Organic-inorganic hybrid {Ti3In} x type crystalline titanium indium oxygen cluster patterned material and preparation method and application thereof

Abstract

The invention provides an organic-inorganic hybrid {Ti3In} x type crystalline titanium indium oxygen cluster patterned material as shown in a formula (I) and a preparation method and application thereof.The patterned material structurally comprises a tetrahedron-shaped [InTi3 (mu3-O) (mu2-OR) 2 (L1) 3] segment, and after three Ti centers in the segment are connected together through a bridging oxygen bond, the three Ti centers in the segment are connected through a bridging oxygen bond; further, three L1 ligands are connected with one In to form a tetrahedral configuration. The patterned material is formed by connecting four tetrahedral [InTi3 (mu3-O) (mu2-OR) 2 (L1) 3] segments together through an organic ligand and bridged oxygen and / or hydroxyl, and additionally adding water and / or methanol which is not deprotonated as an end group ligand. The resolution ratio of a pattern formed after the patterning material provided by the invention is dissolved, filtered, spin-coated, exposed and developed can reach 100 nm and even 50 nm. Formula (I): Hx [InTi3 ([mu] 3-O) ([mu] 2-OR) 2 (L1) 3] a ([mu]-O) b ([mu]-OH) c (L2) d (L3) e.

Description

Technical Field

[0001] The present invention belongs to the technical field of photoresist materials, and particularly relates to an organic-inorganic hybrid {Ti3In} x Type crystalline titanium indium oxygen cluster patterned material and its preparation method and application. Background Art

[0002] As the number of transistors in integrated circuits continues to grow, the resolution requirements for lithography technology have also increased in order to meet the challenges posed by Moore's Law. Against this backdrop, extreme ultraviolet lithography has emerged. It uses a wavelength of 13.5 nanometers for lithography. Compared with deep ultraviolet lithography, extreme ultraviolet lithography provides significantly improved resolution and finer process control. The combination of extreme ultraviolet lithography and extreme ultraviolet photoresist has made it possible to manufacture smaller and higher-density circuits, further promoting the progress of Moore's Law.

[0003] Organic-inorganic hybrid metal oxide cluster photoresists have the characteristics of strong extreme ultraviolet light absorption and good etching resistance, and are widely considered to be the most promising extreme ultraviolet photoresists. At present, the research is mainly focused on the field of metal oxide compounds mainly composed of zirconium, hafnium, zinc, and tin, but there are problems such as the scarcity of photoresist materials and low sensitivity.

[0004] Metallic indium has a high absorption of extreme ultraviolet light, so indium oxygen cluster-based materials are very promising lithographic materials. In the synthesis of indium oxygen clusters, the indium source exists in the form of inorganic indium salts (such as indium nitrate, indium chloride, indium sulfate, etc.), which leads to the problem of difficulty in polymerizing into clusters. Summary of the invention

[0005] The present invention provides an organic-inorganic hybrid {Ti3In} x Type crystalline titanium indium oxygen cluster patterning material and its preparation method and application. An organic-inorganic hybrid {Ti3In} x The crystalline titanium indium oxygen cluster patterning material has a molecular formula as shown in formula (I):

[0006] H x [InTi3(μ3-O)(μ2-OR)2(L1)3] a (μ-O) b (μ-OH) c (L2) d (L3) e

[0007] Formula (I);

[0008] Wherein, R is selected from H, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 6-20 Aryl;

[0009] x≥0; 1≤a≤8; b≥1; c≥0; d≥a; e≥a; b+c+d+e≤24a;

[0010] L1, L2, and L3 are the same or different and are independently selected from ligands capable of coordinating with In and Ti.

[0011] According to an embodiment of the present invention, R is selected from H, C 1-10 Alkyl, C 2-10 Alkenyl, C 2-10 Alkynyl, C 6-10 Aryl.

[0012] According to an embodiment of the present invention, R is selected from H, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 6-10 Aryl.

[0013] According to an embodiment of the present invention, R is selected from H, C 1-4 Alkyl, C 2-4 Alkenyl, C 2-4 Alkynyl, C 6-10 Aryl.

[0014] According to an embodiment of the present invention, R is selected from H, methyl, ethyl, propyl, butyl, vinyl, methylpropenyl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, naphthyl, and the like.

[0015] According to an embodiment of the present invention, L1 may be a single ligand or one or more thereof may coexist in the same ligand.

[0016] According to an embodiment of the present invention, L1 is selected from salicylic acid and its derivatives (for example, methylsalicylic acid, fluorosalicylic acid or nitrosalicylic acid, such as 4-methylsalicylic acid, 5-fluorosalicylic acid, 5-nitrosalicylic acid), 3-hydroxypropionic acid, serine, threonine, catechol, 3,5-pyrazoledicarboxylic acid, triethanolamine, oxalic acid, etc., which are structures obtained by losing H on the carboxyl group and / or hydroxyl group.

[0017] According to an embodiment of the present invention, L2 and L3 are the same or different and are independently selected from ligands containing but not limited to C, O, S, Se, Te, N, P, As, Sb, Cl, Br, I, etc. as coordinating atoms.

[0018] According to an embodiment of the present invention, L2 and L3 are the same or different and are independently selected from alkanes (C 1-20 Alkyl), aromatic hydrocarbons (C 6-20 Aromatic hydrocarbons), olefins (C 2-20 alkenyl), alkynes (C2-20 alkynyl), carboxylic acids, alcohols, thiols, phenols, sulfonic acids, phosphoric / phosphonic acids, phosphines, arsenic acids, nitriles, alcoholamines, pyridines, pyrazoles, imidazoles, piperazines, pyrazines, halogens, H2O, SO4, NO3 or ligands such as the above ions, for example, alcohols and water, such as methanol and water.

