanning electron microscope (SEM) image of the 40 nm line pattern of the Zr-Cp-MBA photoresist in Example 10 obtained by electron beam exposure;

[0043] Figure 3 SEM image of the 25 nm line pattern of the Zr-Cp-TFAA photoresist in Example 23 obtained by EUV exposure. DETAILED DESCRIPTION

[0044] To enable persons skilled in the art to understand the features and effects of the present application, the following is a general description and definition of the terms and phrases mentioned in the specification and claims. Unless otherwise specified, all technical and scientific words used herein have their usual meanings to those skilled in the art of the present application, and in the event of conflict, the definitions in the present specification shall prevail.

[0045] Theories or mechanisms described and disclosed herein, whether correct or not, should not be considered limiting of the scope of the present application, which is limited only by the claims. The present application can be implemented in ways other than those specifically described herein.

[0046] In the present disclosure, the terms "comprise", "include", "contain", and the like, encompass the meanings of "consist essentially of" and "consist of", for example, when the present disclosure discloses "A comprises B and C", "A consists essentially of B and C" and "A consists of B and C" should be considered to have been disclosed herein.

[0047] In the present disclosure, all features defined in the form of numerical ranges or percentage ranges, such as values, amounts, contents, and concentrations, are for the sake of brevity and convenience. Accordingly, the description of numerical ranges or percentage ranges should be considered to have encompassed and specifically disclosed all possible sub-ranges and individual values within the range (including integers and fractions).

[0048] In this document, when describing embodiments or examples, it should be understood that it is not intended to limit the invention to those embodiments or examples. Rather, all alternatives, modifications, and equivalents of the methods and materials described herein are covered within the scope defined by the claims.

[0049] For the sake of brevity, not all possible combinations of the technical features in each implementation scheme or embodiment are described herein. Therefore, as long as there is no contradiction in the combination of these technical features, the technical features in each implementation scheme or embodiment can be combined arbitrarily, and all possible combinations should be considered within the scope of this specification.

[0050] In this invention, alkyl refers to a monovalent saturated group composed of carbon atoms and hydrogen atoms, having a straight-chain or branched structure. In this invention, the number of carbon atoms preceding the group indicates the number of carbon atoms contained in the group; for example, C1 alkyl represents an alkyl group containing one carbon atom, i.e., methyl. Alkyl groups suitable for this invention can be C1 to C10 alkyl groups, such as C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, C9 alkyl, and C10 alkyl.

[0051] In this invention, alkenyl refers to an unsaturated group containing carbon-carbon double bonds, which has a straight-chain or branched structure composed of carbon atoms and hydrogen atoms. The alkenyl groups suitable for this invention can be C2-C10 alkenyl groups, such as C2 alkenyl, C3 alkenyl, C4 alkenyl, C5 alkenyl, C6 alkenyl, C7 alkenyl, C8 alkenyl, C9 alkenyl, and C10 alkenyl.

[0052] In this invention, alkynyl refers to an unsaturated group containing a carbon-carbon triple bond and having a straight-chain or branched structure, composed of carbon atoms and hydrogen atoms. The alkenyl groups suitable for this invention can be C2-C10 alkynyl groups, such as C2 alkynyl, C3 alkynyl, C4 alkynyl, C5 alkynyl, C6 alkynyl, C7 alkynyl, C8 alkynyl, C9 alkynyl, and C10 alkynyl.

[0053] In this invention, cycloalkyl refers to a monovalent saturated group with an aliphatic ring structure composed of carbon atoms and hydrogen atoms, and the cycloalkyl group is connected to other parts of the molecule through carbon atoms on the aliphatic ring. The cycloalkyl groups suitable for this invention can be C3-C10 cycloalkyl groups, such as C3 cycloalkyl, C4 cycloalkyl, C5 cycloalkyl, C6 cycloalkyl, C7 cycloalkyl, C8 cycloalkyl, C9 cycloalkyl, and C10 cycloalkyl.

[0054] In this invention, alkoxy refers to -O-alkyl.

[0055] In the present application, aryl refers to a monovalent group having an aromatic ring structure composed of carbon atoms and hydrogen atoms, and the aryl is connected to other parts of the molecule through a carbon atom on the aromatic ring. The aryl suitable for the present application can be a C6-C20 aryl, such as a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group.

[0056] In the present application, heteroaryl refers to a monovalent group having an aromatic ring structure composed of carbon atoms, hydrogen atoms, and heteroatoms (such as sulfur atoms, nitrogen atoms, oxygen atoms), and the heteroaryl is connected to other parts of the molecule through a carbon atom or a heteroatom on the aromatic ring. The heteroaryl suitable for the present application can be a five- to twenty-membered heteroaryl, and the number of members before the heteroaryl refers to the number of ring-forming atoms of the heteroaromatic ring.

[0057] In the present application, hydrogen atoms include protium, deuterium, and tritium.

[0058] The zirconium cluster coordination compound provided by the present application has a chemical formula of {[(Cp n Zr)3(μ2-OH)3(μ3-O)L3] + Cl -}, wherein μ2-OH represents an -OH group connected to two metal atoms, and μ3-O represents an O atom connected to three zirconium metal atoms.

