Titanium oxo-heterometallic cluster compounds, methods of making and using the same

Abstract

The application discloses a titanium-oxygen heterometallic cluster compound and a preparation method and application thereof. The titanium-oxygen heterometallic cluster compound is synthesized by using a one-pot method. By introducing a salicylic acid ligand, an In metal is butted against a skeleton of a titanium-oxygen cluster and simultaneously subjected to precise ligand modification, so that the synthesis difficulty of the existing titanium-oxygen cluster is solved, the problem of complex conditions is solved, and the problems of easy hydrolysis of titanium oxide and low synthesis purity are avoided. The titanium-oxygen heterometallic cluster compound prepared by the application can reach a line width resolution of 15 nm, and a line width ratio can reach 1:2, so that a finer, denser and more accurate circuit pattern can be engraved on a silicon wafer, the problem of insufficient precision of traditional photoresist photoetching is solved, and the application has a good popularization and application prospect.

Description

Technical Field

[0001] This invention relates to the field of photoresist materials technology, and in particular to a class of titanium oxide heterometallic cluster compounds, their preparation methods and applications. Background Technology

[0002] As the integration density of semiconductor devices continues to increase, the demand for smaller feature sizes continues to drive the evolution of photolithography technology. Currently, photolithography sources in semiconductor manufacturing have evolved to the 13.5 nm extreme ultraviolet (EUV) band. As one of the core technologies of advanced processes, EUV lithography places more stringent requirements on photoresist performance. The photon energy at 13.5 nm is approximately 92 eV, theoretically enabling half-pitch resolution of less than 10 nm. However, due to multiple energy losses caused by the mirror system, the effective dose actually reaching the photoresist surface is less than 2% of the incident energy. Given the limited power (≤100 W) and energy conversion efficiency of the EUV source, the exposure dose must be controlled at ≤10 mJ / cm² to meet yield requirements, thus requiring high sensitivity in the photoresist. Furthermore, EUV lithography can achieve direct imaging with half-pitches of less than 20 nm, which places even higher demands on the size of the photoresist material. While ensuring a line edge roughness (LER) ≤1.5 nm, the size of monomers or clusters must be less than 2 nm and uniformly distributed. Meanwhile, high numerical aperture (NA≥0.55) systems compress the depth of focus to below 50 nm, which means that the photoresist film thickness usually needs to be controlled within 30 nm, thus requiring the material to still have excellent etching resistance under ultra-thin film conditions.

[0003] Furthermore, EUV lithography enables direct imaging with a half-pitch of less than 20 nm, which places higher demands on the size of the photoresist material. While ensuring a line edge roughness (LER) ≤ 1.5 nm, the size of monomers or clusters must be less than 2 nm and uniformly distributed. Simultaneously, high numerical aperture (NA ≥ 0.55) systems compress the depth of focus to below 50 nm, requiring the photoresist film thickness to typically be controlled within 30 nm, thus demanding excellent etching resistance even under ultra-thin film conditions.

[0004] Metal-oxygen cluster photoresists possess the advantages of atomically precise structure and uniform nanoscale size distribution, which are beneficial for improving pattern resolution and reducing the line roughness of exposed patterns. Titanium (Ti) is located in the fourth period. Although this transition metal does not significantly absorb extreme ultraviolet light, titanium clusters can still obtain high-quality patterns under high exposure doses; however, pure titanium clusters cannot be directly used for photolithography due to their poor solubility. However, organotitanium compounds have been used to prepare titanium dioxide thin films on silicon wafers. Under ultraviolet irradiation, organotitanium compounds lose or decompose their organic ligands. In the field of photolithography, research on titanium-oxygen clusters remains very limited. Chinese patent application CN120718066 discloses an organometallic cluster (Ph3Sb)2(μ2-O)(L)2 and its preparation method, which involves dissolving RaM in a solvent, sequentially adding an organic ligand capable of coordinating with M, a peroxide, stirring, and then removing the solvent. However, the resulting cluster exhibits poor photolithographic performance.

[0005] Therefore, there is an urgent need to develop metal oxide cluster photoresist materials that combine excellent photolithography precision and etching resistance. Summary of the Invention

[0006] This invention aims to at least solve one of the aforementioned technical problems existing in the prior art. Therefore, the object of this invention is to provide a class of titanium oxide heterometallic cluster compounds, their preparation method, and applications. This invention employs a one-pot synthesis method for titanium oxide heterometallic cluster compounds. By introducing salicylic acid ligands—specifically, the structure obtained after salicylic acid (o-hydroxybenzoic acid) and its derivatives lose hydrogen from their carboxyl and / or hydroxyl groups—In metal is attached to the Ti oxide cluster framework while simultaneously performing precise ligand modification. The preparation method of this invention solves the problems of difficult and complex synthesis conditions in existing titanium oxide clusters, while also avoiding the problems of easy hydrolysis of titanium oxide and low synthetic purity.

[0007] To achieve the above objectives, the technical solution adopted by the present invention is as follows: In a first aspect, the present invention provides a titanium-oxygen heterometallic cluster compound, wherein the molecular formula of the titanium-oxygen heterometallic cluster compound is In. a Ti b (R') c (O) d (OCH3) e (CH3OH) f (H2O) g (H3O) h , where R' is the structure obtained by salicylic acid and its derivatives after losing hydrogen from the carboxyl group and / or hydroxyl group; 2≤a≤4; 8≤b≤12; 4≤c≤12; 7≤d≤14; 8≤e≤14; 0≤f≤4; 1≤g≤3; 0≤h≤3.

[0008] In some embodiments of the present invention, R' is the structure obtained by dehydrogenating salicylic acid and its derivatives and combining them with the In-Ti metal core of the titanium oxide heterometallic cluster compound.