[0019] According to an embodiment of the present invention, L1, L2, and L3 may be present in any ratio.

[0020] According to an embodiment of the present invention, the organic-inorganic hybrid {Ti3In} x Part or all of the In and Ti ions in the crystalline titanium indium oxide cluster patterned material can be replaced by other elements, such as radiation-sensitive elements. Preferably, the radiation-sensitive element is selected from any one of 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, or a combination thereof.

[0021] According to an embodiment of the present invention, radiation-sensitive functional groups may be further introduced into ligands L1, L2, and L3. The introduction of radiation-sensitive functional groups may enhance the photosensitivity of the patterned material, improve the line edge roughness, and improve the resolution. The radiation-sensitive functional groups are, for example, double bonds, triple bonds, propylene oxide, or a combination thereof.

[0022] According to an embodiment of the present invention, functional groups may be further introduced into L1, L2, and L3. The introduction of functional groups may adjust the light absorption capacity, solubility, film-forming properties and other properties of the patterned material, thereby affecting the film thickness, film roughness, resolution, film adhesion and corrosion resistance.

[0023] According to an embodiment of the present invention, the organic-inorganic hybrid {Ti3In} x The ratio of the coordinating atoms of the ligands to the metal ions in the crystalline titanium indium oxide cluster patterning material can be adjusted to improve the sensitivity, line edge roughness and resolution of the patterning material.

[0024] According to an embodiment of the present invention, the organic-inorganic hybrid {Ti3In} xThe crystalline titanium indium oxygen cluster patterned material has a tetrahedral [InTi3(μ3-O)(μ2-OR)2(L1)3] fragment, in which three Ti centers are linked together through a cross-linked oxygen, and then further connected to an In through three L1 ligands to form a tetrahedral configuration. Preferably, the [InTi3(μ3-O)(μ2-OR)2(L1)3] fragment is a [InTi3(μ3-O)(μ2-OCH3)2(SAD)3] fragment (SAD is salicylic acid and its derivatives).

[0025] According to an embodiment of the present invention, the organic-inorganic hybrid {Ti3In} x The crystalline titanium indium oxide cluster patterning material is selected from the following compounds 1 to 4:

[0026] Compound 1: Ti 12 In4(SA) 12 (μ3-O)4(μ2-OCH3)8(μ2-O) 10 (H2O)6(CH3OH)2;

[0027] Compound 2: Ti 12 In4(SA-CH3) 12 (μ3-O)4(μ2-OCH3)8(μ2-O) 10 (H2O)6(CH3OH)2;

[0028] Compound 3: Ti 12 In4(SA-F) 12 (μ3-O)4(μ2-OCH3)8(μ2-O) 10 (H2O)6(CH3OH)2;

[0029] Compound 4: (H3O)2[Ti 12 In4(SA-NO2) 12 (μ3-O)4(μ2-OCH3)8(μ2-O) 10 (μ2-OH)2(H2O)4];

[0030] Among them, SA represents salicylate, with a molecular formula of C7H4O3; SA-CH3 represents 4-methylsalicylate, with a molecular formula of C8H6O3; SA-F represents 5-fluorosalicylate, with a molecular formula of C7H3FO3; SA-NO2 represents 5-nitrosalicylate, with a molecular formula of C7H3NO5. The salicylate represents a structure obtained after salicylic acid loses the carboxyl group and the H on the hydroxyl group. The 4-methylsalicylate represents a structure obtained after 4-methylsalicylate loses the carboxyl group and the H on the hydroxyl group. The 5-fluorosalicylate represents a structure obtained after 5-fluorosalicylic acid loses the carboxyl group and the H on the hydroxyl group. The 5-nitrosalicylate represents a structure obtained after 5-nitrosalicylic acid loses the carboxyl group and the H on the hydroxyl group.

[0031] According to the embodiment of the present invention, the crystal parameters of compound 1 are: the crystal system is tetragonal, the space group is P-421c, and the unit cell parameter a is b is c is α is 90°, β is 90°, γ is 90°, V is

[0032] According to an embodiment of the present invention, the crystal parameters of compound 2 are: the crystal system is monoclinic, the space group is P121 / n1, and the unit cell parameter a is b is c is α is 90°, β is 107.4470(10)°, γ is 90°, and V is

[0033] According to the embodiment of the present invention, the crystal parameters of compound 3 are: the crystal system is monoclinic, the space group is P121 / n1, and the unit cell parameter a is b is c is α is 90°, β is 104.374(2)°, γ is 90°, and V is

[0034] According to the embodiment of the present invention, the crystal parameters of compound 4 are: the crystal system is monoclinic, the space group is P121 / n1, and the unit cell parameter a is b is c is α is 90°, β is 103.552(2)°, γ is 90°, and V is

[0035] The present invention also provides the above organic-inorganic hybrid {Ti3In} x The method for preparing a crystalline titanium indium oxygen cluster patterned material comprises the following steps:

[0036] The material can be prepared by using an indium source, a titanium source, a ligand and a solvent through a solvothermal synthesis method;

[0037] According to an embodiment of the present invention, the indium source is selected from any one of the following: indium chloride, indium nitrate, indium acetate, indium sulfate, and the like, and hydrates thereof.

[0038] According to an embodiment of the present invention, the titanium source is selected from any one of the following: titanium isopropoxide [Ti(O i Pr)4], titanium ethoxide, titanium butoxide, etc.

[0039] According to an embodiment of the present invention, the ligand is selected from any one of the following: salicylic acid, 4-methylsalicylic acid, 5-fluorosalicylic acid, 5-nitrosalicylic acid, and the like, and derivatives thereof.