[0059] The zirconium cluster coordination compound provided by the present application has a trinuclear metal cluster structure. This trinuclear cluster has a symmetry close to C3, the carboxylate ligand is oriented below the Zr3 triangle plane, and the μ2-OH group is located above the plane, forming a trinuclear cluster, which looks like a three-connected secondary building unit (SBU) and a pyramid geometry.

[0060] In the present application, the sensitivity of the zirconium cluster coordination compound can be improved by introducing F, I, CF3, and the like.

[0061] In the present application, by controlling the alkyl chain of the zirconium cluster coordination compound in the photoresist composition, the film-forming property and solubility of the photoresist can be controlled, thereby optimizing the chemical gradient of the image boundary and reducing the chemical heterogeneity of the image boundary. Controlling the number of carbons in the alkyl chain to C1-C10 is beneficial to improve the film-forming property and solubility of the corresponding photoresist.

[0062] In the present application, the etch resistance of the zirconium cluster coordination compound can be improved by introducing a cyclic hydrocarbon group (such as cyclopentane, cyclohexene) or an aromatic hydrocarbon group (such as a phenyl group, a naphthyl group).

[0063] In the present application, replacing cyclopentadiene with pentamethylcyclopentadiene can control the resolution and etch resistance of the zirconium cluster coordination compound.

[0064] In the present application, n-butylcyclopentadiene is used to replace cyclopentadiene to regulate the film-forming property and solubility of the zirconium cluster coordination compound.

[0065] The zirconium cluster coordination compound of the present application can interact under suitable exposure conditions due to its special structure, so that the polarity of the zirconium cluster material changes, thereby causing the solubility of the zirconium agent to change before and after exposure. Based on this characteristic, the zirconium cluster coordination compound can be used as a component of photoresist to cause the solubility of the exposed part and the non-exposed part of the photoresist to differ in the developer, the solubility of the exposed part in the developer decreases, while the non-exposed part can be dissolved in the developer, so that the non-exposed area can be removed after development, and the desired fine pattern can be obtained. Compared with traditional polymer photoresist and molecular glass photoresist, the zirconium cluster coordination compound of the present application can be used as a component of photoresist due to its special structure, and high resolution, high sensitivity, low line roughness and other more excellent photoetching properties can be achieved.

[0066] The zirconium cluster coordination compound of the present application can be prepared by the following steps:

[0067] S1: dissolving the zirconium source and the organic carboxylic acid in a mixed system of a first organic solvent and water, stirring, filtering to obtain a crude product;

[0068] S2: dispersing the obtained crude product in a second organic solvent, heating at 30-100℃ (for example 55℃, 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃) for 1-3h (for example 1.5h, 2h, 2.5h), and then cooling, standing, filtering, washing and drying to obtain the pure coordination compound.

[0069] In step S1, the molar ratio of zirconium element in the zirconium source to carboxyl group in the organic carboxylic acid can be 1:1-1:6, for example 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5.

[0070] In step S1, the volume ratio of the first organic solvent to water in the mixed system is 1:1-6:1, for example 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1.

[0071] In step S1, the stirring temperature is 20-100℃ (for example 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 70℃, 80℃, 90℃, 100℃), preferably 25-80℃; the stirring time is 1-24 hours (for example 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours).

[0072] The mass ratio of the zirconium cluster coordination compound in the photoresist composition is preferably 0.05wt%-5wt%, for example, 0.05wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.2wt%, 1.3wt%, 1.4wt%, 1.5wt%, 1.6wt%, 1.7wt%, 1.8wt%, 1.9wt%, 2wt%, 2.1wt%, 2.2wt%, 2.3wt%, 2.4wt%, 2.5wt%, 2.6wt%, 2.7wt%, 2.8wt%, 2.9wt%, 3wt%, 3.1wt%, 3.2wt%, 3.3wt%, 3.4wt%, 3.5wt%, 3.6wt%, 3.7wt%, 3.8wt%, 3.9wt%, 4wt%, 4.1wt%, 4.2wt%, 4.3wt%, 4.4wt%, 4.5wt%, 4.6wt%, 4.7wt%, 4.8wt%, 4.9wt%, preferably 0.05wt%-3wt%.

[0073] Compared with traditional organic photoresist, metal photoresist has the advantages of high extreme ultraviolet light absorption efficiency, high etching resistance and high resolution of pattern. Metal organic coordination compound as extreme ultraviolet photoresist material will have great development space, and will become the most promising photoresist material in the next generation of high-resolution lithography. Based on this, the zirconium cluster coordination compound for photoresist in the application contains three metal element cores and organic carboxylic acid ligands in the structure, which has smaller molecular size than the commonly used Sn12 metal cluster, and can obtain better lithography resolution. In addition, compared with the reported zirconium / hafnium metal cluster photoresist, the cyclopentadiene derivative is innovatively introduced into the cluster structure, which can effectively increase the etching resistance, thereby improving the resolution and feature size of the lithography pattern. In addition, the zirconium cluster coordination compound of the application is easy to prepare, and can regulate the structure characteristics and lithography performance of the photoresist through organic ligand regulation. Further, by optimizing the photoresist process (including film process and exposure process), a high-resolution lithography pattern can be obtained. This will be an important reference for the development of new metal photoresist with high sensitivity, high etching resistance and high resolution. At the same time, this kind of zirconium metal photoresist also shows great application potential in the field of extreme ultraviolet photoresist, provides a new solution for extreme ultraviolet lithography, makes certain technical reserves for the development of extreme ultraviolet photoresist, and greatly promotes the practical application of metal lithography technology in the semiconductor field.

