Heterojunction type crystalline metal oxo-cluster patterning material, preparation method and application thereof

Abstract

The application belongs to the technical field of inorganic chemistry, material chemistry and photoresist, and particularly relates to a kind of heterojunction type crystalline metal oxygen cluster patterning material and its preparation method and application, the patterning material is molecular heterojunction, the molecular heterojunction contains metal ions with radiation sensitive ligand, the metal ions are radiation sensitive elements, and the radiation sensitive ligand refers to a structure containing double bond, triple bond, epoxy propane or halogenated hydrocarbon.The resolution of the pattern formed by the coating formed by the spin coating of the patterning material dissolved in solvent and subjected to exposure and development can reach 100 nm, or even 50 nm.

Description

Technical Field

[0001] This invention belongs to the fields of inorganic chemistry, materials chemistry, and photoresist technology, specifically relating to a heterojunction-type crystalline metal-oxygen cluster patterned material, its preparation method, and its application, particularly an organic-inorganic hybrid {Zr3Sn} 12 Heterojunction-type crystalline tin-zirconium oxide cluster patterned materials, their preparation methods, and applications. Background Technology

[0002] Due to their unique interfacial properties and bandgap modulation advantages, heterojunction structures are widely used in various fields, including photocatalysis, gas sensing, humidity sensing, photodetectors, and semiconductor device performance enhancement. Heterojunction structures can effectively promote the exposure of active sites, optimize carrier transport efficiency, and improve overall performance through synergistic effects between different components. These advantages make heterojunctions one of the key materials for improving the performance of various devices.

[0003] However, although heterojunctions have shown significant application potential in many cutting-edge fields, their application in photolithography is mainly used to fabricate heterojunction photovoltaic cells, while research on other applications is almost non-existent.

[0004] Heterojunctions are typically complex to synthesize, and their precise interface structures and compositions are often unclear, making it challenging to clearly reveal their working mechanisms at the molecular level. In contrast, molecular heterojunctions have attracted increasing attention due to their clear interfaces and well-defined, tunable structural and compositional information. Molecular heterojunctions are a class of crystalline materials with well-defined and periodic structures and tunable assembly patterns. They are composed of different building blocks assembled together through coordination or covalent bonds. These heterojunctions, with their precise structures and compositions, not only provide an ideal platform for exploring their intrinsic mechanisms but also open up new avenues for the development of related technologies.

[0005] With the development of photolithography technology, exploring the potential of molecular heterostructures in photolithography and controlling the photolithography mechanism and performance may bring new breakthroughs to semiconductor manufacturing. Summary of the Invention

[0006] This invention provides a heterojunction-type crystalline metal oxide cluster patterned material, its preparation method, and its application.

[0007] The present invention provides a patterned material, wherein the patterned material is a molecular heterojunction, the molecular heterojunction contains metal ions with radiation-sensitive ligands, and the metal ions are radiation-sensitive elements.

[0008] According to an embodiment of the present invention, the radiation-sensitive ligand refers to a structure containing a double bond, a triple bond, propylene oxide, or a halogenated hydrocarbon, preferably the halogenated hydrocarbon is selected from trifluoromethyl.

[0009] According to an embodiment of the present invention, after radiation exposure, the molecular heterojunction exhibits a significant difference in solubility in the developer between the exposed and unexposed molecular heterojunctions. The molecular heterojunction contains metal ions with radiation-sensitive ligands. Under radiation conditions, the material in the irradiated region undergoes structural changes and its solubility changes, while the structure of the unirradiated region remains unchanged. The molecular heterojunctions in the irradiated and unirradiated regions have different dissolution rates, thereby producing a patterned structure.

[0010] According to an embodiment of the present invention, the molecular structure of the molecular heterojunction is shown in formula (I):

[0011] (RA) x B 15-x O y (L) z Formula (I);

[0012] Where x≥1, x+y+z≤120;

[0013] R is selected from one or more of H, C1-20 alkyl, C2-20 alkenyl, C2-20 alkynyl, and C6-20 aryl;

[0014] L is selected from organic or inorganic ligands that can coordinate with Zr and Sn;

[0015] At least one R or L contains a radiation-sensitive ligand, and the A and B are independently selected from different radiation-sensitive elements.

[0016] According to an embodiment of the present invention, the radiation-sensitive element is selected from one or a combination of several of Sn, Zr, Na, Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Cs, Ba, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, and Po.

[0017] According to an embodiment of the present invention, x = 12, y = 8, z = 12, and the molecular structural formula is (RA). 12 B3O 18 (L) 12 .

[0018] According to an embodiment of the present invention, A is Sn, and Sn may be partially replaced by one or more other radiation-sensitive elements.

[0019] According to an embodiment of the present invention, B is Zr, and Zr may be partially replaced by one or more other radiation-sensitive elements.