[0040] According to an embodiment of the present invention, the solvothermal synthesis method is to carry out a heating reaction in a solvent.

[0041] According to an embodiment of the present invention, the solvent is selected from alcohols, phenols, mixed alcohols, and mixed alcohol-phenol solvents.

[0042] According to an embodiment of the present invention, the alcohol solvent is any one of C1-20 alcohols (e.g., C1-10 alcohols, C1-6 alcohols, etc.) or a mixture thereof in any proportion, for example, selected from any one of alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, n-pentanol, isopentanol, neopentyl alcohol, hexanol, heptanol, octanol, decanol, or a mixture thereof in any proportion. The alcohol solvent is preferably methanol, n-butanol, or tert-butanol.

[0043] According to an embodiment of the present invention, the temperature of the solvothermal reaction may be 40 to 200°C, preferably 60 to 120°C.

[0044] According to an embodiment of the present invention, the solvent thermal reaction time may be 1 to 14 days, preferably 3 to 7 days.

[0045] According to an embodiment of the present invention, the solvothermal reaction can be carried out in a sealed glass bottle or a polytetrafluoroethylene pressure reactor.

[0046] According to an embodiment of the present invention, the preparation method further comprises a step of purifying the product.

[0047] According to an embodiment of the present invention, the purification step includes: washing, separating and drying the reaction product at room temperature.

[0048] According to an embodiment of the present invention, an alcohol solvent is used in the washing step, and the alcohol solvent used for washing may be the same as or different from the alcohol added in the reaction.

[0049] The present invention also provides a patterned composition, the patterned composition comprising the above-mentioned organic-inorganic hybrid {Ti3In} x Type crystalline titanium indium oxide cluster patterning material.

[0050] According to an embodiment of the present invention, the patterning composition further includes any one or more of a solvent, a stabilizer, a photosensitizer, and the like.

[0051] According to an embodiment of the present invention, the solvent is selected from one of ethyl lactate and N,N-dimethylformyl.

[0052] The present invention also provides a patterning method, comprising the following steps:

[0053] 1) The above organic-inorganic hybrid {Ti3In} x The crystalline titanium indium oxygen cluster patterned material is dissolved in a solvent, filtered, and attached to a substrate (by spin coating or other methods) to form a patterned coating;

[0054] 2) exposing the patterned coating to radiation;

[0055] 3) The exposed coating is brought into contact with a developer to form a pattern of the coating material.

[0056] According to an embodiment of the present invention, the substrate may be a hydrophilic or hydrophobic surface, such as a silicon wafer.

[0057] According to an embodiment of the present invention, the solvent is a solvent that can dissolve the above-mentioned patterned material; preferably, it includes but is not limited to any one of carboxylic acid esters, alcohols with 1-20 carbon atoms, halogenated hydrocarbons, aromatic hydrocarbons, amides, ketones, water and other solvents, or a mixture in any proportion thereof; further preferably, it is at least one of propylene glycol methyl ether acetate, ethyl lactate, isoacetate, methanol, isopropanol, heptanol, 2-heptanone, N,N-dimethylformamide, and water.

[0058] According to an embodiment of the present invention, examples of the carboxylates include but are not limited to: carboxylic acid ether esters such as 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, etc.; carboxylic acid alkane esters such as ethyl formate, ethyl acetate, n-butyl acetate, ethyl lactate, n-propyl lactate, isopropyl lactate, etc.

[0059] According to an embodiment of the present invention, examples of the alcohol having 1 to 20 carbon atoms include: methanol, ethanol, isopropanol, n-butanol, cyclohexanol, heptanol and the like.

[0060] According to an embodiment of the present invention, examples of the halogenated hydrocarbons include but are not limited to: dichloromethane, chloroform, and the like.

[0061] According to an embodiment of the present invention, examples of the aromatic hydrocarbons include, but are not limited to, benzene, toluene, xylene, and the like.

[0062] According to an embodiment of the present invention, examples of the amides include, but are not limited to, N,N-dimethylformamide, N,N-dimethylacetamide, and the like.

[0063] According to an embodiment of the present invention, examples of ketones include, but are not limited to, acetone, heptanone, and the like.

[0064] According to an embodiment of the present invention, the concentration of the patterning material in the solvent is about 5 mg / mL to 30 mg / mL.

[0065] According to an embodiment of the present invention, after the patterned material is exposed to radiation, the solubility of the exposed and unexposed coating areas in the developer is greatly different. The patterned coating material contains metal ions with radiation-sensitive ligands before irradiation, and the radiation changes the properties of the coating material, thereby producing structures with different dissolution rates.

[0066] According to an embodiment of the present invention, the radiation is selected from electron beams and ultraviolet, deep ultraviolet, extreme ultraviolet or shorter wavelength light sources.

[0067] According to an embodiment of the present invention, the developer is selected from any one of the following solvents or a mixture of any proportions of multiple solvents: a 0.5% to 20% aqueous solution of tetramethylammonium hydroxide (TMAH), heptanone, methanol, isopropanol, heptanol, N,N-dimethylformamide, propylene glycol methyl ether acetate, ethyl lactate, water, benzene, toluene, dichloromethane, etc.

[0068] According to an embodiment of the present invention, the developer is a solvent that can cause different dissolution rates of the material before and after irradiation.

[0069] According to an embodiment of the present invention, the developer is in contact with the patterned coating for no longer than 10 minutes.

[0070] The present invention also provides the above organic-inorganic hybrid {Ti3In} x Application of a crystalline titanium indium oxide cluster patterning material or a patterning composition in the preparation of a photoresist; the photoresist is preferably an electron beam photoresist, a UV photoresist, a DUV photoresist, an EUV photoresist or other photoresists.