[0074] The zirconium cluster coordination compound in the application can be prepared by the following general reaction and specific steps:

[0075]

[0076] The zirconium source (such as bis(cyclopentadienyl)zirconium dichloride, bis(pentamethylcyclopentadienyl)zirconium dichloride or bis(n-butylcyclopentadienyl)zirconium dichloride) and organic carboxylic acid are dissolved in a mixed system of organic solvent and water, wherein the molar ratio of zirconium source (zirconium element) to organic carboxylic acid is 1:1-1:6 (for example 1:1.5, 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, 1:5, 1:5.5), and the organic solvent is selected from one or more of dichloromethane, chloroform, N,N-dimethylformamide, tetrahydrofuran, dioxane, toluene, chlorobenzene, acetone, ethyl acetate, acetonitrile, methanol, ethanol, n-hexane. After stirring at 20-100°C (for example 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 70°C, 80°C, 90°C, 100°C) for 1-24 hours, the clear solution becomes turbid and a large amount of white solid is produced. After standing and filtration, the white solid is washed with an appropriate amount of water and organic solvent 3-5 times, and the organic solvent used for washing is preferably selected from one or more of n-hexane, dichloromethane, chloroform, acetone, ethyl acetate, acetonitrile, methanol, ethanol. After washing, the obtained white solid is dispersed in an appropriate amount of organic solvent, and the re-dissolution solvent is preferably selected from one or more of n-hexane, cyclohexane, dichloromethane, chloroform, N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, toluene, acetone, ethyl acetate, acetonitrile, methanol and ethanol. After dissolution, the reaction system is heated at 30-100°C (for example 40°C, 50°C, 55°C, 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, 90°C, 95°C) for 1-3 hours, and then cooled to room temperature. After standing for 5-48 hours, the white solid is obtained, which is collected by filtration and dried in a vacuum drying oven at 50°C to obtain the coordination compound in the present application.

[0077] The photoresist composition in the present application can be prepared by the following steps: dispersing the zirconium cluster coordination compound in an organic solvent, ultrasonicating for 1-30 min, dissolving the zirconium cluster coordination compound in the organic solvent, preparing a photoresist solution of 0.05wt%-5wt% (for example, 0.05wt%, 0.1wt%, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, 1.2wt%, 1.4wt%, 1.6wt%, 1.8wt%, 2wt%, 2.2wt%, 2.4wt%, 2.6wt%, 2.8wt%, 3wt%, 3.2wt%, 3.4wt% 3.6wt%, 3.8wt%, 4wt%, 4.2wt%, 4.4wt%, 4.6wt%, 4.8wt%) and then filtering with a 0.1 μm filter head to obtain the desired photoresist composition. The organic solvent used can be one or more selected from the group consisting of tetrahydrofuran, acetonitrile, dioxane, chloroform, 4-methyl-2-pentanol, methyl isobutyl ketone, cyclohexanone, acetone, 2-heptanone, dichloroethane, propylene glycol, ethyl acetate, cyclohexane, N,N-dimethylformamide, isoamyl acetate, propyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, isobutyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, methyl isobutyl carbinol, propylene glycol methyl ether acetate (PGMEA), 1-ethoxy-2-propanol, methanol, ethanol, isopropanol and n-butanol.

[0078] The zirconium cluster coordination compound of the present application exhibits more outstanding comprehensive performance as an emerging photoetching material: (1) Its atomic-level precise molecular structure and monodisperse characteristics fundamentally solve the size unevenness problem of nanoparticles, effectively inhibit the scattering effect in electron beam or EUV photoetching, and realize sub-20 nm high-resolution patterning; (2) In terms of optical performance, the zirconium cluster coordination compound has stronger photon absorption capacity in the EUV band due to higher metal atom density, which can significantly improve the photoresist sensitivity and greatly reduce the exposure dose requirement; (3) The unique localized surface plasmon resonance (LSPR) effect can also precisely regulate the near-field light intensity distribution, significantly improving the pattern edge definition and line width roughness; (4) The inorganic core structure of the zirconium cluster coordination compound endows the material with excellent etching resistance, and exhibits higher structural stability than traditional zirconium nanoparticles in the development and pattern transfer processes. Through precise ligand engineering regulation, the zirconium cluster coordination compound in the present application not only has the above photoetching performance, but also has better process compatibility and film formation uniformity. These excellent characteristics make the zirconium cluster coordination compound of the present application an ideal choice for breaking through the limit of existing photoetching technology, and provide an innovative material solution for the next generation of high-precision photoetching technology.