[0020] According to an embodiment of the present invention, the (RA) 12 B3O 18 (L) 12 In the heterojunction, the highest occupied molecular orbitals (HOMOs) are distributed on the R groups connected to the {A3O4} units, while the lowest unoccupied molecular orbitals (LUMOs) are concentrated on the ligands L coordinated to the {B6O7} units.

[0021] According to embodiments of the present invention, R is selected from H, C1-10 alkyl, C2-10 alkenyl, C2-10 alkynyl, and C6-10 aryl.

[0022] According to embodiments of the present invention, R is selected from H, C1-6 alkyl, C2-6 alkenyl, C2-6 alkynyl, and C6-10 aryl.

[0023] According to embodiments of the present invention, R is selected from H, C1-4 alkyl, C2-4 alkenyl, C2-4 alkynyl, and C6-10 aryl.

[0024] According to embodiments of the present invention, R is selected from H, methyl, ethyl, propyl, butyl, vinyl, methacryl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, naphthyl, etc.

[0025] According to an embodiment of the present invention, the H in R can be replaced by one or more groups, the substituting groups being selected from alkyl, alkenyl, alkyne, halogen, and radiation-sensitive functional groups, for example selected from radiation-sensitive functional groups, which are selected from groups containing one or more of double bonds, triple bonds, propylene oxide, and halogenated hydrocarbons such as trifluoromethyl.

[0026] According to embodiments of the present invention, L is selected from organic or inorganic ligands containing, but not limited to, one or more of C, O, S, Se, Te, N, P, As or Sb as coordinating atoms.

[0027] According to embodiments of the present invention, L is selected from one or more ligands such as carboxylic acids, alcohols, thiols, phenols, sulfonic acids, phosphoric acid / phosphonic acid, phosphine, arsenic acid, nitriles, alkanolamines, pyridines, pyrazoles, imidazoles, piperazines, pyrazines, SO4 ions, etc., for example, a carboxylic acid ligand.

[0028] According to an embodiment of the present invention, L is selected from the same or different ligands, and when different ligands are selected, the different ligands can exist in any proportion.

[0029] According to an embodiment of the present invention, when the L contains H, the H can be replaced by one or more groups, the substituting groups being selected from alkyl, alkenyl, alkynyl, halogen, haloalkyl, haloalkenyl, haloalkynyl, hydroxyl, phenolic, sulfonate, etc., for example selected from radiation-sensitive functional groups, the radiation-sensitive functional groups being selected from one or more of double bonds, triple bonds, propylene oxide, and halogenated hydrocarbons, the halogenated hydrocarbon being, for example, trifluoromethyl.

[0030] According to an embodiment of the present invention, the ratio of metal ions A and B in the material can be adjusted to improve sensitivity, line edge roughness, and resolution.

[0031] According to an embodiment of the present invention, the functional groups introduced in R and L can adjust properties such as light absorption capacity, solubility, and film-forming properties, thereby affecting film thickness, film roughness, resolution, film adhesion, and corrosion resistance.

[0032] According to an embodiment of the present invention, the radiation-sensitive functional groups introduced in R and L can enhance their photosensitivity, improve line edge roughness, and increase resolution.

[0033] According to an embodiment of the present invention, the (RA) 12 B3O 18 (L) 12 For (RSn) 12 Zr3O 18 (L) 12 .

[0034] According to an embodiment of the present invention, (RSn) 12 Zr3O 18 (L) 12 It has a "sandwich" type intramolecular heterojunction, which is formed by the connection of cap-shaped {Sn6O7} units and {Zr3O4} and {Sn3O4} units through bridging oxygen, with 12 ligands to form a complete zirconium tin oxide cluster.

[0035] According to an embodiment of the present invention, the (RSn) 12 Zr3O 18 (L) 12 It is one or more of compounds 1 to 3:

[0036] Compound 1: ( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA-mCH3) 12 ;

[0037] Compound 2: ( n BuSn) 12 Zr3(μ3-O) 15(μ4-O)3(BA) 12 ;

[0038] Compound 3: ( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA-oF) 12 ;

[0039] Wherein, BA represents benzoate, with the molecular formula C7H5O2; BA-mCH3 represents m-methylbenzoate, with the molecular formula C8H7O2; and BA-oF represents p-fluorobenzoate, with the molecular formula C7H4O2F.

[0040] According to an embodiment of the present invention, the crystal parameters of compound 1 are: trigonal crystal system, space group R3c, and cell parameter a. b is c is α is 90°, β is 90°, γ is 120°, and V is...

[0041] According to an embodiment of the present invention, compound 1 has essentially the following properties: Figure 2 The diagram shown is a structural schematic.

[0042] According to an embodiment of the present invention, compound 1 has essentially the following properties: Figure 5 The infrared spectrum shown.