[0071] Beneficial Effects

[0072] Metallic indium has a high absorption of extreme ultraviolet light, so indium oxygen cluster-based materials are highly promising photolithographic materials. In the synthesis of indium oxygen clusters, the indium source exists in the form of inorganic indium salts (such as indium nitrate, indium chloride, indium sulfate, etc.), which has the problem of difficulty in polymerizing into clusters. The present invention introduces titanium isopropoxide, which is very easy to hydrolyze into clusters, as a titanium source in the above system, and can controllably form indium titanium oxygen clusters, which can enrich the structural types of indium titanium metal oxygen clusters and regulate the solubility, film-forming properties, and photolithographic performance of indium titanium oxygen clusters.

[0073] The present invention provides a type of organic-inorganic hybrid metal oxide cluster patterning material, in which there is a tetrahedral [InTi3(μ3-O)(μ2-OR)2(L1)3] fragment in the structure of the patterning material, in which three Ti centers are linked together through a cross-linked oxygen, and then further connected to an In through three L1 ligands to form a tetrahedral configuration. This type of patterning material is formed by four tetrahedral [InTi3(μ3-O)(μ2-OR)2(L1)3] fragments connected together through organic ligands and cross-linked oxygen and / or hydroxyl groups, and non-deprotonated water and / or methanol are added as terminal ligands. The resolution of the pattern formed by the patterning material provided by the present invention after dissolution, filtration, spin coating, exposure and development can reach 100nm, or even 50nm.

[0074] The patterned material of the present invention contains adjustable cross-linked ligands, different radiation-responsive metals and terminal ligands. By introducing functional groups into the ligands, adjusting the types and proportions of different metals, and regulating the types and quantities of terminal ligands, its solubility, film-forming properties, light absorption capacity, photosensitivity, line edge roughness, and resolution can be further enhanced, thereby regulating the photolithographic performance of the patterned material.

[0075] The crystalline indium titanium oxide cluster provided by the present invention has the characteristics of accurate structural information, high solution stability, high-quality film-forming property, etc. Moreover, the raw materials are simple and easy to obtain, the crystal material synthesis method is simple, the yield is high, and it can be prepared in large quantities, and it is a very potential candidate photoresist material. BRIEF DESCRIPTION OF THE DRAWINGS

[0076] Figure 1 Ti 12 In4(SA) 12 (μ3-O)4(μ2-OCH3)8(μ2-O) 10 Schematic diagram of the structure of (H2O)6(CH3OH)2, in which the tetrahedral [InTi3(μ3-O)(μ2-OCH3)(SA)3] fragments are connected by cross-linked oxygen.

[0077] Figure 2 Ti 12 In4(SA-CH3) 12(μ3-O)4(μ2-OCH3)8(μ2-O) 10 Schematic diagram of the structure of (H2O)6(CH3OH)2, in which the tetrahedral [InTi3(μ3-O)(μ2-OCH3)(SA-CH3)3] fragments are connected by cross-linked oxygen.

[0078] Figure 3 Ti 12 In4(SA-F) 12 (μ3-O)4(μ2-OCH3)8(μ2-O) 10 Schematic diagram of the structure of (H2O)6(CH3OH)2, in which the tetrahedral [InTi3(μ3-O)(μ2-OCH3)(SA-F)3] fragments are connected by cross-linked oxygen.

[0079] Figure 4 (H3O)2[Ti 12 In4(SA-NO2) 12 (μ3-O)4(μ2-OCH3)8(μ2-O) 10 Schematic diagram of the structure of [(μ2-OH)2(H2O)4], in which the tetrahedral [InTi3(μ3-O)(μ2-OCH3)(SA-NO2)3] fragments are connected by cross-linked oxygen and hydroxyl groups.

[0080] Figure 5 Ti 12 In4(SA) 12 (μ3-O)4(μ2-OCH3)8(μ2-O) 10 Infrared spectrum of (H2O)6(CH3OH)2.

[0081] Figure 6 Ti 12 In4(SA-CH3) 12 (μ3-O)4(μ2-OCH3)8(μ2-O) 10 Infrared spectrum of (H2O)6(CH3OH)2.

[0082] Figure 7 Ti 12 In4(SA-F) 12 (μ3-O)4(μ2-OCH3)8(μ2-O) 10 Infrared spectrum of (H2O)6(CH3OH)2.

[0083] Figure 8 (H3O)2[Ti 12 In4(SA-NO2) 12(μ3-O)4(μ2-OCH3)8(μ2-O) 10 Infrared spectrum of [(μ2-OH)2(H2O)4].

[0084] Fig. 9 Ti 12 In4(SA) 12 (μ3-O)4(μ2-OCH3)8(μ2-O) 10 Energy dispersive X-ray spectrum (EDX) of (H2O)6(CH3OH)2.

[0085] Fig.10 Ti 12 In4(SA-CH3) 12 (μ3-O)4(μ2-OCH3)8(μ2-O) 10 Energy dispersive X-ray spectrum (EDX) of (H2O)6(CH3OH)2.

[0086] Fig.11 Ti 12 In4(SA-F) 12 (μ3-O)4(μ2-OCH3)8(μ2-O) 10 Energy dispersive X-ray spectrum (EDX) of (H2O)6(CH3OH)2.

[0087] Fig.12 (H3O)2[Ti 12 In4(SA-NO2) 12 (μ3-O)4(μ2-OCH3)8(μ2-O) 10 Energy dispersive X-ray spectrum (EDX) of [(μ2-OH)2(H2O)4].