[0079] The present application will be described below in the manner of specific examples. It should be understood that these examples are merely illustrative and are not intended to limit the scope of the present application. The methods, reagents and materials used in the examples are conventional in the art unless otherwise specified. The raw material compounds in the examples can be purchased through commercial channels.

[0080] Synthesis Example 1

[0081] Preparation of zirconium-based resist (Zr-Cp-AA): 1.46 g (5.0 mmol) of bis(cyclopentadienyl)zirconium dichloride [Zr(Cp)2Cl2] (wherein Cp represents cyclopentadiene) was weighed into a round-bottom flask, and then 30 mL of dichloromethane (DCM) was added to dissolve it. Subsequently, 0.36 g (5.0 mmol) of acrylic acid (AA) was weighed and slowly added to the above solution. After stirring at room temperature for 6 hours, the clear solution became turbid. Then, an appropriate amount of DCM was removed by rotary evaporation, and the white solid was collected by standing and filtering. Subsequently, it was dispersed in 30 mL of ethyl acetate / DCM (v / v = 5:1) solvent, heated to 50°C. Then, the white solid was collected by standing and filtering, and dried in a drying oven to obtain the target product Zr-Cp-AA. Mass spectrometry test was performed on the prepared zirconium-based resist, and ESI-MS m / z: 748.8745 (Calcd m / z: 748.8739 for [(CpZr)3(μ2-OH)3(μ3-O)(C3O2H3)3] + ).

[0082] Synthesis Example 2

[0083] The Zr-based resist (Zr-Cp-MAA) in Synthesis Example 2 was prepared in a similar manner as in Synthesis Example 1, except that acrylic acid was replaced with equimolar amount of methacrylic acid (MAA) to obtain Zr-Cp-MAA The prepared Zr-based resist was subjected to mass spectrometry test, ESI-MS m / z: 790.9236 (Calcd m / z: 790.9229 for [(CpZr)3(μ2-OH)3(μ3-O)(C3O2H3)3] + ).

[0084] Synthesis Example 3

[0085] The Zr-based resist (Zr-Cp-BAA) in Synthesis Example 3 was prepared in a similar manner as in Synthesis Example 1, except that acrylic acid was replaced with equimolar amount of 2-bromoacrylic acid (BAA) to obtain Zr-Cp-BAA The prepared Zr-based resist was subjected to mass spectrometry test, ESI-MS m / z: 984.6050 (Calcd m / z: 984.6056 for [(CpZr)3(μ2-OH)3(μ3-O)(C3BrO2H2)3] + ).

[0086] Synthesis Example 4

[0087] The Zr-based resist (Zr-Cp-FAA) in Synthesis Example 4 was prepared in a similar manner as in Synthesis Example 1, except that acrylic acid was replaced with equimolar amount of 2-fluoroacrylic acid (FAA) to obtain Zr-Cp-FAA The prepared Zr-based resist was subjected to mass spectrometry test, ESI-MS m / z: 802.8471 (Calcd m / z: 802.8466 for [(CpZr)3(μ2-OH)3(μ3-O)(C3FO2H2)3] + ).

[0088] Synthesis Example 5

[0089] The Zr-based resist (Zr-Cp-TFAA) in Synthesis Example 5 was prepared in a similar manner as in Synthesis Example 1, except that acrylic acid was replaced with equimolar amount of 2-(trifluoromethyl)acrylic acid (TFAA) to obtain Zr-Cp-TFAA The prepared Zr-based resist was subjected to mass spectrometry test, ESI-MS m / z: 952.8380 (Calcd m / z: 952.8375 for [(CpZr)3(μ2-OH)3(μ3-O)(C4F3O2H2)3]+ ).

[0090] Synthesis Example 6

[0091] The Zr-based resist (Zr-Cp-PA) in Synthesis Example 6 was prepared by a similar method as in Synthesis Example 1, except that acrylic acid was replaced by equimolar amount of n-propionic acid (PA) to obtain Zr-Cp-PA The prepared Zr-based resist was tested by mass spectrometry, ESI-MS m / z: 754.9227 (Calcd m / z: 754.9220 for [(CpZr)3(μ2-OH)3(μ3-O)(C3O2H5)3] + ).

[0092] Synthesis Example 7

[0093] The Zr-based resist (Zr-Cp-YA) in Synthesis Example 7 was prepared by a similar method as in Synthesis Example 1, except that acrylic acid was replaced by equimolar amount of propiolic acid (YA) to obtain Zr-Cp-YA The prepared Zr-based resist was tested by mass spectrometry, ESI-MS m / z: 784.8765 (Calcd m / z: 784.8758 for [(CpZr)3(μ2-OH)3(μ3-O)(C4O2H3)3] + ).