[0043] According to an embodiment of the present invention, compound 1 has essentially the following properties: Figure 8 The EDX graph shown.

[0044] According to an embodiment of the present invention, the crystal parameters of compound 2 are: trigonal crystal system, space group R3c, and cell parameter a. b is c is α is 90°, β is 90°, γ is 120°, and V is...

[0045] According to an embodiment of the present invention, compound 2 has essentially the following properties: Figure 3 The diagram shown is a structural schematic.

[0046] According to an embodiment of the present invention, compound 2 has essentially the following properties: Figure 6 The infrared spectrum shown.

[0047] According to an embodiment of the present invention, compound 2 has essentially the following properties: Figure 9 The EDX graph shown.

[0048] According to an embodiment of the present invention, the crystal parameters of compound 3 are: monoclinic crystal system, space group Cc, and cell parameter a. b is c is α is 90°, β is 94.244(6)°, γ is 90°,

[0049] According to an embodiment of the present invention, compound 3 has essentially the following properties: Figure 4 The diagram shown is a structural schematic.

[0050] According to an embodiment of the present invention, compound 3 has essentially the following properties: Figure 7 The infrared spectrum shown.

[0051] According to an embodiment of the present invention, compound 3 has essentially the following properties: Figure 10 The EDX graph shown.

[0052] This invention also provides a method for preparing the above-mentioned patterned material, the method comprising the following steps:

[0053] The patterned material is prepared by a solvothermal synthesis method using a tin source, a zirconium source, a ligand, and a solvent.

[0054] According to an embodiment of the present invention, the tin source is selected from any of the following: butylstannic acid, dibutyltin chloride, dibutylstannic acid, phenyltin chloride, etc.

[0055] According to an embodiment of the present invention, the zirconium source is selected from any of the following: zirconium oxychloride, zirconium n-butoxide, zirconium n-propoxide, etc.

[0056] According to an embodiment of the present invention, the ligand source is selected from any one of the following: benzoic acid, m-methylbenzoic acid, o-fluorobenzoate, and their derivatives.

[0057] According to an embodiment of the present invention, the solvothermal synthesis method involves heating the reaction in a solvent.

[0058] According to an embodiment of the present invention, the solvent is selected from alcohols, phenols, mixed alcohols, and mixed alcohol-phenol solvents.

[0059] According to an embodiment of the present invention, the alcohol is any one of C1-20 alcohols (e.g., C1-10 alcohols, C1-6 alcohols, etc.) or a mixture thereof in any proportion. Preferably, the alcohol is selected from any one of methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, n-pentanol, isopentanol, neopentanol, hexanol, heptanol, octanol, decanol, etc. or a mixture thereof in any proportion. More preferably, the alcohol is one or more of methanol, ethanol, n-propanol, isopropanol, and n-butanol.

[0060] According to an embodiment of the present invention, the temperature of the solvothermal reaction is 40–200°C, preferably 60–120°C, and more preferably 60–100°C.

[0061] According to an embodiment of the present invention, the solvothermal reaction takes 1 to 14 days, and preferably the temperature of the solvothermal reaction is 3 to 7 days.

[0062] According to an embodiment of the present invention, the solvothermal container can be carried out in a sealed glass bottle or a polytetrafluoroethylene pressure reactor.

[0063] According to an embodiment of the present invention, the preparation method further includes a purification step of the product.

[0064] According to an embodiment of the present invention, the purification step includes: washing, separating, and air-drying the product after reaction at room temperature.

[0065] According to an embodiment of the present invention, the cleaning step uses an alcohol solvent, and the alcohol solvent used for cleaning can be the same as or different from the alcohol added in the reaction.

[0066] The present invention also provides a patterning composition comprising the above-described patterning material.

[0067] According to an embodiment of the present invention, the patterned composition further includes any one or more of a solvent, a stabilizer, a photosensitizer, etc.

[0068] The present invention also provides a method for forming a pattern, the method comprising the following steps:

[0069] 1) Dissolve the above patterned material in a solvent, filter, and attach it to the substrate to form a patterned coating;

[0070] 2) The patterned coating is subjected to radiation exposure treatment;

[0071] 3) The exposed coating comes into contact with the developer to form a patterned coating material.

[0072] According to an embodiment of the present invention, the substrate has a hydrophilic or hydrophobic surface.

[0073] According to an embodiment of the present invention, the solvent is a solvent capable of dissolving the above-mentioned patterned material; preferably, the solvent includes, but is not limited to, any one of solvents such as carboxylic acid esters, alcohols having 1-20 carbon atoms, halogenated hydrocarbons, aromatic hydrocarbons, amides, ketones, and water, or a mixture thereof in any proportion; more preferably, the solvent is one or more of propylene glycol methyl ether acetate, ethyl lactate, isoethyl acetate, methanol, isopropanol, heptanol, 2-heptanone, N,N-dimethylformamide, and water.