[0088] Fig.13 Ti 12 In4(SA) 12 (μ3-O)4(μ2-OCH3)8(μ2-O) 10 (H2O)6(CH3OH)2 material at 1000μC / cm 2 After patterning by exposure and development at a certain dose, SEM analysis showed that the width of the exposed line was 100 nm.

[0089] Fig.14 Ti 12 In4(SA) 12 (μ3-O)4(μ2-OCH3)8(μ2-O) 10 (H2O)6(CH3OH)2 material at 1000μC / cm 2After patterning by exposure and development at a certain dose, SEM analysis showed that the width of the exposed line was 50 nm.

[0090] Fig.15 Schematic diagram of the structure of the tetrahedral [InTi3(μ3-O)(μ2-OCH3)2(SA)3] fragment. The three Ti centers are linked together through a cross-linked oxygen and then further connected to an In through three SA ligands to form a tetrahedral configuration.

[0091] Fig.16 Schematic diagram of the structure of the tetrahedral [InTi3(μ3-O)(μ2-OCH3)2(SA-CH3)3] fragment. The three Ti centers are linked together through a cross-linked oxygen and then further connected to an In through three SA-CH3 ligands to form a tetrahedral configuration.

[0092] Fig.17 Schematic diagram of the structure of the tetrahedral [InTi3(μ3-O)(μ2-OCH3)2(SA-F)3] fragment. The three Ti centers are linked together through a cross-linked oxygen and then further connected to an In through three SA-F ligands to form a tetrahedral configuration.

[0093] Fig.18 Schematic diagram of the structure of the tetrahedral [InTi3(μ3-O)(μ2-OCH3)2(SA-NO2)3] fragment. The three Ti centers are linked together through an oxygen atom and then further connected to an In through three SA-NO2 ligands to form a tetrahedral configuration.

[0094] Fig.19 Show Ti 12 In4(SA) 12 (μ3-O)4(μ2-OCH3)8(μ2-O) 10 Schematic diagram of the structure of the In terminal group in (H2O)6(CH3OH)2 containing coordinated non-deprotonated methanol and water molecules.

[0095] Fig. 20 Show Ti 12 In4(SA-CH3) 12 (μ3-O)4(μ2-OCH3)8(μ2-O) 10 Schematic diagram of the structure of the In terminal group in (H2O)6(CH3OH)2 containing coordinated non-deprotonated methanol and water molecules.

[0096] Fig.21 Show Ti 12 In4(SA-F) 12 (μ3-O)4(μ2-OCH3)8(μ2-O) 10Schematic diagram of the structure of the In terminal group in (H2O)6(CH3OH)2 containing coordinated non-deprotonated methanol and water molecules.

[0097] Fig. 22 Show Ti 12 In4(SA-NO2) 12 (μ3-O)4(μ2-OCH3)8(μ2-O) 10 Schematic diagram of the structure of the In terminal group in (H2O)6(CH3OH)2 containing a coordinated, non-deprotonated water molecule.

[0098] SA represents salicylate, with the molecular formula C7H4O3; SA-CH3 represents 4-methylsalicylate, with the molecular formula C8H6O3; SA-F represents 5-fluorosalicylate, with the molecular formula C7H3FO3; SA-NO2 represents 5-nitrosalicylate, with the molecular formula C7H3NO5.

[0099] In order to make the structure clearer, some oxygen, carbon, nitrogen, hydrogen and other atoms are omitted in the schematic diagram. DETAILED DESCRIPTION

[0100] The technical scheme of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only exemplary descriptions and explanations 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 included in the scope that the present invention is intended to protect.

[0101] Unless otherwise specified, the raw materials and reagents used in the following examples are commercially available or can be prepared by known methods.

[0102] The solvent methanol and metal salt used in the present application contain a certain amount of water, and water will also be generated during the reaction. The water in the terminal ligands in the obtained material comes from the water in the above materials or the water generated during the reaction.

[0103] Example 1 Preparation and characterization of mixed organic-inorganic hybrid metal oxide cluster patterned materials

[0104] 1. Ti 12 In4(SA) 12 (μ3-O)4(μ2-OCH3)8(μ2-O) 10 (H2O)6(CH3OH)2 (SA stands for salicylic acid, with the molecular formula C7H4O3)

[0105] In a 20 mL glass reaction bottle, Ti(O iPr)4 (0.15mL, 0.49mmol), indium nitrate (0.50mmol, 150mg), salicylic acid (1mmol, 138mg) and methanol (3mL~8mL) were mixed, the lid was tightened, and the mixture was heated to 80℃. After 5 days, the mixture was cooled to room temperature and crystals were precipitated. The yield was about 25%. The crystals were separated and washed with methanol.

[0106] Referring to the above steps, the reaction temperature is adjusted to 60-120° C., and the reaction time is 3-7 days; the yield is 20%-30%.

[0107] The crystallographic data are as follows: the crystal system is tetragonal, the space group is P-421c, and the unit cell parameter a is b is c is α is 90°, β is 90°, γ is 90°, V is

[0108] Ti 12 In4(SA) 12 (μ3-O)4(μ2-OCH3)8(μ2-O) 10 The structural diagram of (H2O)6(CH3OH)2 is as follows Figure 1 As shown, the infrared spectrum is Figure 5 As shown, the energy dispersive X-ray spectrum (EDX) is as follows Fig. 9 shown.

[0109] 2. Ti 12 In4(SA-CH3) 12 (μ3-O)4(μ2-OCH3)8(μ2-O) 10 (H2O)6(CH3OH)2 (SA-CH3 represents 4-methyl salicylate, molecular formula is C8H6O3)

[0110] In a 20 mL glass reaction bottle, Ti(O i Pr)4 (0.15mL, 0.49mmol), indium nitrate (0.50mmol, 150mg), 4-methylsalicylic acid (1mmol, 152mg) were mixed with methanol (1-3mL) and tert-butyl alcohol (1-3mL), and the lid was tightened, heated to 80°C, and cooled to room temperature after 5 days, and crystals precipitated. The yield was about 25%. The crystals were separated and rinsed with methanol.