[0094] Synthesis Example 8

[0095] Preparation of Zr-based resist (Zr-Cp-MCA): 1.46 g (5.0 mmol) of Zr(Cp)2Cl2 was weighed into a round bottom flask, and 20 mL of chloroform was added to the flask to completely dissolve the Zr(Cp)2Cl2. Next, 6 mL of water was added to the resulting solution and the solution was thoroughly mixed and homogenized by magnetic stirring. After that, 0.7 g (5.0 mmol) of 4-methylene cyclohexane carboxylic acid (MCA) was dissolved in 10 mL of chloroform. Then, the MCA solution was added to the previously prepared mixed solution of Zr(Cp)2Cl2. After stirring at room temperature for 6 hours, the clear solution became turbid, producing a large amount of white solid, which was left to stand and filtered, and washed with water and DCM, and the white solid was collected. Subsequently, it was dispersed in 30 mL of tetrahydrofuran / chloroform (v / v = 5:1) solvent, and heated to 50°C. After about 2 hours, the heating was stopped to room temperature, left to stand and filtered, and the white solid was collected by washing with acetone, chloroform, and then vacuum dried in an oven at 50°C to obtain the product Zr-Cp-MCA The prepared Zr-based resist was tested by mass spectrometry, ESI-MS m / z: 953.0646 (Calcd m / z: 953.0641 for [(CpZr)3(μ2-OH)3(μ3-O)(C8O2H11 )3] + )。

[0096] Take 20 mg Zr-Cp-MCA dissolved in 4 mL methanol solution, and slowly evaporate it. After three days, colorless block crystals are obtained, and their crystal structure is characterized by single crystal diffraction, as shown in Figure 1

[0097] Synthesis Example 9

[0098] Zr-based resist (Zr-Cp-CEA) in Synthesis Example 9 is prepared by using a similar method as in Synthesis Example 8, but the difference is that MCA is replaced by 3-cyclopentene carboxylic acid (CEA) of equal molar amount, to obtain Zr-Cp-CEA The prepared Zr-based resist is tested by mass spectrometry, ESI-MS m / z: 868.9710 (Calcd m / z: 868.9704 for [(CpZr)3(μ2-OH)3(μ3-O)(C6O2H7)3] + )。

[0099] Synthesis Example 10

[0100] Preparation of Zr-based resist (Zr-Cp-MBA): Take 1.46 g (5.0 mmol) Zr(Cp)2Cl2 and add it to a round-bottom flask, then dissolve it in 20 mL tetrahydrofuran and 6 mL water. Then, take 0.68 g (5.0 mmol) m-toluic acid (MBA) and dissolve it in 5.0 tetrahydrofuran 10 mL, and add it dropwise to the above solution. After stirring at 50°C for 10 hours, cool to room temperature, concentrate by rotary evaporation to remove an appropriate amount of solvent, stand and filter, and rinse with water and acetone, chloroform, n-hexane, collect white solid, then disperse in 30 mL tetrahydrofuran / ethyl acetate (v / v=3:1) solvent, heat to 50°C. Stop heating to room temperature after about 2 hours, stand and filter, and rinse with ethyl acetate, chloroform, collect white solid, and then vacuum dry oven at 50°C to obtain the product Zr-Cp-MBA The prepared Zr-based resist is tested by mass spectrometry, ESI-MS m / z: 940.9786 (Calcd m / z: 940.9782 for [(CpZr)3(μ2-OH)3(μ3-O)(C8O2H7)3] + )。

[0101] Synthesis Example 11

[0102] ​Preparation of Zr-based resist (Zr-Cp-VBA): Weigh 1.46 g (5.0 mmol) of Zr(Cp)2Cl2into a round bottom flask, then add 20 mL of tetrahydrofuran and 6 mL of water to dissolve it. Subsequently, weigh 1.12 g (5.0 mmol) of 4-(4-vinylphenyl)benzoic acid (VBA) in 10 mL of N,N-dimethylformamide and add it to the above solution. After stirring at 80°C for 10 hours, cool to room temperature. Then remove the organic solvent by rotary evaporation, then disperse in 30 mL of chloroform / methanol (v / v = 5:1) solvent, heat to 50°C. Stop heating to room temperature after about 2 hours, stand for filtration, and collect the white solid by washing with ethyl acetate, chloroform, and then vacuum drying oven at 50°C to dry the product Zr-Cp-VBA Mass spectrometry test of the prepared zirconium-based resist, ESI-MS m / z: 1205.0645 (Calcd m / z: 1205.06439 for [(CpZr)3(μ2-OH)3(μ3-O)(C8O2H7)3] + ).

[0103] Synthesis Example 12

[0104] The zirconium-based resist (Zr-pCp-VBA) in Synthesis Example 12 is prepared by a similar method to that in Synthesis Example 1, except that Zr(Cp)2Cl2is replaced by an equimolar amount of bis(pentamethylcyclopentadienyl)zirconium dichloride [Zr(pCp)2Cl2] (where pCp represents pentamethylcyclopentadiene), to obtain Zr-pCp-VBA Mass spectrometry test of the prepared zirconium-based resist, ESI-MS m / z: 959.1104 (Calcd m / z: 959.1100 for [(pCpZr)3(μ2-OH)3(μ3-O)(C3O2H3)3] + ).