[0074] According to embodiments of the present invention, the carboxylic acid esters include, but are not limited to, one or more of propylene glycol methyl ether formate, ethylene glycol ethyl ether formate, propylene glycol ethyl ether formate, ethylene glycol methyl ether acetate, propylene glycol methyl ether acetate, and carboxylic acid ether esters; preferably, the carboxylic acid esters include, but are not limited to, one or more of ethyl formate, ethyl acetate, n-butyl acetate, ethyl lactate, n-propyl lactate, isopropyl lactate, and carboxylic acid alkane esters.

[0075] According to embodiments of the present invention, alcohols with 1-20 carbon atoms include methanol, ethanol, isopropanol, n-butanol, cyclohexanol, heptanol, etc.

[0076] According to an embodiment of the present invention, the halogenated hydrocarbons include, but are not limited to, dichloromethane, trichloromethane, etc.

[0077] According to embodiments of the present invention, the aromatic hydrocarbons include, but are not limited to, benzene, toluene, xylene, etc.

[0078] According to embodiments of the present invention, the amides include, but are not limited to, N,N-dimethylformamide, N,N-dimethylacetamide, etc.

[0079] According to embodiments of the present invention, the ketones include, but are not limited to, acetone, heptanone, etc.

[0080] According to an embodiment of the present invention, the concentration of the material in the solvent is about 5 mg / mL to 30 mg / mL.

[0081] According to an embodiment of the present invention, after radiation exposure, the patterned material exhibits a significant difference in solubility in the developer between the exposed and unexposed coating areas. The patterned coating material contains metal ions with radiation-sensitive ligands before irradiation. The radiation alters the properties of the coating material, resulting in different dissolution rates between the irradiated and unirradiated areas, thereby producing a patterned structure.

[0082] According to an embodiment of the present invention, the radiation is selected from electron beams and light sources of ultraviolet, deep ultraviolet, extreme ultraviolet, or shorter wavelengths.

[0083] According to an embodiment of the present invention, the developer is selected from at least one of tetramethylammonium hydroxide (TMAH) aqueous solution, heptanone, methanol, isopropanol, heptanol, N,N-dimethylformamide, propylene glycol methyl ether acetate, ethyl lactate, water, benzene, toluene, dichloromethane, etc.

[0084] According to an embodiment of the present invention, the patterning material has different dissolution rates before and after irradiation after being immersed in the developing solution.

[0085] According to an embodiment of the present invention, the concentration of the tetramethylammonium hydroxide (TMAH) aqueous solution is 0.5% to 20%, preferably 5% to 10%.

[0086] According to an embodiment of the present invention, the developing solution is in contact with the patterned coating for no more than 10 minutes.

[0087] The present invention also provides the application of the above-mentioned patterning material or patterning composition in the preparation of photoresist; preferably, electron beam photoresist, DUV photoresist, EUV photoresist and other photoresists.

[0088] Beneficial effects

[0089] 1) The organic-inorganic hybrid metal-oxygen cluster patterned material of this invention has a structure of (RA). 12 B3O 18 (L) 12 The material has a classic "sandwich" type intramolecular heterojunction, which is formed by cap-shaped {Sn6O7} units and {Zr3O4} and {Sn3O4} units connected by bridging oxygen, plus 12 ligands to form a complete zirconium tin oxide cluster. The patterned material of the present invention is dissolved in a solvent and the coating is formed by spin coating. After exposure and development, the pattern formed can achieve a resolution of 100nm or even 50nm.

[0090] 2) The present invention can improve the performance of patterned materials by adjusting the type and composition of ligands and radiation-responsive metals. For example, by introducing functional groups into the ligands, adjusting the type and ratio of different metals, and controlling the type and quantity of ligands, the solubility, film-forming properties, light absorption capacity, photosensitivity, improvement of line edge roughness, and improvement of resolution of the patterned materials can be further enhanced, thereby controlling the photolithography performance of the patterned materials.

[0091] 3) This invention constructs a heterojunction interface in tin-zirconium oxide clusters, adjusts the electronic structure of the clusters, and combines a ligand regulation strategy to regulate the photolithography mechanism and improve the performance of tin-zirconium oxide clusters. The crystalline tin-zirconium oxide cluster compound in this invention has the characteristics of accurate structural information, high solution stability, and excellent film-forming properties. Moreover, the raw materials are simple and readily available, the crystal material synthesis method is simple, the yield is high, and it can be prepared in large quantities, making it a highly promising candidate material for photoresist.