[0009] In some embodiments of the present invention, the range of c is 7 ≤ c ≤ 12.

[0010] In some embodiments of the present invention, the derivatives of salicylic acid include 4-fluoro-2-hydroxybenzoic acid, 2-hydroxy-4-methylbenzoic acid, 2-hydroxy-4-(trifluoromethyl)benzoic acid, 3,5-di-tert-butylsalicylic acid, and 4-hydroxy-2-hydroxybenzoic acid. At least one of ethylene-2-hydroxybenzoic acid, 3,4-difluoro-2-hydroxybenzoic acid, 2-fluoro-6-hydroxybenzoic acid, 2,3-difluoro-6-hydroxybenzoic acid, 2-chloro-6-hydroxybenzoic acid, and 2-bromo-6-hydroxybenzoic acid.

[0011] In some embodiments of the present invention, the molecular formula of the titanium oxide heterometallic cluster compound includes at least one of the following: In2Ti8(SA)9O7(OCH3) 10 (H₂O)₂·MeOH;In₂Ti 10 (SA)7O 10 (OCH3) 14 (CH3OH)(H2O)·MeOH; In4Ti 12 (SA)8(SA-F)4O 14 (OCH3)8(CH3OH)4(H2O)2(H3O)3·MeOH; In4Ti 12 (SA-F) 12 O 14 (OCH3)8(CH3OH)2(H2O)2·MeOH; In4Ti 12 (SA-2F) 12 O 14 (OCH3)8(CH3OH)4(H2O)3(H3O)2·MeOH; In this context, SA represents salicylate, with the molecular formula C7H4O3; SA-F represents 5-fluorosalicylate, with the molecular formula C7H3FO3; SA-2F represents 2,3-difluoro-6-hydroxybenzoate, with the molecular formula C7H2F2O3; and MeOH represents methanol.

[0012] In some embodiments of the present invention, a in the molecular formula of the titanium oxide heterometallic cluster compound is 2, 3 or 4.

[0013] In some embodiments of the present invention, b is 8, 9, 10, 11 or 12 in the molecular formula of the titanium oxide heterometallic cluster compound.

[0014] In some embodiments of the present invention, the molecular formula of the titanium oxide heterometallic cluster compound is c 4, 5, 6, 7, 8, 9, 10, 11 or 12.

[0015] In some embodiments of the present invention, the molecular formula of the titanium oxide heterometallic cluster compound is d, which is 7, 8, 9, 10, 11 or 12.

[0016] In some embodiments of the present invention, the molecular formula of the titanium oxide heterometallic cluster compound is 8, 9, 10, 11, 12, 13 or 14.

[0017] In some embodiments of the present invention, f is 0, 1, 2, 3 or 4 in the molecular formula of the titanium oxide heterometallic cluster compound.

[0018] In some embodiments of the present invention, g in the molecular formula of the titanium oxide heterometallic cluster compound is 1, 2 or 3.

[0019] In some embodiments of the present invention, the molecular formula of the titanium oxide heterometallic cluster compound is 0, 1, 2 or 3.

[0020] A second aspect of the present invention provides a patterned composition comprising the titanium oxide heterometallic cluster compound described in the above aspects.

[0021] A third aspect of the present invention provides a method for preparing the titanium oxide heterometallic cluster compound described above, the method comprising the following steps: Dissolve salicylic acid and / or its derivatives, indium salt hydrate in an organic solvent, add titanate ester and mix evenly, heat at 50-100℃ for 1-7 days, and crystallize to obtain the titanium oxide heterometallic cluster compound. The indium salt hydrate includes at least one of indium chloride hydrate, indium nitrate hydrate, indium sulfate hydrate, indium acetate hydrate, and indium perchlorate hydrate; The titanate includes at least one of tetrabutyl titanate, tetraisopropyl titanate, and tetraethyl titanate.

[0022] In some embodiments of the present invention, the molar ratio of the indium salt hydrate, salicylic acid, salicylic acid derivative and titanate is (1-3):(0-3):(0-3):(1-3); wherein the molar ratio of salicylic acid and salicylic acid derivative is not simultaneously 0.

[0023] In some embodiments of the present invention, the molar ratio of the indium salt hydrate, salicylic acid, salicylic acid derivative and titanate is (1-2):(0-2):(0-2):(1-2); wherein the molar ratio of salicylic acid and salicylic acid derivative is not simultaneously 0.

[0024] In some embodiments of the present invention, the organic solvent includes at least one selected from methanol, ethanol, dichloromethane, trichloromethane, chlorobenzene, o-dichlorobenzene, 2-methoxyethanol, tetrahydrofuran, anisole, acetone, toluene, ethyl acetate, and butyl acetate.

[0025] In some embodiments of the present invention, dissolving salicylic acid and / or its derivatives, indium salt hydrates in an organic solvent includes dissolving salicylic acid and / or its derivatives, indium salt hydrates in methanol.

[0026] In some embodiments of the present invention, the indium hydrate includes at least one of In(OAc)3·H2O and In(NO3)3·H2O.

[0027] In some embodiments of the present invention, the titanate includes n-butyl titanate and isobutyl titanate.

[0028] In some embodiments of the present invention, the titanate is Ti(OBu)4.

[0029] In some embodiments of the present invention, the heating is carried out for 1-5 days.

[0030] In some embodiments of the present invention, the heating is carried out for 1-3 days.

[0031] In some embodiments of the present invention, the preparation method further includes a purification step of the reaction product.

[0032] In some embodiments of the present invention, the purification step includes filtration after crystallization and washing with an alcohol solvent.