[0105] Synthesis Example 13

[0106] The zirconium-based resist (Zr-pCp-VBA) in Synthesis Example 12 is prepared by a similar method to that in Synthesis Example 1, except that Zr(Cp)2Cl2is replaced by an equimolar amount of bis(pentamethylcyclopentadienyl)zirconium dichloride [Zr(pCp)2Cl2] (where pCp represents pentamethylcyclopentadiene), to obtain Zr-pCp-VBA Mass spectrometry test of the prepared zirconium-based resist, ESI-MS m / z: 959.1104 (Calcd m / z: 959.1100 for [(pCpZr)3(μ2-OH)3(μ3-O)(C3O2H3)3] + ).

[0107] Synthesis Example 14

[0108] The Zr-based resist (Zr-pCp-TFAA) in Synthesis Example 14 was prepared by a similar method to that in Synthesis Example 5, except that Zr(Cp)2Cl2was replaced with an equimolar amount of Zr(pCp)2Cl2to give Zr-pCp-TFAA The prepared Zr-based resist was subjected to mass spectrometry test, ESI-MS m / z: 1163.0758 (Calcd m / z: 1163.0763 for [(pCpZr)3(μ2-OH)3(μ3-O)(C4F3O2H2)3] + ).

[0109] Synthesis Example 15

[0110] The Zr-based resist (Zr-bCp-TFAA) in Synthesis Example 15 was prepared by a similar method to that in Synthesis Example 1, except that Zr(Cp)2Cl2was replaced with an equimolar amount of Zr(bCp)2Cl2to give Zr-bCp-TFAA The prepared Zr-based resist was subjected to mass spectrometry test, ESI-MS m / z: 917.0625 (Calcd m / z: 917.0621 for [(bCpZr)3(μ2-OH)3(μ3-O)(C3O2H3)3] + ).

[0111] Synthesis Example 16

[0112] The Zr-based resist (Zr-bCp-TFAA) in Synthesis Example 15 was prepared by a similar method to that in Synthesis Example 1, except that Zr(Cp)2Cl2was replaced with an equimolar amount of Zr(bCp)2Cl2to give Zr-bCp-TFAA The prepared Zr-based resist was subjected to mass spectrometry test, ESI-MS m / z: 959.1097 (Calcd m / z: 959.1091 for [(bCpZr)3(μ2-OH)3(μ3-O)(C3O2H5)3] + ).

[0113] Synthesis Example 17

[0114] Preparation of Zr-based resist (Zr-bCp-IAA): Weigh 1.46 g (50 mmol) of Zr(bCp)2Cl2into a round bottom flask, then add 15 mL of chloroform and 4 mL of water to dissolve it. Weigh 0.99 g (5.0 mmol) of 3-iodoacrylic acid (MAA) into 10 mL of ethanol, and slowly drop it into the above solution. After stirring at 60°C for 10 hours, cool to room temperature, concentrate and remove the solvent by rotary evaporation, then disperse in 15 mL of tetrahydrofuran / DCM (v / v = 3:1) solvent, and heat to 50°C. Stop heating to room temperature after about 2 hours, stand and filter, and collect the white solid by washing with ethyl acetate and chloroform, and then dry in a vacuum oven at 50°C to obtain the product Zr-bCp-IAA Mass spectrometry test of the prepared Zr-based resist, ESI-MS m / z: 1294.7531 (Calcd m / z: 1294.7535 for [(bCpZr)3(μ2-OH)3(μ3-O)(C3IO2H2)3] + ).

[0115] Synthesis Example 18

[0116] The Zr-based resist (Zr-bCp-MCA) in Synthesis Example 18 is prepared by a method similar to that in Synthesis Example 8, except that Zr(Cp)2Cl2is replaced by an equal molar amount of Zr(bCp)2Cl2to obtain Zr-bCp-MCA Mass spectrometry test of the prepared Zr-based resist, ESI-MS m / z: 1294.7531 (Calcd m / z: 1294.7535 for [(bCpZr)3(μ2-OH)3(μ3-O)(C3IO2H2)3] + ).

[0117] Synthesis Example 19

[0118] The Zr-based resist (Zr-bCp-MBA) in Synthesis Example 19 is prepared by a method similar to that in Synthesis Example 10, except that Zr(Cp)2Cl2is replaced by an equal molar amount of Zr(bCp)2Cl2to obtain Zr-bCp-MBA Mass spectrometry test of the prepared Zr-based resist, ESI-MS m / z: 1111.2087 (Calcd m / z: 1111.2083 for [(bCpZr)3(μ2-OH)3(μ3-O)(C8O2H7)3] + ).