[0092] 4) Compound 3 in this invention ( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA-oF) 12 Among them, fluorine in the ligand o-fluorobenzoic acid has a higher absorption capacity for EUV, thus exhibiting the highest patterning sensitivity. Specifically, compounds 1-3 require energies of 75 μC / cm² to achieve 50 nm line resolution. 2 100μC / cm 2 25μC / cm 2 .

[0093] 5) This invention modulates the electronic structure of compounds by constructing heterojunctions inside metal-oxygen clusters. Specifically, the highest occupied molecular orbitals (HOMOs) are mainly distributed on the butyl chain connected to the {Sn3O4} unit in the heterojunction, while the lowest unoccupied molecular orbitals (LUMOs) are concentrated on the carboxylic acid ligands coordinated to the {Sn6O7} unit in the heterojunction. The distribution of HOMO-LUMO orbitals provides strong evidence for potential photolithography mechanisms.

[0094] 6) This invention modulates the patterning mechanism by constructing heterojunctions within metal-oxygen clusters to control the electronic structure of compounds. The highest occupied molecular orbital (HOMO) loses electrons through ionization, resulting in the breakage of the butyl chain on the {Sn3O4} unit in the heterojunction. The lowest unoccupied molecular orbital (LUMO) dissociates the carboxylic acid ligand coordinated to the {Sn6O7} unit in the heterojunction through dissociative electron attachment. Both mechanisms can induce changes in the compound structure, thereby causing dissolution changes and pattern formation.

[0095] 7) This invention constructs a heterojunction within a metal-oxygen cluster and further modulates the electronic structure and composition of the heterojunction through a ligand modulation strategy. Benzoic acid, m-methylbenzoic acid, and o-fluorobenzoic acid are used for modulation, respectively, resulting in differences in the final photolithography performance, such as photolithography sensitivity. The compound modified with o-fluorobenzoic acid exhibits the highest photolithography sensitivity at 25 μC / cm². 2At a specific exposure dose, patterning is achieved by exposure and development, resulting in line widths of 50 nm. However, compounds modified with benzoic acid and m-methylbenzoic acid require higher exposure doses, ranging from 75 to 100 μC / cm. 2 Only by using exposure and development at a specific dosage to form patterns can a line width of 50nm be obtained. Attached Figure Description

[0096] Figure 1 This is a sandwich heterojunction (RSn) formed by cap-shaped {Sn6O7} units and {Zr3O4} and {Sn3O4} units connected by bridging oxygen. 12 Zr3O 18 A structural diagram.

[0097] Figure 2 for( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA-mCH3) 12 A structural diagram.

[0098] Figure 3 for( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA) 12 A structural diagram.

[0099] Figure 4 for( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA-oF) 12 A structural diagram.

[0100] Figure 5 for( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA-mCH3) 12 The infrared spectrum.

[0101] Figure 6 for( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA) 12 The infrared spectrum.

[0102] Figure 7 for( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA-oF)12 The infrared spectrum.

[0103] Figure 8 for( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA-mCH3) 12 Energy dispersive X-ray spectrum (EDX).

[0104] Figure 9 for( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA) 12 Energy dispersive X-ray spectrum (EDX).

[0105] Figure 10 for( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA-oF) 12 Energy dispersive X-ray spectrum (EDX).

[0106] Figure 11 for( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA-mCH3) 12 The material at 75 μC / cm 2 After patterning is formed by exposure and development at a certain dose, the line width of the exposure is characterized by SEM as 50 nm.

[0107] Figure 12 for( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA) 12 The material is at 100 μC / cm 2 After patterning is formed by exposure and development at a certain dose, the line width of the exposure is characterized by SEM as 50 nm.

[0108] Figure 13 for( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA-oF) 12 The material at 25 μC / cm 2 After patterning is formed by exposure and development at a certain dose, the line width of the exposure is characterized by SEM as 50 nm.

[0109] Figure 14 for(n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA-mCH3) 12 The highest occupied molecular orbitals (HOMOs) are distributed on the butyl chain connected to the {Sn3O4} unit in the heterostructure.

[0110] Figure 15 for( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA-mCH3) 12 The lowest unoccupied molecular orbitals (LUMOs) are concentrated on the carboxylic acid ligands coordinated with the {Sn6O7} unit in the heterostructure.