[0033] A fourth aspect of the present invention provides a patterning method, the method comprising the following steps: The titanium oxide heterometallic cluster compound described above is dissolved in an organic solvent, coated onto a substrate to form a coating, and the coating is subjected to radiation exposure and development to obtain a patterned coating.

[0034] In some embodiments of the present invention, the developing solution is a solvent that can cause materials before and after irradiation to have different dissolution rates.

[0035] In some embodiments of the invention, the development includes developing with at least one of isopropanol, methyl isobutyl ketone, ethylene glycol monoethyl ether, 2-heptanone, and 5-nonanone.

[0036] In some embodiments of the invention, the developing process uses 2-heptanone and methyl isobutyl ketone.

[0037] In some embodiments of the present invention, the volume ratio of the amount of 2-heptanone to methyl isobutyl ketone used is 1-5:1.

[0038] In some embodiments of the present invention, the volume ratio of the amount of 2-heptanone to methyl isobutyl ketone used is 1-3:1.

[0039] In some embodiments of the present invention, the volume ratio of the amount of 2-heptanone to methyl isobutyl ketone used is 3:1.

[0040] In some embodiments of the present invention, the developing time is 10-120 seconds.

[0041] In some embodiments of the present invention, the developing time is 60 seconds.

[0042] In some embodiments of the present invention, the exposure dose is 50-1000 μC / cm. 2 .

[0043] In some embodiments of the present invention, the concentration of the titanium oxide heterometallic cluster compound dissolved in the organic solvent is 5-15 mg / mL.

[0044] In some embodiments of the present invention, the concentration of the titanium oxide heterometallic cluster compound dissolved in the organic solvent is 10 mg / mL.

[0045] In some embodiments of the present invention, dissolving the titanium oxide heterometallic cluster compound in an organic solvent includes dissolving the titanium oxide heterometallic cluster compound in at least one of propylene glycol methyl ether, dipropylene glycol methyl ether acetate, propylene glycol methyl ether, and ethyl lactate; the solvent for dissolving the titanium oxide heterometallic cluster compound is selected based on its high solubility and good film-forming properties after spin coating.

[0046] In some embodiments of the present invention, the radiation is selected from electron beams and light sources of ultraviolet, deep ultraviolet, extreme ultraviolet or shorter wavelengths.

[0047] A fifth aspect of the present invention provides the use of the titanium oxide heterometallic cluster compounds described above in the preparation of photoresists.

[0048] In some embodiments of the present invention, the photoresist includes at least one of electron beam photoresist, UV photoresist, DUV photoresist, and EUV photoresist.

[0049] The beneficial effects of this invention are: This invention discloses a class of titanium-oxygen heterometallic cluster compounds, their preparation methods, and applications. By introducing salicylic acid ligands—specifically, the structures obtained by losing hydrogen from the carboxyl and / or hydroxyl groups of salicylic acid (o-hydroxybenzoic acid) and its derivatives—and simultaneously performing precise ligand modification on the framework of the titanium-oxygen cluster, this invention aims to overcome the limitations of In-Ti oxygen cluster types and synthesis methods. It not only enriches the cluster structures but also allows for the co-assembly of photochemically reactive groups and In atoms with high extreme ultraviolet (EUV) absorption cross-sections with Ti elements with low EUV absorption cross-sections. As a polynuclear In-Ti oxide cluster compound, it helps to improve the sensitivity of photoresist materials, solves the problem of low absorption of titanium oxide clusters by EUV, increases the possibility of Ti oxide clusters as photoresist materials, and expands their application in the field of photolithography. At the same time, the present invention demonstrates through experiments that the salicylic acid ligand modified polynuclear metal In-Ti cluster compound prepared in this invention can achieve a linewidth resolution of 15nm, and the linewidth ratio can reach 1:2, which means that it can etch finer, denser and more precise circuit patterns on silicon wafers, solving the problem of insufficient photolithography precision of traditional photoresists.

[0050] This invention simplifies the synthesis of titanium oxide clusters by employing a one-pot method and introducing salicylic acid ligands, enhancing their designability and solving the problem of low EUV absorption by titanium oxide clusters. Existing methods for synthesizing titanium oxide clusters not only involve extremely demanding synthesis conditions but also result in the easy hydrolysis of the synthesized clusters. This invention's method for preparing salicylic acid ligand-modified polynuclear metal In-Ti cluster compounds overcomes the difficulties and complex conditions of existing titanium oxide cluster synthesis methods, while also avoiding the problems of easy hydrolysis of titanium oxide and low synthetic purity.

[0051] Meanwhile, the titanium oxide heterometallic cluster compounds of this invention enhance the patterning application of designable and synthesizable In-Ti oxide clusters. Existing patterned titanium oxide cluster compounds used in photolithography largely lack inherent photolithographic activity in their titanium oxide materials, making it difficult to undergo effective and necessary chemical reactions under electron beam irradiation. This invention modifies titanium oxide clusters by introducing the high EUV absorption element In in conjunction with salicylic acid ligands, adding photochemically reactive groups to the clusters and investigating their application in photolithography. This provides valuable reference for the synthesis of novel In-Ti oxide clusters and their application in photolithography. Furthermore, this invention significantly improves the etching resistance of these clusters by increasing the metal element content ratio and using salicylic acid ligands with rigid structures, solving the problem of poor etching resistance in traditional photoresists. Attached Figure Description

[0052] Figure 1 The compound of this invention is In2Ti8(SA)9O7(OCH3). 10 Schematic diagram of the structure of (H2O)2·MeOH.

[0053] Figure 2 The compound In2Ti of this invention 10 (SA)7O 10 (OCH3) 14 Schematic diagram of the structure of (CH3OH)(H2O)·MeOH.

