A cycloalkyl carboxylic acid ligand modified hexanuclear selenium drum type organotin oxygen cluster compound, a preparation method and application thereof

Abstract

The application belongs to the technical field of crystal material preparation and photoresist technology, and discloses a cycloalkyl carboxylic acid ligand modified hexanuclear selenium drum type organotin oxygen cluster compound as well as a preparation method and application thereof. The cycloalkyl carboxylic acid ligand modified hexanuclear selenium drum type organotin oxygen cluster compound is a zero-dimensional cluster, the organotin oxygen core is arranged in a selenium drum type, six organotin atoms are contained in the cluster compound, and the peripheral ligand is a cycloalkyl carboxylic acid ligand. The chemical general formula of the cycloalkyl carboxylic acid ligand modified hexanuclear selenium drum type organotin oxygen cluster compound is [(R1Sn)6(mu3-O)6L6]. R1 is selected from one of C1-C8 alkyl, C1-C6 alkenyl, C1-C6 alkynyl, phenyl, phenalkenyl, phenalkynyl or benzyl. L is a cycloalkyl carboxylic acid ligand. Mu3 indicates that the coordination atom is connected with three metals. The cluster compound is used for preparing a negative photoresist composition and can be applied to various photoetching technical fields such as 248 nm photoetching and extreme ultraviolet photoetching.

Description

Technical Field

[0001] This invention belongs to the field of crystal material preparation and photoresist technology, specifically relating to a hexanuclear selenium drum-type organotin oxide cluster modified with cycloalkyl carboxylic acid ligands, its preparation method and application. Background Technology

[0002] As semiconductor manufacturing processes advance towards 2 nanometers and below, extreme ultraviolet (EUV) lithography, as a core patterning method, places stringent demands on the performance of lithography materials. Traditional polymer photoresists face a "triangle dilemma" where sensitivity, resolution, and etching resistance are difficult to balance. However, metal-based photoresists, especially structurally precise metal-oxygen clusters, have become an important direction for overcoming the performance bottleneck of photoresists due to their high EUV absorption, molecular-level uniformity, and tunable chemical properties.

[0003] Organotin oxide clusters have attracted attention due to their well-defined molecular structures. Their cores consist of a stable metal-oxygen cluster framework constructed from tin and oxygen atoms, exhibiting excellent extreme ultraviolet light absorption and intrinsic etching resistance. The peripheral alkyl chains and organic ligands endow them with organic solvent solubility and exposure-induced solubility variation characteristics. However, the ligands currently used to construct organotin oxide clusters are mainly phenylcarboxylic acids, which limits the further development of their structure and properties. There is an urgent need to develop novel ligand-modified organotin oxide clusters. Summary of the Invention

[0004] To address the aforementioned problems, this invention proposes a hexanuclear selenium drum-type organotin oxide cluster compound modified with cycloalkyl carboxylic acid ligands, its preparation method, and its application.

[0005] To achieve the above objectives, the present invention adopts the following technical solution: A hexanuclear selenium drum-shaped organotin oxide cluster modified with cycloalkyl carboxylic acid ligands is a zero-dimensional cluster with the organotin oxide core arranged in a selenium drum shape. The cluster contains six organotin atoms, and the peripheral ligands are cycloalkyl carboxylic acid ligands. The general chemical formula of the hexanuclear selenium drum-shaped organotin oxide cluster modified with cycloalkyl carboxylic acid ligands is [(R1Sn)6(µ3-O)6L6]; wherein R1 is selected from one of C1-C8 alkyl, C1-C6 alkenyl, C1-C6 alkynyl, phenyl, benzoenyl, benzoynyl or benzyl; L is a cycloalkyl carboxylic acid ligand; µ3 refers to the coordinating atom connected to three metals.

[0006] Preferably, the cycloalkylcarboxylic acid ligand is selected from one of the following structures: .