[0111] To make the structure clearer, some oxygen, carbon, nitrogen, and hydrogen atoms have been omitted in the diagram. Detailed Implementation

[0112] The following detailed description, in conjunction with specific embodiments, further illustrates the heterojunction-type crystalline metal oxide cluster patterned material, its preparation method, and its applications according to the present invention. It should be understood that the following embodiments are merely illustrative and explanatory of the present invention and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0113] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0114] Example 1: Preparation and Characterization of Hybrid Organic-Inorganic Metal-Oxide Cluster Patterned Materials

[0115] 1.( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA-mCH3) 12 Preparation of (BA-mCH3 represents m-methylbenzoate, molecular formula C8H7O2)

[0116] In a 20 mL glass reaction flask, zirconium propoxide (0.32 mmol, 100 μL), butylstannic acid (0.48 mmol, 100 mg), and m-methylbenzoic acid (1 mmol, 136 mg) were mixed with methanol (2.5 mL) and isopropanol (2.5 mL), and 100 μL of formic acid was added. The flask was then capped and heated to 80 °C. After 3 days, the mixture was cooled to room temperature, and crystals precipitated. The yield was 20%–30%. The crystals were separated and washed with methanol to obtain (…). n BuSn) 12Zr3(μ3-O) 15 (μ4-O)3(BA-mCH3) 12 Crystal.

[0117] ( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA-mCH3) 12 The crystallographic data are as follows: crystal system is trigonal, space group is R3c, and cell parameter a is... b is c is α is 90°, β is 90°, γ is 120°, and V is...

[0118] 2.( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA) 12 Preparation of (BA represents benzoate, molecular formula C7H5O2)

[0119] In a 20 mL glass reaction flask, zirconium propoxide (0.32 mmol, 100 μL), butylstannic acid (0.48 mmol, 100 mg), benzoic acid (1 mmol, 122 mg), methanol (2.5 mL), and ethanol (2.5 mL) were mixed. 100 μL of formic acid was added, the flask was tightened, and the mixture was heated to 100 °C. After 4 days, the mixture was cooled to room temperature, and crystals precipitated. The yield was 20%–30%. The crystals were separated and washed with methanol to obtain (…). n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA) 12 Crystal.

[0120] ( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA) 12 The crystallographic data are as follows: crystal system is trigonal, space group is R3c, and cell parameter a is... b is c is α is 90°, β is 90°, γ is 120°, and V is...

[0121] 3.( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA-oF) 12Preparation of crystals (BA-oF represents p-fluorobenzoate, molecular formula C7H4O2F)

[0122] In a 20 mL glass reaction flask, zirconium propoxide (0.32 mmol, 100 μL), butylstannic acid (0.48 mmol, 100 mg), o-fluorobenzoic acid (1 mmol, 140 mg), and methanol (5 mL) were mixed, and 100 μL of formic acid was added. The flask was then capped and heated to 60 °C. After 7 days, the mixture was cooled to room temperature, and crystals precipitated. The yield was 20%–30%. The crystals were separated and washed with methanol to obtain (…). n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA-oF) 12 Crystal.

[0123] ( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA-oF) 12 The crystallographic data are as follows: crystal system is monoclinic, space group is Cc, and cell parameter a is... b is c is α is 90°, β is 94.244(6)°, γ is 90°,

[0124] (RSn) 12 Zr3O 18 (L) 12 The foundation of the structure is as follows Figure 1 The Sn9Zr3O shown 15 Sn9Zr3O 15 There exists a classic "sandwich" type intramolecular heterojunction, which is formed by cap-shaped {Sn6O7} units and {Zr3O4} and {Sn3O4} units connected by bridging oxygen (RSn). 12 Zr3O 18 (L) 12 The above-mentioned "sandwich" structure of Sn is modified with 12 ligands to form a complete zirconium tin oxide cluster. n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA-mCH3) 12 、( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA) 12 、( n BuSn) 12 Zr3(μ3-O)15 (μ4-O)3(BA-oF) 12 Structural diagram as follows Figure 2-4 As shown,

[0125] ( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA-mCH3) 12 、( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA) 12 、( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA-oF) 12 Infrared spectrum as shown Figure 5-7 As shown, the energy-dispersive X-ray spectrum (EDX) is as follows: Figure 8-10 As shown, patterned lines are as follows Figure 11-13 .

[0126] Figure 5 for( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA-mCH3) 12 Infrared spectrum, 800–400 cm⁻¹ –1 The peak originates from the vibration of MOM (M: Zr or Sn), at 1550 cm⁻¹. –1 The vibrational peak originates from the asymmetric stretching vibration of the carboxyl group, at 1390 cm⁻¹. –1 The vibrational peak originates from the symmetric stretching vibration of the carboxyl group, and the presence of the characteristic peak of the carboxyl group proves that m-methylbenzoic acid has been successfully coordinated to the metal-oxygen cluster nucleus.

[0127] Figure 6 for( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA) 12 Infrared spectrum, 800–400 cm⁻¹ –1 The peak originates from the vibration of MOM (M: Zr or Sn), at 1550 cm⁻¹. –1 The vibrational peak originates from the asymmetric stretching vibration of the carboxyl group, at 1390 cm⁻¹. –1 The vibrational peak originates from the symmetric stretching vibration of the carboxyl group, and the presence of the characteristic peak of the carboxyl group proves that benzoic acid has been successfully coordinated to the metal-oxygen cluster nucleus.