[0054] Figure 3 The compound In4Ti of this invention 12 (SA)8(SA-F)4O 14 Schematic diagram of the structure of (OCH3)8(CH3OH)4(H2O)2(H3O)3·MeOH.

[0055] Figure 4 The compound In4Ti of this invention 12 (SA-F) 12 O 14 Schematic diagram of the structure of (OCH3)8(CH3OH)2(H2O)2·MeOH.

[0056] Figure 5 The compound In4Ti of this invention 12 (SA-2F) 12 O 14 Schematic diagram of the structure of (OCH3)8(CH3OH)4(H2O)3(H3O)2·MeOH.

[0057] Figure 6 The compound of this invention is In2Ti8(SA)9O7(OCH3). 10 X-ray diffraction pattern (P-XRD) of (H2O)2·MeOH.

[0058] Figure 7 The compound In2Ti of this invention 10 (SA)7O 10 (OCH3) 14 X-ray diffraction pattern (P-XRD) of (CH3OH)(H2O)·MeOH.

[0059] Figure 8 The compound In4Ti of this invention 12 (SA)8(SA-F)4O 14 X-ray diffraction pattern (P-XRD) of (OCH3)8(CH3OH)4(H2O)2(H3O)3·MeOH.

[0060] Figure 9 The compound In4Ti of this invention 12 (SA-F) 12 O 14X-ray diffraction pattern (P-XRD) of (OCH3)8(CH3OH)2(H2O)2·MeOH.

[0061] Figure 10 The compound In4Ti of this invention 12 (SA-2F) 12 O 14 X-ray diffraction pattern (P-XRD) of (OCH3)8(CH3OH)4(H2O)3(H3O)2·MeOH.

[0062] Figure 11 The compound of this invention is In2Ti8(SA)9O7(OCH3). 10 Nuclear magnetic resonance (NMR) spectrum of (H2O)2·MeOH.

[0063] Figure 12 The compound In2Ti of this invention 10 (SA)7O 10 (OCH3) 14 Nuclear magnetic resonance (NMR) spectrum of (CH3OH)(H2O)·MeOH.

[0064] Figure 13 The compound In4Ti of this invention 12 (SA)8(SA-F)4O 14 Nuclear magnetic resonance (NMR) spectrum of (OCH3)8(CH3OH)4(H2O)2(H3O)3·MeOH.

[0065] Figure 14 The compound In4Ti of this invention 12 (SA-F) 12 O 14 Nuclear magnetic resonance (NMR) spectrum of (OCH3)8(CH3OH)2(H2O)2·MeOH.

[0066] Figure 15 The compound In4Ti of this invention 12 (SA-2F) 12 O 14 Nuclear magnetic resonance (NMR) spectrum of (OCH3)8(CH3OH)4(H2O)3(H3O)2·MeOH.

[0067] Figure 16 The compound of this invention is In2Ti8(SA)9O7(OCH3). 10 Fourier transform infrared (FTIR) spectrum of (H2O)2·MeOH.

[0068] Figure 17 The compound In2Ti of this invention10 (SA)7O 10 (OCH3) 14 Fourier transform infrared (FTIR) spectrum of (CH3OH)(H2O)·MeOH.

[0069] Figure 18 The compound In4Ti of this invention 12 (SA)8(SA-F)4O 14 Fourier transform infrared (FTIR) spectrum of (OCH3)8(CH3OH)4(H2O)2(H3O)3·MeOH.

[0070] Figure 19 The compound In4Ti of this invention 12 (SA-F) 12 O 14 Fourier transform infrared (FTIR) spectrum of (OCH3)8(CH3OH)2(H2O)2·MeOH.

[0071] Figure 20 The compound In4Ti of this invention 12 (SA-2F) 12 O 14 Fourier transform infrared (FTIR) spectrum of (OCH3)8(CH3OH)4(H2O)3(H3O)2·MeOH.

[0072] Figure 21 The In2Ti8(SA)9O7(OCH3) of Embodiment 1 of the present invention 10 (H₂O)₂·MeOH cluster compounds at 72 μC / cm 2 Atomic force microscopy observation of the matrix pattern formed under the exposure dose.

[0073] Figure 22 The In2Ti8(SA)9O7(OCH3) of Embodiment 1 of the present invention 10 (H₂O)₂·MeOH cluster compounds at 50 μC / cm 2 An atomic force microscope image showing the formation of the school emblem pattern under the specified exposure dose.

[0074] Figure 23 The In2Ti8(SA)9O7(OCH3) of Embodiment 1 of the present invention 10 (H₂O)₂·MeOH cluster compounds at 683 μC / cm 2 Atomic force microscopy observation of the matrix pattern formed under the exposure dose.

[0075] Figure 24 The In2Ti8(SA)9O7(OCH3) of Embodiment 1 of the present invention10 (H₂O)₂·MeOH cluster compounds at 683 μC / cm 2 Atomic force microscopy observation of the matrix pattern formed under the exposure dose.

[0076] Figure 25 The In2Ti8(SA)9O7(OCH3) of Embodiment 1 of the present invention 10 (H₂O)₂·MeOH cluster compounds at 445 μC / cm 2 Atomic force microscopy observation of the matrix pattern formed under the exposure dose.

[0077] Figure 26 The In2Ti8(SA)9O7(OCH3) of Embodiment 1 of the present invention 10 (H₂O)₂·MeOH cluster compounds at 800 μC / cm 2 Scanning electron microscope image showing the matrix pattern formed under the exposure dose.

[0078] Figure 27 The In2Ti8(SA)9O7(OCH3) of Embodiment 1 of the present invention 10 (H₂O)₂·MeOH cluster compounds at 800 μC / cm 2 Scanning electron microscope image showing the matrix pattern formed under the exposure dose.