[0007] A method for preparing a hexanuclear selenium drum-shaped organotin oxide cluster modified with a cycloalkyl carboxylic acid ligand includes the following steps: S1. Mix the organotin precursor, cycloalkyl carboxylic acid ligand and organic solvent uniformly in a molar ratio of 1: (0.1-50): (1-500); S2. After mixing thoroughly, sonicate for 10 min and then heat under reflux. S3. The clear liquid obtained after heating and reflux reaction is subjected to vacuum distillation to obtain a white or pale yellow solid powder. The powder is then volatilized and recrystallized in an organic solvent to obtain a hexanuclear selenium drum-shaped organotin oxide cluster modified with cycloalkyl carboxylic acid ligands.

[0008] Preferably, in step S1, the organotin precursor is one of C1-C8 alkyltin compounds, C1-C6 alkenyltin compounds, C1-C6 alkynyltin compounds, phenyltin compounds, benzo-alkenyltin compounds, benzo-alkynyltin compounds, or benzyltin compounds.

[0009] Preferably, in steps S1 and S3, the organic solvent is one or more of methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, ethylene glycol, n-pentanol, isopentanol, 1,2-propanediol, 1,3-propanediol, toluene, n-hexane, n-heptane, n-octane, isohexane, isooxane, isooctane, cyclohexane, cyclopentane, petroleum ether, dichloromethane, chloroform, 1,2-dichloroethane, carbon tetrachloride, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, formamide, or deionized water.

[0010] Preferably, in step S2, the reaction temperature of the heating reflux reaction is 40-120 °C, and the reaction time is 2-72 h.

[0011] Application of a hexanuclear selenium drum-type organotin oxide cluster modified with cycloalkyl carboxylic acid ligands, wherein the hexanuclear selenium drum-type organotin oxide cluster modified with cycloalkyl carboxylic acid ligands is used to prepare photoresist compositions and applied in the field of photolithography technology.

[0012] Preferably, the photoresist composition is a negative photoresist, consisting of a hexanuclear selenium drum-type organotin oxide cluster modified with the cycloalkyl carboxylic acid ligand and a photoresist solvent; the hexanuclear selenium drum-type organotin oxide cluster modified with the cycloalkyl carboxylic acid ligand accounts for 0.1-5 wt% of the total mass of the photoresist composition, with the remainder being the photoresist solvent.

[0013] Preferably, the photoresist solvent is one or more of tetrahydrofuran, 1,4-dioxane, benzene, toluene, p-xylene, o-xylene, m-xylene, mesitylene, chlorobenzene, fluorobenzene, propylene glycol monomethyl ether acetate, propylene glycol ethyl ether, ethylene glycol methyl ether acetate, ethyl acetate, butyl acetate, chloroform, dichloromethane, methanol, ethanol, 2-ethoxyethanol, 1,2-dichloroethane, N,N-dimethylformamide, or N,N-dimethylacetamide.

[0014] Preferably, the patterning method of the photoresist composition includes: dissolving the hexanuclear selenium drum-type organotin oxide cluster compound modified with the cycloalkyl carboxylic acid ligand in a photoresist solvent, filtering, and spin-coating it onto a substrate to form a photoresist film; subjecting the photoresist film to electron beam or radiation exposure treatment; contacting the exposed photoresist film with a developer at room temperature for 1-300 s to complete development and achieve patterning; the developer is one or more of n-propanol, isopropanol, n-butanol, isobutanol, toluene, o-xylene, m-xylene, p-xylene, mesitylene, 4-methyl-2-pentanol, 4-methyl-2-pentanone, methyl ethyl ketone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol methyl ether acetate, 2-butanone, 2-heptanone, ethanol, 2-ethoxyethanol, N,N-dimethylformamide, N,N-diethylformamide, acetonitrile, ultrapure water, n-hexane, or cyclohexane; the patterned photoresist film is used in 248 193 nm lithography, extreme ultraviolet lithography, super ultraviolet lithography, nanoimprint lithography, or electron beam lithography.

[0015] By adopting the above technical solution, the present invention has the following beneficial effects: 1. The preparation method of the hexanuclear selenium drum-type organotin oxide cluster compound modified by cycloalkyl carboxylic acid ligands of the present invention is simple, has low requirements for the purity of raw materials, the raw materials are readily available and inexpensive, and chemically pure reagents can be purchased directly without additional purification, which is convenient for large-scale production.