[0128] Figure 7 for( nBuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA-oF) 12 Infrared spectrum, 800–400 cm⁻¹ –1 The peak originates from the vibration of MOM (M: Zr or Sn), 1230 cm⁻¹ –1 The vibrational peak is attributed to the C–F bond on the benzene ring, at 1550 cm⁻¹. –1 The vibrational peak originates from the asymmetric stretching vibration of the carboxyl group, at 1390 cm⁻¹. –1 The vibrational peak originates from the symmetric stretching vibration of the carboxyl group, and the presence of the characteristic peak of the carboxyl group proves that o-fluorobenzoic acid has been successfully coordinated to the metal-oxygen cluster nucleus.

[0129] Figure 8 for( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA-mCH3) 12 Energy-dispersive X-ray spectroscopy (EDX) confirmed the presence of C, O, Zr, and Sn elements in the compound, but EDX could not detect the very light hydrogen element.

[0130] Figure 9 for( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA) 12 Energy-dispersive X-ray spectroscopy (EDX) confirmed the presence of C, O, Zr, and Sn elements in the compound, but EDX could not detect the very light hydrogen element.

[0131] Figure 10 for( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA-oF) 12 Energy-dispersive X-ray spectroscopy (EDX) confirmed the presence of C, O, F, Zr, and Sn elements in the compound, but EDX could not detect the very light hydrogen element.

[0132] Figure 11 for( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA-mCH3) 12 The material at 75 μC / cm 2 After patterning is formed by exposure and development at a certain dose, the line width of the exposure is characterized by SEM as 50 nm.

[0133] Figure 12 for(n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA) 12 The material is at 100 μC / cm 2 After patterning is formed by exposure and development at a certain dose, the line width of the exposure is characterized by SEM as 50 nm.

[0134] Figure 13 for( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA-oF) 12 The material at 25 μC / cm 2 After patterning is formed by exposure and development at a certain dose, the line width of the exposure is characterized by SEM as 50 nm.

[0135] ( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA-mCH3) 12 、( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA) 12 、( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA-oF) 12 The HOMO and LUMO orbital distributions are as follows Figure 14-15 As shown, the highest occupied molecular orbital (HOMO) is mainly distributed on the butyl chain connected to the {Sn3O4} unit in the heterojunction, while the lowest unoccupied molecular orbital (LUMO) is concentrated on the carboxylic acid ligand coordinated to the {Sn6O7} unit in the heterojunction. Thus, it can be seen that the electronic structure of the compound can be controlled by constructing a heterojunction inside the metal-oxygen cluster.

[0136] Example 2

[0137] 1. Silicon wafer processing

[0138] The silicon wafer is cleaned in an acidic or alkaline solution for 15–30 minutes, then rinsed with deionized water, followed by isopropanol. Before use, the surface liquid is dried with an air gun to obtain the silicon substrate.

[0139] 2. Membrane preparation

[0140] Take 5-30 mg of the mixed organometallic oxygen cluster patterned material prepared in Example 1. n BuSn) 12Zr3(μ3-O) 15 (μ4-O)3(BA-mCH3) 12 、( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA) 12 or( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA-oF) 12 Dissolve the propylene glycol methyl ether acetate in 1 mL of solvent, filter the solution, take an appropriate amount of the filtered solution, and spin-coat it onto the surface of the treated silicon substrate to form a patterned material film.

[0141] 3. Exposure

[0142] When a patterned material film is selectively irradiated with an electron beam, a chemical change occurs in the irradiated area, altering its solubility. This means that the solubility of the exposed and unexposed areas of the patterned material film in the developing solution differs significantly, resulting in the formation of a pattern.

[0143] 4. Development

[0144] During the development process, a developing solution is used to contact the exposed film layer to dissolve and remove some of the patterned material. The dissolved portion can be either the exposed film layer or the unexposed film layer.

[0145] The developer used in this embodiment is a mixture of N,N-dimethylformamide or isopropanol and water (volume ratio range 10:1 to 1:10), and the development time is 5s to 120s.

[0146] 5. Pattern Representation

[0147] The pattern of the above-exposed and developed coating material was characterized using scanning electron microscopy (SEM), and the results are as follows: Figure 11-13 As shown.

[0148] The mixed organometallic oxide cluster patterning materials compounds 1-3 in Example 1, after being dissolved, filtered, spin-coated, and exposed and developed, can all form patterns with a resolution of 100nm or even 50nm.

[0149] The specific embodiments of the present invention have been described above by way of example. However, the scope of protection of the present invention is not limited to the above exemplary embodiments. Any modifications, equivalent substitutions, improvements, etc., made by those skilled in the art within the spirit and principles of the present invention should be included within the scope of protection of the claims of the present invention.