[0079] Figure 28 This is an atomic force microscope image taken before etching for the etching test.

[0080] Figure 29 This is an atomic force microscope image of the etching process after etching. Detailed Implementation

[0081] The present invention will be further described in detail below through specific embodiments. Unless otherwise specified, the raw materials, reagents, or apparatus used in the embodiments and comparative examples are all available from conventional commercial sources or can be obtained by existing technical methods. Unless otherwise specified, the experimental or testing methods are conventional methods in the art.

[0082] This invention employs a one-pot synthesis method for titanium-oxygen heterometallic cluster compounds. By introducing salicylic acid ligands, In metal is attached to the framework of Ti oxygen clusters while undergoing precise ligand modification, thus preparing a class of salicylic acid ligand-modified polynuclear Ti compounds, namely the titanium-oxygen heterometallic cluster compounds described in this invention. In these compounds, all Ti atoms are six-coordinated, with different types of oxygen atoms bridging to form the central framework. Both ends are coordinated with In by one or two salicylic acid ligands, as shown in the following general formula: In a Ti b (R')c (O) d (OCH3) e (CH3OH) f (H2O) g (H3O) h , where R' is the structure obtained by salicylic acid and its derivatives after losing hydrogen from the carboxyl group and / or hydroxyl group; 2≤a≤4; 8≤b≤12; 4≤c≤12; 7≤d≤14; 8≤e≤14; 0≤f≤4; 1≤g≤3; 0≤h≤3.

[0083] The present invention specifically prepared the following titanium-oxygen heterometallic cluster compounds: In2Ti8(SA)9O7(OCH3) 10 (H2O)2·MeOH; In2Ti 10 (SA)7O 10 (OCH3) 14 (CH3OH)(H2O)·MeOH; In4Ti 12 (SA)8(SA-F)4O 14 (OCH3)8(CH3OH)4(H2O)2(H3O)3·MeOH; In4Ti 12 (SA-F) 12 O 14 (OCH3)8(CH3OH)2(H2O)2·MeOH; In4Ti 12 (SA-2F) 12 O 14 (OCH3)8(CH3OH)4(H2O)3(H3O)2·MeOH.

[0084] SA represents salicylate, with the molecular formula C7H4O3; SA-F represents 5 Fluorosalicylate ion, with the molecular formula C7H3FO3; SA-2F represents 2,3-difluoro-6-hydroxybenzoate ion, with the molecular formula C7H2F2O3; MeOH represents methanol.

[0085] The steps for preparing photoresist using the compound of this invention for patterning applications include: 1. Silicon wafer processing: Cleaning the silicon wafers; 2. Film preparation: The prepared compound is dissolved in an organic solvent, spin-coated onto a silicon wafer to form a coating, and then the organic solvent is removed; 3. Exposure: The above material is exposed to selective electron beam irradiation. The irradiated part of the patterned material film undergoes a chemical change, and the solubility changes. The unirradiated part retains its original good solubility. The solubility of the exposed and unexposed areas in the developer solution is significantly different. During development, the unirradiated area is dissolved and removed, while the irradiated area is retained, forming the target pattern.

[0086] 4. Development: The silicon wafer is developed using a developer; the preferred developer is 2-heptanone and methyl isobutyl ketone, which can significantly improve the pattern quality; the preferred volume ratio of 2-heptanone and methyl isobutyl ketone is (1-3):1.

[0087] The present invention will now be described in detail through specific embodiments.

[0088] Example 1 This embodiment provides the compound In2Ti8(SA)9O7(OCH3) of the present invention. 10 The reagents used in the preparation of (H2O)2·MeOH were all from Shanghai Adamas Reagent Co., Ltd. (Adamas-beta), and all were of analytical grade (AR). The specific steps are as follows.

[0089] In(OAc)3·H2O (150 mg, approximately 0.5 mmol) and o-hydroxybenzoic acid (138 mg, approximately 1 mmol) were dissolved in 5 mL of methanol and sonicated for 10 min. Then, Ti(OBu)4 (170 μL, approximately 0.5 mmol) was added to the system and sonicated until homogeneous. The mixture was transferred to a sealed glass sample vial and placed in an 80 °C oven for 1 day. After the reaction, the sample was transferred to room temperature and allowed to stand to allow crystallization. When crystals precipitated and the mother liquor volume was reduced to 2 / 3, the solid product was obtained by filtration. The solid product was washed several times with excess ethanol to obtain pure, transparent, golden-yellow needle-like single crystals. These crystals were then placed at room temperature to obtain the compound In2Ti8(SA)9O7(OCH3). 10 (H₂O)₂·MeOH has the following crystal parameters: space group P₂₁, cell parameters a = 11.9132(4) Å, b = 20.3944 Å, c = 21.9193(8) Å, α = 90°, β = 98.043(2)°, γ = 90°, and V = 5273.2(3) Å. 3 .

[0090] Compound In2Ti8(SA)9O7(OCH3) 10 The structure of (H2O)2·MeOH is as follows: Figure 1As shown, the tetrahedral [In1Ti4O3(OCH3)5(SA)4] fragments are linked together by ligands of oxygen and salicylic acid. Compound In2Ti8(SA)9O7(OCH3) 10 The X-ray diffraction pattern (P-XRD) of (H2O)2·MeOH is shown below. Figure 6 As shown, the synthesized In-Ti clusters have high purity. The nuclear magnetic resonance (NMR) spectrum is shown below. Figure 11 As shown, the integral number and peak position match the single-crystal XRD data, NMR data: 1 ¹H NMR (500 MHz, DMSO-d⁶) δ 7.91–7.75 (m, 14H), 7.55–7.23 (m, 15H), 7.01–6.85 (m, 22H), 6.49 (d, J = 49.3 Hz, 5H), 3.17 (s, 3H). Fourier transform infrared (FTIR) spectrum as follows: Figure 16 As shown, 3000-2800cm -1 Significant CH stretching vibration absorption was observed in the region (approximately 2900 cm). -1 The strongest, corresponding to asymmetric CH2 / CH3; 2800 cm -1 (for symmetrical expansion and contraction), and at 3000 cm -1 There are faint spikes nearby (classified as sp). 2 CH or olefin / aromatic CH), at 2700 cm -1 There is a weak peak at that point (possibly the Fermi resonance absorption of the aldehyde group).