[0111] Referring to the above steps, the reaction temperature is adjusted to 60-120° C., and the reaction time is 3-7 days; the yield is 20%-30%.

[0112] The crystallographic data are: the crystal system is monoclinic, the space group is P121 / n1, and the unit cell parameter a is b is c is α is 90°, β is 107.4470(10)°, γ is 90°, and V is

[0113] Ti 12 In4(SA-CH3) 12 (μ3-O)4(μ2-OCH3)8(μ2-O) 10 The structural diagram of (H2O)6(CH3OH)2 is as follows Figure 2 As shown, the infrared spectrum is Figure 6 As shown in the energy dispersive X-ray spectrum (EDX) Fig.10 shown.

[0114] 3. Ti 12 In4(SA-F) 12 (μ3-O)4(μ2-OCH3)8(μ2-O) 10 (H2O)6(CH3OH)2 (SA-F represents 5-fluorosalicylate, molecular formula is C7H3FO3)

[0115] In a 20 mL glass reaction bottle, Ti(O i Pr)4 (0.15mL, 0.49mmol), indium nitrate (0.50mmol, 150mg), 5-fluorosalicylic acid (1mmol, 156mg) and methanol (3mL-8mL) were mixed, the lid was tightened, heated to 80°C, cooled to room temperature after 5 days, and crystals precipitated. The yield was 25%. The crystals were separated and rinsed with methanol.

[0116] Referring to the above steps, the reaction temperature is adjusted to 60-120° C., and the reaction time is 3-7 days; the yield is 20%-25%.

[0117] The crystallographic data are: the crystal system is monoclinic, the space group is P121 / n1, and the unit cell parameter a is b is c is α is 90°, β is 104.374(2)°, γ is 90°, and V is

[0118] Ti 12 In4(SA-F) 12 (μ3-O)4(μ2-OCH3)8(μ2-O) 10 The structural diagram of (H2O)6(CH3OH)2 is as follows Figure 3 As shown, the infrared spectrum is Figure 7 As shown in the energy dispersive X-ray spectrum (EDX) Fig.11 shown.

[0119] 4.(H3O)2[Ti 12 In4(SA-NO2) 12 (μ3-O)4(μ2-OCH3)8(μ2-O) 10 (μ2-OH)2(H2O)4] (SA-NO2 represents 5-nitrosalicylic acid, with the molecular formula C7H3NO5)

[0120] In a 20 mL glass reaction bottle, Ti(O i Pr)4 (0.15mL, 0.49mmol), indium nitrate (0.50mmol, 150mg), 5-nitrosalicylic acid (1mmol, 152mg) were mixed with methanol (1-3mL) and n-butanol (1-3mL), and the lid was tightened, heated to 80°C, cooled to room temperature after 5 days, and crystals precipitated. The yield was 25%. The crystals were separated and rinsed with methanol.

[0121] Referring to the above steps, the reaction temperature is adjusted to 60-120° C., and the reaction time is 3-7 days; the yield is 20%-30%.

[0122] The crystallographic data are: the crystal system is monoclinic, the space group is P121 / n1, and the unit cell parameter a is b is c is α is 90°, β is 103.552(2)°, γ is 90°, and V is

[0123] (H3O)2[Ti 12 In4(SA-NO2) 12 (μ3-O)4(μ2-OCH3)8(μ2-O) 10 The structural diagram of (μ2-OH)2(H2O)4] is shown in Figure 4 As shown, the infrared spectrum is Figure 8 As shown in the energy dispersive X-ray spectrum (EDX) Fig.12 shown.

[0124] Analysis shows that the structural characteristics of the above four mixed-type organometallic oxygen cluster crystal materials are:

[0125] 1) There is a tetrahedral [InTi3(μ3-O)(μ2-OR)2(L1)3] fragment, in which three Ti centers are linked together through a cross-linked oxygen and further connected to an In through three L1 ligands to form a tetrahedral configuration (such as Figure 15-18As shown). This type of material is formed by four tetrahedral [InTi3(μ3-O)(μ2-OR)2(L1)3] fragments connected together by organic ligands and cross-linked oxygen or hydroxyl groups, and with the addition of undeprotonated water or methanol as the end group ligand. The specific structural features are as follows Figure 1-4 As shown; Figure 1 , Ti 12 In4(SA) 12 (μ3-O)4(μ2-OCH3)8(μ2-O) 10 In (H2O)6(CH3OH)2, tetrahedral [InTi3(μ3-O)(μ2-OCH3)(SA)3] fragments are linked together by cross-linked oxygen and are formed by the addition of undeprotonated water and methanol as terminal ligands; Figure 2 , Ti 12 In4(SA-CH3) 12 (μ3-O)4(μ2-OCH3)8(μ2-O) 10 In (H2O)6(CH3OH)2, tetrahedral [InTi3(μ3-O)(μ2-OCH3)(SA-CH3)3] fragments are linked together by cross-linked oxygen and are formed by the addition of undeprotonated water and methanol as terminal ligands; Figure 3 , Ti 12 In4(SA-F) 12 (μ3-O)4(μ2-OCH3)8(μ2-O) 10 In (H2O)6(CH3OH)2, tetrahedral [InTi3(μ3-O)(μ2-OCH3)(SA-F)3] fragments are linked together by cross-linked oxygen and are formed by the addition of undeprotonated water and methanol as terminal ligands; Figure 4 , (H3O)2[Ti 12 In4(SA-NO2) 12 (μ3-O)4(μ2-OCH3)8(μ2-O) 10 In the [(μ2-OH)2(H2O)4], the tetrahedral [InTi3(μ3-O)(μ2-OCH3)(SA-NO2)3] fragments are connected together by cross-linked oxygen and hydroxyl groups, and undeprotonated water is added as the terminal ligand to form.