[0016] 2. The photoresist composition of the present invention is an integrated non-chemical amplification photoresist, which does not require the addition of photoacid-generating agents, and the ligand unit does not require acid-sensitive groups, making it convenient to implement and cost-effective.

[0017] 3. The hexanuclear selenium drum-type organotin oxide clusters modified with cycloalkyl carboxylic acid ligands of the present invention have excellent chemical and thermal stability, are soluble in common photoresist organic solvents, have a well-defined structure, and are convenient for conducting component analysis and photolithography mechanism research before and after exposure.

[0018] 4. The photoresist composition of the present invention can prepare uniform thin films with high thermal decomposition temperature. It has strong temperature regulation during the pre-baking, post-baking, and hard baking processes of photolithography. The film structure does not change under high-temperature baking, and the patterning resolution can reach about 50 nm, which meets the application requirements of advanced photolithography technology. Attached Figure Description

[0019] Figure 1 The crystal structure diagrams are those prepared in Examples 1 and 2 of this invention; Figure 2 Thermogravimetric analysis curves of the crystals prepared in Examples 1 and 2 of this invention; Figure 3The infrared spectra of the crystals prepared in Examples 1 and 2 of this invention are shown below. Figure 4 The image shows a scanning electron microscope (SEM) image of the 50 nm stripe pattern of the crystal prepared in Experimental Example 1 of this invention. Detailed Implementation

[0020] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to examples. It should be understood that the specific examples described herein are merely illustrative and not intended to limit the invention.

[0021] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods. See Figures 1 to 4 . Example 1:

[0022] (1) Synthesis of organotin oxide cluster compound [(C4H9Sn)6(µ3-O)6(C4H5O2)6] Butylstannic acid (1040 mg, 5 mmol), cyclopropanecarboxylic acid (430 mg, 5 mmol), and toluene (50 ml) were mixed evenly in a 100 mL round-bottom flask. After thorough mixing, the mixture was sonicated for 10 min, heated to 60 °C and refluxed for 4 h. The supernatant was distilled under reduced pressure to obtain a white crude product. The crude product was then volatilized and recrystallized in a mixed solvent of dichloromethane (1 mL) and ethanol (1 mL) to obtain a pure white product, which is the hexanuclear selenium drum-shaped organotin oxide cluster modified with cycloalkyl carboxylic acid ligands. The structure of this hexanuclear selenium drum-shaped organotin oxide cluster [(C4H9Sn)6(µ3-O)6(C4H5O2)6] is as follows: Figure 1 As shown (for clarity, Figure 1 (Hydrogen atoms are omitted in the text), and the crystal parameters are shown in Table 1.

[0023] (2) Characterization analysis of cluster properties like Figure 2 As shown, thermal analysis tests indicate that the organotin clusters possess excellent thermal stability. Solubility test: A comparative solubility experiment was conducted on the prepared pure hexanuclear selenium drum-type organotin oxide clusters modified with cycloalkyl carboxylic acid ligands. The hexanuclear selenium drum-type organotin oxide clusters modified with cycloalkyl carboxylic acid ligands are soluble in most commonly used laboratory organic solvents, such as dichloromethane, trichloromethane, toluene, xylene, and alkane solvents like 1,2-dibromoethane, but insoluble in water, methanol, N,N-dimethylformamide, N,N-diethylformamide, propylene glycol monomethyl ether acetate, and other solvents.

[0024] Example 2: (1) Synthesis of organotin oxide cluster compound [(C4H9Sn)6(µ3-O)6(C6H9O2)6] Butylstannic acid (1040 mg, 5 mmol), cyclopentanoic acid (570 mg, 5 mmol), and toluene (50 ml) were mixed evenly in a 100 mL round-bottom flask. After thorough mixing, the mixture was sonicated for 10 min, heated to 60 °C and refluxed for 4 h. The supernatant was distilled under reduced pressure to obtain a white crude product. The crude product was then volatilized and recrystallized in a mixed solvent of chloroform (1 mL) and ethanol (1 mL) to obtain a pure white product, which is the hexanuclear selenium drum-shaped organotin oxide cluster modified with cycloalkyl carboxylic acid ligands. The structure of this hexanuclear selenium drum-shaped organotin oxide cluster [(C4H9Sn)6(µ3-O)6(C6H9O2)6] is as follows: Figure 1 As shown (for clarity, Figure 1 (Hydrogen atoms are omitted in the text), and the crystal parameters are shown in Table 1. (2) Characterization analysis of cluster properties