[0091] Example 2 This embodiment provides the compound In2Ti of the present invention. 10 (SA)7O 10 (OCH3) 14 The reagents used in the preparation of (CH3OH)(H2O)·MeOH were all from Shanghai Adamas Reagent Co., Ltd. (Adamas-beta), and all were of analytical grade (AR). The specific steps are as follows.

[0092] In(OAc)3·H2O (309 mg, approximately 1 mmol), o-hydroxybenzoic acid (138 mg, approximately 1 mmol), and 2-fluoro-6-hydroxybenzoic acid (156 mg, 1 mmol) were mixed thoroughly and placed in a 20 mL glass vial. 10 mL of methanol was added, and the mixture was sonicated for 10 min to dissolve. Then, Ti(OBu)4 (340 μL, approximately 1 mmol) was added to the system and sonicated thoroughly. The mixture was transferred to a sealed glass sample vial and placed in an 80 °C oven for 3 days. After allowing it to stand at room temperature to evaporate, pure, yellow, transparent, blocky single crystals were obtained, which is the compound In2Ti. 10 (SA)7O 10 (OCH3) 14 (CH3OH)(H2O)·MeOH has the following crystal parameters: space group P21 / c, cell parameters a = 16.9038(5) Å, b = 19.9698(5) Å, c = 15.9058(5) Å, α = 90°, β = 108.699(3)°, γ = 90°, and V = 5085.8(3) Å. 3 .

[0093] compound In2Ti 10 (SA)7O 10 (OCH3) 14 The structure of (CH3OH)(H2O)·MeOH is as follows: Figure 2 As shown, the tetrahedral [In1Ti5O5(OCH3)7(SA)3] segments are linked together by bridging oxygen atoms. Compound In2Ti 10 (SA)7O 10 (OCH3) 14 The X-ray diffraction pattern (P-XRD) of (CH3OH)(H2O)·MeOH is shown below. Figure 7 As shown, the synthesized InTi clusters have high purity. The nuclear magnetic resonance (NMR) spectrum is shown below. Figure 12 As shown, the integral number and peak position match the single-crystal XRD data, NMR data: 1 H NMR (500 MHz, DMSO- d 6) δ 7.79 (dd, J =8.0, 1.8 Hz, 22H), 7.54-7.30 (m,25H), 6.98-6.87(m, 42H), 6.71 (dd, J =26.4 (8.3 Hz, 2H), 3.17 (s, 2H). Fourier transform infrared (FTIR) spectrum as follows: Figure 17 As shown, it is located at 3400 cm. -1The broad absorption peak in the vicinity is attributed to the stretching vibration of coordinated methanol and OH groups in water. (1720 cm⁻¹) -1 There is no free carboxylic acid C=O peak at this location, but a broadened COO peak is observed. - The spectral bands confirm that the carboxylic acid ligand was successfully coordinated at the In / Ti center. 1100–1000 cm⁻¹ -1 The strong absorption in the region corresponds to CO and MOC vibrations, while at 800 cm⁻¹ -1 The following low-frequency band confirms the formation of metal-oxygen bond networks such as In-O-Ti and Ti-O-Ti.

[0094] Example 3 This embodiment provides the compound In4Ti of the present invention. 12 (SA)8(SA-F)4O 14 The preparation of (OCH3)8(CH3OH)4(H2O)2(H3O)3·MeOH used reagents from Shanghai Adamas Reagent Co., Ltd. (Adamas-beta), all of which were of analytical grade (AR). The specific steps are as follows.

[0095] In(NO3)3·H2O (300 mg, approx. 1 mmol), o-hydroxybenzoic acid (138 mg, approx. 1 mmol), and 2-fluoro-6-hydroxybenzoic acid (156 mg, approx. 1 mmol) were mixed thoroughly and placed in a 20 mL glass vial. 10 mL of methanol was added, and the mixture was sonicated for 10 min to dissolve. Then, Ti(OBu)4 (340 μL, approx. 1 mmol) was added to the system and sonicated thoroughly. The mixture was transferred to a sealed glass sample vial and placed in an 80 °C oven for 3 days. After allowing it to stand at room temperature to evaporate, pure, yellow, transparent, blocky single crystals were obtained, which is the compound In4Ti. 12 (SA)8(SA-F)4O 14 The crystal parameters of (OCH3)8(CH3OH)4(H2O)2(H3O)3·MeOH are as follows: space group P42 / nmc, cell parameters a = 20.1322(11) Å, b = 20.1322(11) Å, c = 15.9853(12) Å, α = 90°, β = 90°, γ = 90°, and V = 6478.9(9) Å. 3 .