[0119] Synthesis Example 20

[0120] A zirconium-based resist (Zr-bCp-CCA) in Synthesis Example 20 was prepared by using a similar method as in Synthesis Example 18, except that MCA was replaced by 3-cyclohexene-1-carboxylic acid (CCA) in an equimolar amount, to obtain Zr-bCp-CCA The prepared zirconium-based resist was subjected to mass spectrometry test, ESI-MS m / z: 1081.2545 (Calcd m / z: 1081.2542 for [(bCpZr)3(μ2-OH)3(μ3-O)(C7O2H9)3] + )。

[0121] Example

[0122] 1. An appropriate amount of zirconium cluster coordination compound and organic solvent (including tetrahydrofuran, acetonitrile, dioxane, chloroform, 4-methyl-2-pentanol, methyl isobutyl ketone, cyclohexanone, acetone, 2-heptanone, N,N-dimethylformamide, dichloroethane, propylene glycol, ethyl acetate, cyclohexane, isoamyl acetate, propyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, isobutyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, propylene glycol methyl ether acetate, 1-ethoxy-2-propanol, methanol, ethanol, n-propanol, isopropanol, n-butanol, etc.) were weighed, and a photoresist solution with a solid content of 0.05wt%-5wt% was prepared, dissolved by ultrasonic oscillation, and filtered for use.

[0123] 2. The silicon wafer was pretreated with hexamethyldisilazane (HMDS) at 90-180°C for 2-10 min, then spin-coated on a spin coater at a speed of 500-8000 rpm for 30-180 s (the specific parameters were adjusted according to the desired film thickness), a small amount of photoresist solution was coated on the surface of the silicon wafer, and the organic solvent was removed by pre-baking at 60-100°C to obtain a pre-film layer.

[0124] 3. An electron beam light source or EUV light source was used to expose the pre-film layer through a mask (a pre-set pattern).

[0125] 4. After the exposure is completed, the silicon wafer is taken out and post-baked at a temperature of 20-100°C, and then developed using an organic solvent (one or more of the following organic solvents can be selected according to actual needs: indene, indane, quinoline, methyl isobutyl ketone, methyl isobutyl carbinol, propylene glycol, 2-heptanone, acetone, cyclohexanone, 1-methylnaphthalene, toluene, o-xylene, m-xylene, ethyl acetate, butyl acetate, methanol, ethanol, n-propanol, isopropanol, n-butanol, chloroform, dichloromethane, dichloroethane, decaline, tetralin, n-hexane, cyclohexane, isoamyl acetate, propyl formate, butyl formate, isobutyl formate, amyl formate, isoamyl formate, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate, amyl lactate, isoamyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenylacetate, benzyl formate, phenethyl formate, methyl 3-phenylpropionate, benzyl propionate, ethyl phenylacetate, 2-phenylethyl acetate, etc.).

[0126] 5. After the development is completed, the silicon wafer is blown dry with a nitrogen gun, and then the sample is subjected to a hardening treatment at a temperature of 90-180°C, and after the completion, the sample is observed.

[0127] 6. The lithographic imaging result is observed under a scanning electron microscope.

[0128] The composition of the photoresist composition of the specific embodiments, the exposure conditions and the line width of the exposed area are shown in Table 1.

[0129] Table 1: Composition of the photoresist composition of Examples 1-29, exposure conditions and line width of the exposed area

[0130]

[0131]

[0132]

[0133] Sensitivity and resolution are key evaluation indicators of the performance of the photoresist. Specifically, the smaller the exposure dose value, the higher the sensitivity of the photoresist composition; and the smaller the resolution value, the higher the resolution of the photoresist composition.

[0134] As can be seen from Table 1, the photoresist compositions of the zirconium cluster coordination compounds (Examples 1-29) of the present application all exhibit high lithographic resolution, with a resolution value of ≤50 nm. In addition, as can be seen from Table 1, the photoresist compositions of the zirconium cluster coordination compounds (Examples 1-29) of the present application all exhibit high sensitivity, with an exposure dose value of ≤100 mJ / cm2. Figure 2 It can be seen that the photoresist using the Zr-Cp-MBA formulation can form a clear 40 nm stripe pattern after electron beam exposure; Figure 3It is shown that the photoresist of the Zr-Cp-TFAA formulation can realize high-resolution pattern of 25 nm under EUV exposure. Therefore, the new photoresist based on the zirconium cluster coordination compound of the application exhibits excellent sensitivity and resolution under both electron beam and EUV exposure modes.

[0135] It should be further clarified that in the embodiments of the application, each embodiment does not contain only one independent technical solution. These embodiments are only used to help understand the technical solutions of the application and are not a limitation on the protection scope of the application. Any modification, equivalent replacement, improvement, etc. based on the technical concept of the application and for the technical solutions of the application should be covered within the protection scope of the application.

Claims

1. A coordination compound, characterized in that, The chemical formula of the coordination compound is {[(Cp n Zr)3(μ2-OH)3(μ3-O)L3] + Cl - }, Among them, Cp n For the structure of formula I In Formula I, R1, R2, R3, R4, and R5 are each independently selected from hydrogen atoms, unsubstituted or substituted C1-C10 alkyl groups, and unsubstituted or substituted C2-C10 alkenyl groups. Zr represents zirconium atoms; L is a ligand formed by the loss of a hydrogen atom from the carboxyl group of an organic carboxylic acid. The chemical formula of the organic carboxylic acid ligand is Y-COOH, where Y is an organic group.

2. The coordination compound according to claim 1, characterized in that, The substituents on R1, R2, R3, R4, and R5 are selected from halogen atoms and trifluoromethyl groups.