Claims

1. A patterned material, characterized in that, The patterned material is a molecular heterojunction, which contains metal ions with radiation-sensitive ligands. The metal ions are radiation-sensitive elements, and the radiation-sensitive ligands refer to structures containing double bonds, triple bonds, propylene oxide, or halogenated hydrocarbons.

2. The patterned material according to claim 1, characterized in that, The molecular structure of the molecular heterojunction is shown in formula (I): (RA) x B 15-x O y (L) z Formula (I); Where x≥1, x+y+z≤120; R is selected from one or more of H, C1-20 alkyl, C2-20 alkenyl, C2-20 alkynyl, and C6-20 aryl; L is selected from organic or inorganic ligands that can coordinate with Zr and Sn; At least one R or L contains a radiation-sensitive ligand, and the A and B are independently selected from different radiation-sensitive elements.

3. The patterned material according to claim 1, characterized in that, The radiation-sensitive element is selected from one or more of Sn, Zr, Na, Mg, Al, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Rb, Sr, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Cs, Ba, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Pb, Bi, and Po.

4. The patterned material according to claim 1, characterized in that, x = 12, y = 8, z = 12, and the molecular structure formula is (RA) 12 B3O 18 (L) 12 . Preferably, A is Sn, and Sn can be partially replaced by one or more other radiation-sensitive elements. Preferably, B is Zr, and Zr may be partially replaced by one or more other radiation-sensitive elements. Preferably, the (RA) 12 B3O 18 (L) 12 In the heterojunction, the highest occupied molecular orbitals (HOMOs) are distributed on the R groups connected to the {A3O4} units, while the lowest unoccupied molecular orbitals (LUMOs) are concentrated on the ligands L coordinated to the {B6O7} units. Preferably, L is selected from one or more ligands such as carboxylic acids, alcohols, thiols, phenols, sulfonic acids, phosphoric acid / phosphonic acid, phosphine, arsenic acid, nitriles, alkanolamines, pyridines, pyrazoles, imidazoles, piperazines, pyrazines, SO4 ions, etc.

5. The patterned material according to any one of claims 1-4, characterized in that, The (RA) 12 B3O 18 (L) 12 For (RSn) 12 Zr3O 18 (L) 12 . Preferably, (RSn) 12 Zr3O 18 (L) 12 It has a "sandwich" type intramolecular heterojunction, which is formed by the connection of cap-shaped {Sn6O7} units and {Zr3O4} and {Sn3O4} units through bridging oxygen, with 12 ligands to form a complete zirconium tin oxide cluster. Preferably, the (RSn) 12 Zr3O 18 (L) 12 It is one or more of compounds 1 to 3: Compound 1: ( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA-mCH3) 12 ; Compound 2: ( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA) 12 ; Compound 3:( n BuSn) 12 Zr3(μ3-O) 15 (μ4-O)3(BA-oF) 12 ; Wherein, BA represents benzoate, with the molecular formula C7H5O2; BA-mCH3 represents m-methylbenzoate, with the molecular formula C8H7O2; and BA-oF represents p-fluorobenzoate, with the molecular formula C7H4O2F.

6. The patterned material according to claim 5, characterized in that, The crystal parameters of compound 1 are: trigonal crystal system, space group R3c, and cell parameter a. c is α is 90°, β is 90°, γ is 120°, and V is... Preferably, the crystal parameters of compound 2 are: trigonal crystal system, space group R3c, and cell parameter a. c is α is 90°, β is 90°, γ is 120°, and V is... Preferably, the crystal parameters of compound 3 are: monoclinic crystal system, space group Cc, and cell parameter a. b is c is α is 90°, β is 94.244(6)°, γ is 90°, 7. A method for preparing the patterned material according to any one of claims 1-6, the method comprising the following steps: The patterned material is prepared by a solvothermal synthesis method using a tin source, a zirconium source, a ligand, and a solvent. Preferably, the temperature of the solvothermal reaction is 40–200°C, and more preferably, the temperature of the solvothermal reaction is 60–100°C. Preferably, the solvothermal reaction takes 1 to 14 days, and more preferably, the solvothermal reaction takes 3 to 7 days.

8. A patterned composition comprising the patterned material according to any one of claims 1-6. Preferably, the patterned composition further includes one or more of a solvent, a stabilizer, a photosensitizer, etc.

9. A method for forming a pattern, the method comprising the following steps: 1) Dissolve the above patterned material in a solvent, filter, and attach it to the substrate to form a patterned coating; 2) The patterned coating is subjected to radiation exposure treatment; 3) The exposed coating comes into contact with the developer to form a patterned coating material.

10. The use of a patterning material according to any one of claims 1-6 or a patterning composition according to claim 8 in the preparation of photoresist; preferably, electron beam photoresist, DUV photoresist, EUV photoresist or other photoresist.

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