[0126] 2) Some metal terminal ligands are undeprotonated water and / or alcohols. Such terminal water or alcohol ligands are easily replaced by other ligands, so the active site can regulate the technical indicators of patterning performance; the specific structural features are terminal coordinated water or alcohol molecules such as Figure 19-22 shown.

[0127] Example 2

[0128] 1. Silicon wafer processing

[0129] Clean the silicon wafer in an acidic or alkaline solution for 15 to 30 minutes, then wash it with deionized water and then with isopropyl alcohol. Use an air gun to blow dry the surface liquid before use.

[0130] 2. Film preparation

[0131] Take 10 mg of the mixed organometallic oxygen cluster patterning material prepared in Example 1, dissolve it in 1 mL of ethyl lactate or N,N-dimethylformamide, filter the solution, and take an appropriate amount of the filtered solution to form a coating on the surface of the treated silicon substrate by spin coating.

[0132] Referring to the above steps, 5 to 30 mg of the mixed organometallic oxygen cluster patterning material prepared in Example 1 is dissolved in 1 mL of ethyl lactate or N,N-dimethylformamide, and the solution is filtered. An appropriate amount of the filtered solution is transferred and a coating is formed on the surface of the treated silicon substrate by spin coating.

[0133] 3. Exposure

[0134] After the electron beam selectively irradiates the patterned material film layer, the irradiated part undergoes chemical changes and changes in solubility. That is, the solubility of the exposed and unexposed film layer areas in the developer is greatly different, thus forming a pattern.

[0135] 4. Development

[0136] During the development process, a developer is used to contact the exposed film layer to dissolve and remove part of the patterned material film layer. The dissolved part is the exposed film layer or the unexposed film layer.

[0137] The developer used is a mixture of N,N-dimethylformamide or isopropyl alcohol and water (volume ratio range is 10:1 to 1:10). The developing time is 5s to 120s.

[0138] 5. Pattern Characterization

[0139] The pattern of the coating material after exposure and development was characterized by a scanning electron microscope (SEM). The results are as follows: Fig.13 and 14 shown.

[0140] The resolution of the pattern formed by the mixed organometallic oxygen cluster patterning material compound 1 in Example 1 after dissolution, filtration, spin coating, exposure and development can reach 100 nm, or even 50 nm.

[0141] The above is an explanation of the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. An organic-inorganic hybrid {Ti3In} x A crystalline titanium indium oxide cluster patterned material, characterized in that: Its molecular formula is shown in formula (I): H x [InTi3(μ3-O)(μ2-OR)2(L1)3] a (m-O) b (μ-OH) c (L2) d (L3) e Formula (I); Wherein, R is selected from H, C 1-20 Alkyl, C 2-20 Alkenyl, C 2-20 Alkynyl, C 6-20 Aryl; x≥0; 1≤a≤8; b≥1; c≥0; d≥a; e≥a; b+c+d+e≤24a; L1, L2, and L3 are the same or different and are independently selected from ligands capable of coordinating with In and Ti.

2. The organic-inorganic hybrid {Ti3In} according to claim 1 x A crystalline titanium indium oxide cluster patterned material, characterized in that: R is selected from H, C 1-10 Alkyl, C 2-10 Alkenyl, C 2-10 Alkynyl, C 6-10 Aryl; Preferably, R is selected from H, C 1-6 Alkyl, C 2-6 Alkenyl, C 2-6 Alkynyl, C 6-10 Aryl. Preferably, R is selected from H, C 1-4 Alkyl, C 2-4 Alkenyl, C 2-4 Alkynyl, C 6-10 Aryl. Preferably, R is selected from H, methyl, ethyl, propyl, butyl, vinyl, methacryl, propenyl, butenyl, ethynyl, propynyl, butynyl, phenyl, naphthyl. Preferably, L1 is selected from salicylic acid and its derivatives (e.g., methylsalicylic acid, fluorosalicylic acid or nitrosalicylic acid, such as 4-methylsalicylic acid, 5-fluorosalicylic acid, 5-nitrosalicylic acid), 3-hydroxypropionic acid, serine, threonine, catechol, 3,5-pyrazoledicarboxylic acid, triethanolamine, and oxalic acid, and the structure obtained by losing H on the carboxyl group and / or hydroxyl group. Preferably, L2 and L3 are the same or different and are independently selected from ligands containing C, O, S, Se, Te, N, P, As, Sb, Cl, Br, I, etc. as coordinating atoms.