3. The coordination compound according to claim 1, characterized in that, Cp n for Or, structure II In Formula II, R6 is an unsubstituted or substituted C1-C10 alkyl or an unsubstituted or substituted C2-C10 alkenyl; preferably, the substituent on R6 is selected from halogen atoms and trifluoromethyl; preferably, R6 is n-butyl.

4. The coordination compound according to claim 1, characterized in that, Y represents an unsubstituted or substituted C1-C10 alkyl, an unsubstituted or substituted C2-C10 alkenyl, an unsubstituted or substituted C2-C10 alkynyl, an unsubstituted or substituted C3-C8 cycloalkyl, an unsubstituted or substituted C5-C10 cycloalkenyl, methylenecyclobutyl, methylenecyclopentyl, methylenecyclohexyl, adamantyl, C6-C10 aryl, biphenyl, or a structure of formula III. In Formula III, * indicates the position attached to -COOH, and R is a halogen atom, trifluoromethyl, methyl, tert-butyl, methoxy, or phenyl; preferably, the substituent on Y is selected from halogen atoms, hydroxyl, trifluoromethyl, C1-C10 alkyl, C2-C10 alkenyl, C2-C10 alkynyl, C5-C10 cycloalkyl, C5-C10 cycloalkenyl, C5-C10 cycloalkynyl, C6-C10 aryl, and biphenyl; Preferably, the structure of Formula III is the following Formula III-1, Formula III-2, or Formula III-3: In formula III-1, R is F, Br, or methyl; In Formula III-2, R is trifluoromethyl, F, methyl, tert-butyl, methoxy, or phenyl; In formula III-3, R is F, Cl, Br, methyl or methoxy.

5. The coordination compound according to claim 1, characterized in that, The coordination compound has the structural formula of formula A, formula B, or formula C:

6. The coordination compound according to claim 1, characterized in that, The coordination compound is selected from the following compounds:

7. A method for preparing the coordination compound according to any one of claims 1-6, characterized in that, The method includes the following steps: S1: The zirconium source and organic carboxylic acid are dissolved in a mixture of the first organic solvent and water, and the crude product is obtained after stirring and filtration. S2: The crude product obtained is redispersed in a second organic solvent, heated at 30-100℃ for 1-3 hours, and then cooled, allowed to stand, filtered, washed and dried to obtain the coordination compound.

8. The method as described in claim 7, characterized in that, The method meets one or more of the following characteristics: In step S1, the zirconium source is bis(cyclopentadienyl)zirconia, bis(pentamethylcyclopentadienyl)zirconia, or bis(n-butylcyclopentadienyl)zirconia. In step S1, the molar ratio of the zirconium source to the carboxyl group in the organic carboxylic acid is 1:1 to 1:6; In step S1, the volume ratio of the first organic solvent to water in the mixed system is 1:1 to 6:

1. In step S1, the first organic solvent is one or more selected from dichloromethane, chloroform, N,N-dimethylformamide, tetrahydrofuran, dioxane, toluene, chlorobenzene, acetone, ethyl acetate, acetonitrile, methanol, ethanol, and n-hexane; In step S1, the stirring temperature is 20-100℃ and the stirring time is 1-24 hours; In step S1, the intermediate product is washed with water and a third organic solvent during filtration. The third organic solvent is one or more selected from n-hexane, petroleum ether, diethyl ether, tetrahydrofuran, dioxane, dichloromethane, chloroform, acetone, ethyl acetate, acetonitrile, methanol, and ethanol. In step S2, the second organic solvent is one or more selected from n-hexane, cyclohexane, dichloromethane, chloroform, N,N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran, dioxane, toluene, acetone, ethyl acetate, acetonitrile, methanol, and ethanol.

9. A coordination compound, characterized in that, The coordination compound is prepared by the method according to claim 7 or 8.

10. A photoresist composition, characterized in that, The photoresist composition comprises the coordination compound according to any one of claims 1-6 and 9; preferably, the photoresist composition further comprises a fourth organic solvent, wherein the fourth organic solvent is preferably selected from tetrahydrofuran, acetonitrile, dioxane, chloroform, 4-methyl-2-pentanol, methyl isobutyl ketone, cyclohexanone, acetone, 2-heptanone, N,N-dimethylformamide, dichloroethane, propylene glycol, ethyl acetate, cyclohexane, isoamyl acetate, propyl formate, butyl formate, isobutyl formate, amyl formate, formic acid The photoresist composition contains one or more of the following: isoamyl ester, methyl valerate, methyl pentenoate, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, isobutyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, propylene glycol methyl ether acetate, 1-ethoxy-2-propanol, methanol, ethanol, n-propanol, isopropanol, and n-butanol; the mass percentage of the coordination compound in the photoresist composition is preferably 0.05 wt% to 5 wt%.

11. The use of the photoresist composition of claim 11 in the preparation of photolithographic patterns.

12. Use of the coordination compound of any one of claims 1-6 and 9 in ultraviolet lithography, KrF lithography, ArF lithography, extreme ultraviolet lithography, nanoimprint lithography, electron beam lithography or X-ray lithography.

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