[0025] like Figure 2 As shown, thermal analysis tests indicate that the organotin clusters possess excellent thermal stability. Solubility test: A comparative solubility experiment was conducted on the prepared pure hexanuclear selenium drum-type organotin oxide clusters modified with cycloalkyl carboxylic acid ligands. The hexanuclear selenium drum-type organotin oxide clusters modified with cycloalkyl carboxylic acid ligands are soluble in most commonly used laboratory organic solvents, such as dichloromethane, trichloromethane, toluene, xylene, and alkane solvents like 1,2-dibromoethane, but insoluble in water, methanol, N,N-dimethylformamide, N,N-diethylformamide, propylene glycol monomethyl ether acetate, and other solvents.

[0026] Table 1: Crystal parameters of the hexanuclear selenium drum-shaped organotin oxide clusters modified with cycloalkyl carboxylic acid ligands obtained in Examples 1 and 2 Experimental Example 1: (1) A negative photoresist composition formulation and corresponding thin film preparation conditions

[0027] The hexanuclear selenium drum-type organotin oxide cluster compound modified with cycloalkyl carboxylic acid ligands obtained in Example 2 was dissolved in chloroform to prepare a solution with a mass concentration of 15 mg / mL. The solution was filtered through a microporous filter with a pore size of 0.22 μm to obtain a spin-coating solution. Spin-coating was performed on a silicon substrate under the following conditions: homogenization at 1000 rpm for 5 s and spin-coating at 3000 rpm for 30 s. (2) Verification of the patterning performance of the photoresist composition

[0028] The photoresist composition film prepared above was exposed on an electron beam exposure machine at an exposure dose of 30 µC / cm.2 After exposure, the exposed substrate is overdeveloped using a developer solution containing chloroform. The development time is 30-180 seconds. The resulting stripe pattern has a resolution of approximately 50 nm. Figure 4 As shown.

[0029] The above description is merely a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A hexanuclear selenium drum-shaped organotin oxide cluster compound modified with a cycloalkyl carboxylic acid ligand, characterized in that: The hexanuclear selenium drum-shaped organotin oxide cluster modified with the cycloalkyl carboxylic acid ligand is a zero-dimensional cluster. The organotin oxide core is arranged in a selenium drum shape. The cluster contains six organotin atoms, and the outer ligand is a cycloalkyl carboxylic acid ligand. The general chemical formula of the hexanuclear selenium drum-shaped organotin oxide cluster modified with the cycloalkyl carboxylic acid ligand is [(R1Sn)6(µ3-O)6L6]; wherein, R1 is selected from one of C1-C8 alkyl, C1-C6 alkenyl, C1-C6 alkynyl, phenyl, benzoenyl, benzoynyl or benzyl; L is a cycloalkyl carboxylic acid ligand; µ3 refers to the coordinating atom connected to three metals.

2. The hexanuclear selenium drum-type organotin oxide cluster compound modified with cycloalkyl carboxylic acid ligands as described in claim 1, characterized in that, The cycloalkylcarboxylic acid ligand is selected from one of the following structures: 。 3. A method for preparing a hexanuclear selenium drum-type organotin oxide cluster compound modified with a cycloalkyl carboxylic acid ligand as described in any one of claims 1-2, characterized in that, Includes the following steps: S1. Mix the organotin precursor, cycloalkyl carboxylic acid ligand and organic solvent uniformly in a molar ratio of 1: (0.1-50): (1-500); S2. After mixing thoroughly, sonicate for 10 min and then heat under reflux. S3. The clear liquid obtained after heating and reflux reaction is subjected to vacuum distillation to obtain a white or pale yellow solid powder. The powder is then volatilized and recrystallized in an organic solvent to obtain a hexanuclear selenium drum-shaped organotin oxide cluster modified with cycloalkyl carboxylic acid ligands.