3. The organic-inorganic hybrid {Ti3In} according to claim 1 or 2 x A crystalline titanium indium oxide cluster patterned material, characterized in that: L2 and L3 are the same or different and are independently selected from alkanes (C 1-20 Alkyl), aromatic hydrocarbons (C 6-20 Aromatic hydrocarbons), olefins (C 2-20 alkenyl), alkynes (C 2-20 alkynyl), carboxylic acids, alcohols, thiols, phenols, sulfonic acids, phosphoric / phosphonic acids, phosphines, arsenic acids, nitriles, alcoholamines, pyridines, pyrazoles, imidazoles, piperazines, pyrazines, halogens, H2O, SO4, NO3 or ligands such as the above ions, for example, alcohols and water, such as methanol and water. Preferably, L1, L2, L3 may be present in any ratio. Preferably, the organic-inorganic hybrid {Ti3In} x Part or all of the In and Ti ions in the crystalline titanium indium oxide cluster patterned material can be replaced by other elements, such as radiation-sensitive elements. Preferably, the radiation-sensitive element is selected from any one of 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, or a combination thereof. Preferably, radiation-sensitive functional groups may be further introduced into ligands L1, L2, and L3. The introduction of radiation-sensitive functional groups can enhance the photosensitivity of the patterned material, improve the line edge roughness, and increase the resolution. The radiation-sensitive functional groups are, for example, double bonds, triple bonds, propylene oxide, or a combination thereof. Preferably, functional groups can be further introduced into L1, L2 and L3. The introduction of functional groups can adjust the light absorption ability, solubility, film-forming properties and other properties of the patterned material, thereby affecting the film thickness, film roughness, resolution, film adhesion and corrosion resistance. Preferably, the organic-inorganic hybrid {Ti3In} x The ratio of the coordinating atoms of the ligands to the metal ions in the crystalline titanium indium oxide cluster patterning material can be adjusted to improve the sensitivity, line edge roughness and resolution of the patterning material. Preferably, the organic-inorganic hybrid {Ti3In} x The crystalline titanium indium oxide cluster patterned material has a tetrahedral [InTi3(μ3-O)(μ2-OR)2(L1)3] fragment, in which three Ti centers are linked together through a cross-linked oxygen and further connected to an In through three L1 ligands to form a tetrahedral configuration. Preferably, the [InTi3(μ3-O)(μ2-OR)2(L1)3] fragment is a [InTi3(μ3-O)(μ2-OCH3)2(SAD)3] fragment, wherein SAD is salicylate and its derivatives.

4. The organic-inorganic hybrid {Ti3In} according to any one of claims 1 to 3 x A crystalline titanium indium oxide cluster patterned material, characterized in that: The organic-inorganic hybrid {Ti3In} x The crystalline titanium indium oxide cluster patterning material is selected from the following compounds 1 to 4: Compound 1: Ti 12 In4(SA) 12 (μ3-O)4(μ2-OCH3)8(μ2-O) 10 (H2O)6(CH3OH)2; Compound 2: Ti 12 In4(SA-CH3) 12 (μ3-O)4(μ2-OCH3)8(μ2-O) 10 (H2O)6(CH3OH)2; Compound 3: Ti 12 In4(SA-F) 12 (μ3-O)4(μ2-OCH3)8(μ2-O) 10 (H2O)6(CH3OH)2; Compound 4: (H3O)2[Ti 12 In4(SA-NO2) 12 (μ3-O)4(μ2-OCH3)8(μ2-O) 10 (μ2-OH)2(H2O)4]; Among them, SA represents salicylate, with the molecular formula C7H4O3; SA-CH3 represents 4-methylsalicylate, with the molecular formula C8H6O3; SA-F represents 5-fluorosalicylate, with the molecular formula C7H3FO3; SA-NO2 represents 5-nitrosalicylate, with the molecular formula C7H3NO5.

5. The organic-inorganic hybrid {Ti3In} according to any one of claims 1 to 4 x A crystalline titanium indium oxide cluster patterned material, characterized in that: The crystal parameters of compound 1 are: the crystal system is tetragonal, the space group is P-421c, and the unit cell parameter a is b is c is α is 90°, β is 90°, γ is 90°, V is Preferably, the crystal parameters of compound 2 are: the crystal system is monoclinic, the space group is P121 / n1, and the unit cell parameter a is b is c is α is 90°, β is 107.4470(10)°, γ is 90°, and V is Preferably, the crystal parameters of compound 3 are: the crystal system is monoclinic, the space group is P121 / n1, and the unit cell parameter a is b is c is α is 90°, β is 104.374(2)°, γ is 90°, and V is Preferably, the crystal parameters of compound 4 are: the crystal system is monoclinic, the space group is P121 / n1, and the unit cell parameter a is b is c is α is 90°, β is 103.552(2)°, γ is 90°, and V is 6. The organic-inorganic hybrid {Ti3In} according to any one of claims 1 to 5 x A method for preparing a crystalline titanium indium oxide cluster patterned material, characterized in that: The following steps are involved: The material can be prepared by using an indium source, a titanium source, a ligand and a solvent through a solvent thermal synthesis method.

7. The preparation method according to claim 6, characterized in that: The indium source is selected from any one of the following: indium chloride, indium nitrate, indium acetate, indium sulfate and hydrates thereof; The titanium source is selected from any one of the following: titanium isopropoxide [Ti(O i Pr)4], titanium ethoxide, titanium butoxide; The ligand is selected from any one of the following: salicylic acid, 4-methylsalicylic acid, 5-fluorosalicylic acid, 5-nitrosalicylic acid and derivatives thereof.

8. A patterned composition, characterized in that The organic-inorganic hybrid {Ti3In} comprising any one of claims 1 to 5 x Type crystalline titanium indium oxide cluster patterning material.

9. A patterning method, characterized in that: The following steps are involved: 1) The organic-inorganic hybrid {Ti3In} according to any one of claims 1 to 5 x The crystalline titanium indium oxygen cluster patterned material is dissolved in a solvent, filtered, and attached to a substrate to form a patterned coating; 2) exposing the patterned coating to radiation; 3) The exposed coating is brought into contact with a developer to form a pattern of the coating material.

10. The organic-inorganic hybrid {Ti3In} according to any one of claims 1 to 5 x Application of crystalline titanium indium oxygen cluster patterning materials in the preparation of photoresists; Preferably, the photoresist is electron beam photoresist, UV photoresist, DUV photoresist, or EUV photoresist.

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