[0096] compound In4Ti 12 (SA)8(SA-F)4O 14 The structure of (OCH3)8(CH3OH)4(H2O)2(H3O)3·MeOH is as follows: Figure 3As shown, the tetrahedral [In2Ti6O7(OCH3)4(SA)4(SA-F)2] segments are linked together by oxygen linkages. The compound In4Ti 12 (SA)8(SA-F)4O 14 The X-ray diffraction pattern (P-XRD) of (OCH3)8(CH3OH)4(H2O)2(H3O)3·MeOH is shown below. Figure 8 As shown, the synthesized InTi clusters have high purity. The nuclear magnetic resonance (NMR) spectrum is shown below. Figure 13 As shown, the integral number and peak position match the single-crystal XRD data, NMR data: 1 H NMR (500MHz, DMSO- d 6) δ 7.79 (dd, J =7.8,1.8Hz, 20H), 7.54-7.47 (m, 20H), 7.37 (td, J = 8.4, 6.5 Hz, 11H), 6.97-6.88 (m, 40H), 6.78-6.66 (m, 19H), 3.17 (s, 6H). Fourier transform infrared spectrum (FTIR) as follows: Figure 18 As shown, 3400 cm -1 The broad absorption peaks in the vicinity are attributed to the OH stretching vibrations of coordinated methanol, water molecules, and residual hydroxyl groups. Compared to the unfluorinated sample, the CH stretching vibration intensity is reduced, indicating that some hydrogen-containing ligands have been replaced by fluorinated ligands. (1600–1400 cm⁻¹) -1 The strong and split absorption peaks in the region confirm that various carboxylic acid ligands coordinate with the metal center under different coordination conditions. (1300–1000 cm⁻¹) -1 The enhanced absorption between them corresponds to the overlap of CF, CO and MOC vibrations, which verifies that the fluorinated ligand has been introduced into the cluster structure.

[0097] Example 4 This embodiment provides the compound In4Ti of the present invention. 12 (SA-F) 12 O 14 The preparation of (OCH3)8(CH3OH)2(H2O)2·MeOH used reagents from Shanghai Adamas Reagent Co., Ltd. (Adamas-beta), all of which were of analytical grade (AR). The specific steps are as follows.

[0098] In(NO3)3·H2O (300 mg, approximately 1 mmol) and 2-fluoro-6-hydroxybenzoic acid (312 mg, approximately 2 mmol) were mixed thoroughly and placed in a 20 mL glass vial. 10 mL of methanol was added, and the mixture was sonicated for 10 min to dissolve. Then, Ti(OBu)4 (340 μL, approximately 1 mmol) was added to the system and sonicated thoroughly. The mixture was transferred to a sealed glass sample vial and placed in an 80 °C oven for 5 days. After allowing it to stand at room temperature to evaporate, pure, yellow, transparent, blocky single crystals were obtained, which is the compound In4Ti. 12 (SA-F) 12 O 14 The crystal parameters of (OCH3)8(CH3OH)2(H2O)2·MeOH are as follows: space group P-421c, cell parameters a = 20.2118(9) Å, b = 20.2118(9) Å, c = 16.1648(11) Å, α = 90°, β = 90°, γ = 90°, and V = 6603.6(7) Å. 3 .

[0099] compound In4Ti 12 (SA-F) 12 O 14 The structure of (OCH3)8(CH3OH)2(H2O)2·MeOH is as follows: Figure 4 As shown, the tetrahedral [In2Ti6O7(OCH3)4(SA-F)6] segments are linked together by oxygen linkages. The compound In4Ti 12 (SA-F) 12 O 14 The X-ray diffraction pattern (P-XRD) of (OCH3)8(CH3OH)2(H2O)2·MeOH is shown below. Figure 9 As shown, the synthesized In-Ti clusters have high purity. The nuclear magnetic resonance (NMR) spectrum is as follows: Figure 14 As shown, the integral number and peak position match the single-crystal XRD data, NMR data: 1 H NMR (500 MHz, DMSO- d 6) δ 7.41-7.34 (m, 21H), 6.71(d, J =8.5 Hz,12H), 6.66-6.59 (m,16H), 6.31(dd, J =11.2 (8.0 Hz, 14H), 3.17 (s, 14H). Fourier transform infrared (FTIR) spectrum as follows: Figure 19 As shown, 3000–2800 cm -1The weakening of C–H stretching vibrations in the region indicates that hydrogen-containing ligands have been extensively substituted by fluorinated ligands; 1300–1000 cm -1 The strong absorption primarily originates from the C–F stretching vibration, which overlaps with C–O and M–O–C vibrations, confirming that the fluorinated ligands are dominantly bound to the cluster framework. The carboxylate-related absorption becomes sharper and more resolved, indicating a more homogeneous coordination environment between the In and Ti centers. (800 cm⁻¹) -1 The following strong low-wavenumber absorption confirms the formation of a highly condensed and ordered metal-oxygen framework composed of In–O–Ti and Ti–O–Ti bonds. These results demonstrate that fluorination promotes the structural homogeneity and degree of condensation of the metal-oxygen clusters.

[0100] Example 5 This embodiment provides the compound In4Ti of the present invention. 12 (SA-2F) 12 O 14 The preparation of (OCH3)8(CH3OH)4(H2O)3(H3O)2·MeOH used reagents from Shanghai Adamas Reagent Co., Ltd. (Adamas-beta), all of which were of analytical grade (AR). The specific steps are as follows.

[0101] In(NO3)3·H2O (150 mg, approximately 1 mmol) and 2,3-difluoro-6-hydroxybenzoic acid (174.1 mg, approximately 1 mmol) were mixed thoroughly and placed in a 20 mL glass vial. 10 mL of methanol was added, and the mixture was sonicated for 10 min to dissolve. Then, Ti(OBu)4 (170 μL, approximately 0.5 mmol) was added to the system and sonicated thoroughly. The mixture was transferred to a sealed glass sample vial and reacted in an 80 °C oven for 5 days. Afterward, the mixture was allowed to stand at room temperature to evaporate, yielding pure, yellow, transparent, blocky single crystals, which is the compound In4Ti. 12 (SA-2F) 12 O 14 The crystal parameters of (OCH3)8(CH3OH)4(H2O)3(H3O)2·MeOH are as follows: space group P-1, cell parameters a = 18.1949(5) Å, b = 19.1721(5) Å, c = 21.3658(6) Å, α = 80.6050(10)°, β = 88.6550(10)°, γ = 85.1690(10)°, and V = 7326.7(3) Å. 3 .