4. The method for preparing the hexanuclear selenium drum-shaped organotin oxide cluster modified with cycloalkyl carboxylic acid ligands as described in claim 3, characterized in that: In step S1, the organotin precursor is one of C1-C8 alkyltin compounds, C1-C6 alkenyltin compounds, C1-C6 alkynyltin compounds, phenyltin compounds, benzo-alkenyltin compounds, benzo-alkynyltin compounds, or benzyltin compounds.

5. The method for preparing the hexanuclear selenium drum-shaped organotin oxide cluster modified with cycloalkyl carboxylic acid ligands as described in claim 3, characterized in that: In steps S1 and S3, the organic solvent is one or more of methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, ethylene glycol, n-pentanol, isopentanol, 1,2-propanediol, 1,3-propanediol, toluene, n-hexane, n-heptane, n-octane, isohexane, isooxane, isooctane, cyclohexane, cyclopentane, petroleum ether, dichloromethane, chloroform, 1,2-dichloroethane, carbon tetrachloride, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, formamide, or deionized water.

6. The method for preparing the hexanuclear selenium drum-shaped organotin oxide cluster modified with cycloalkyl carboxylic acid ligands as described in claim 3, characterized in that: In step S2, the reaction temperature of the heating reflux reaction is 40-120 °C, and the reaction time is 2-72 h.

7. The application of a hexanuclear selenium drum-type organotin oxide cluster modified with a cycloalkyl carboxylic acid ligand as described in any one of claims 1 or 2, characterized in that: The hexanuclear selenium drum-type organotin oxide clusters modified with cycloalkyl carboxylic acid ligands are used to prepare photoresist compositions and applied in the field of photolithography.

8. The application of the hexanuclear selenium drum-type organotin oxide cluster compound modified with cycloalkyl carboxylic acid ligands as described in claim 7, characterized in that: The photoresist composition is a negative photoresist, consisting of a hexanuclear selenium drum-type organotin oxide cluster modified with the cycloalkyl carboxylic acid ligand and a photoresist solvent; the hexanuclear selenium drum-type organotin oxide cluster modified with the cycloalkyl carboxylic acid ligand accounts for 0.1-5 wt% of the total mass of the photoresist composition, with the remainder being the photoresist solvent.

9. The application of the hexanuclear selenium drum-type organotin oxide cluster compound modified with cycloalkyl carboxylic acid ligands as described in claim 8, characterized in that: The photoresist solvent is one or more of the following: tetrahydrofuran, 1,4-dioxane, benzene, toluene, p-xylene, o-xylene, m-xylene, mesitylene, chlorobenzene, fluorobenzene, propylene glycol monomethyl ether acetate, propylene glycol ethyl ether, ethylene glycol methyl ether acetate, ethyl acetate, butyl acetate, chloroform, dichloromethane, methanol, ethanol, 2-ethoxyethanol, 1,2-dichloroethane, N,N-dimethylformamide, or N,N-dimethylacetamide.

10. The application of the hexanuclear selenium drum-type organotin oxide cluster compound modified with cycloalkyl carboxylic acid ligands as described in claim 8, characterized in that, The patterning method of the photoresist composition includes: dissolving the hexanuclear selenium drum-type organotin oxide cluster modified with the cycloalkyl carboxylic acid ligand in a photoresist solvent, filtering, and spin-coating onto a substrate to form a photoresist film; subjecting the photoresist film to electron beam or radiation exposure treatment; contacting the exposed photoresist film with a developer at room temperature for 1-300 s to complete development and achieve patterning; the developer is one or more of the following: n-propanol, isopropanol, n-butanol, isobutanol, toluene, o-xylene, m-xylene, p-xylene, mesitylene, 4-methyl-2-pentanol, 4-methyl-2-pentanone, methyl ethyl ketone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol methyl ether acetate, 2-butanone, 2-heptanone, ethanol, 2-ethoxyethanol, N,N-dimethylformamide, N,N-diethylformamide, acetonitrile, ultrapure water, n-hexane, or cyclohexane; the patterned photoresist film is used for 248 nm photolithography, 193 nm photolithography, and other photolithography methods. nm lithography, extreme ultraviolet lithography, super extreme ultraviolet lithography, nanoimprint lithography, or electron beam lithography.

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