[0102] compound In4Ti 12 (SA-2F) 12 O 14 The structure of (OCH3)8(CH3OH)4(H2O)3(H3O)2·MeOH is as follows: Figure 5 As shown, the tetrahedral [In2Ti6O7(OCH3)4(SA-2F)6] segments are linked together by oxygen linkages. The compound In4Ti 12 (SA-2F) 12 O 14 The X-ray diffraction pattern (P-XRD) of (OCH3)8(CH3OH)4(H2O)3(H3O)2·MeOH is shown below. Figure 10 As shown, the synthesized InTi clusters have high purity. The nuclear magnetic resonance (NMR) spectrum is shown below. Figure 15 As shown, the integral number and peak position match the single-crystal XRD data, NMR data: 1 H NMR (500 MHz, DMSO- d 6) δ 7.44 (q, J =9.5 Hz, 46H), 7.22 (t, J =9.6 Hz, 7H), 6.72(ddd, J =9.4, 3.9, 1.9Hz, 35H), 6.40(s, 12H), 6.19(s, 7H), 3.17(s, 6H). Fourier transform infrared (FTIR) spectrum as follows: Figure 20 As shown, 1600–1400 cm -1 The strong splitting of the carboxylate absorption interval indicates enhanced metal-carboxylate interactions, suggesting that the coordination environments of In and Ti centers are becoming more ionic. (1300–900 cm⁻¹) -1 The highly enhanced and complex absorption regions primarily arise from the overlap of C–F, C–O, and M–O–C vibrations, confirming the dominant binding of difluorinated ligands to the cluster framework. (800 cm⁻¹) -1 The sharp absorption below indicates the formation of a highly ordered metal-oxygen network consisting of In–O–Ti and Ti–O–Ti bonds.

[0103] Example 6 This embodiment provides the In2Ti8(SA)9O7(OCH3) obtained in Example 1. 10 The following are the specific steps for testing the preparation of photoresist using (H2O)2·MeOH compounds for patterning applications.

[0104] 1. Silicon wafer processing Immerse the silicon wafer in acetone and ultrasonically clean it for 5-15 minutes. Remove the silicon wafer and ultrasonically clean it in isopropanol (IPA) for 5-10 minutes. Dry it with nitrogen gas. Then, put the treated silicon wafer into deionized water and ultrasonically clean it for 5-10 minutes. Dry it with nitrogen gas. Heat it to 100°C and then let it cool naturally to obtain a clean and dry silicon wafer surface for subsequent patterning processing. 2. Film preparation The compound In2Ti8(SA)9O7(OCH3) prepared in Example 1 was used. 10 (H2O)2·MeOH was dissolved in propylene glycol methyl ether at a final concentration of 10 mg / mL. The solution was filtered through a filter membrane, and then the filtered solution was directly spin-coated onto a silicon wafer with a hydrophilic surface to form a coating. The specific spin-coating steps were as follows: first, spin-coating was performed at 1000 rpm for 10 seconds to spread the solution evenly, and then spin-coating was performed at 4000 rpm for 1 minute. After spin-coating, pre-baking was performed at 85°C for 60 seconds to remove the solvent. 3 Exposure The material was exposed using electron beam lithography (EBL) at an accelerating voltage of 20 keV and a beam current of 0.01043 nA to form a line pattern. Specifically, after selective electron beam irradiation, the irradiated portions of the patterned material film underwent chemical changes, resulting in altered solubility. The unirradiated portions, however, retained their original good solubility. This created a significant difference in solubility between the exposed and unexposed areas in the developing solution. During development, the unirradiated areas were dissolved and removed, while the irradiated areas were preserved, thus forming the target pattern.

[0105] 4. Development The silicon wafer was developed by immersing it in 2-heptanone and methyl isobutyl ketone (volume ratio 3:1) for 60 seconds at room temperature. The wafer was then removed and rinsed in isopropanol (IPA) for 30 seconds to terminate the development. Finally, it was dried with a nitrogen gun and the pattern was characterized using atomic force microscopy (AFM) and scanning electron microscopy (SEM).

[0106] Experimental results are as follows Figure 21-27 As shown, all patterned end products are negative patterned. Figure 21 The exposure dose is 72 μC / cm 2 The width of the exposed rectangle was 2 μm, as characterized by atomic force microscopy (AFM). Figure 22 The exposure dose is 50 μC / cm 2 The width of the exposed school emblem was characterized as 5 μm using atomic force microscopy (AFM). Figure 23 The exposure dose was 683 μC / cm. 2 The exposed matrix pattern width was characterized using atomic force microscopy (AFM). Figure 24 The exposure dose was 683 μC / cm. 2 The exposed matrix pattern width was characterized using atomic force microscopy (AFM). Figure 25 The exposure dose was 445 μC / cm. 2 The exposed matrix pattern width was characterized using atomic force microscopy (AFM). Figure 26The exposure dose is 800 μC / cm 2 The exposed matrix pattern width was characterized using scanning electron microscopy (SEM). Figure 27 The exposure dose is 800 μC / cm 2 The exposed matrix pattern width was characterized using scanning electron microscopy (SEM). The AFM and SEM pattern data above clearly demonstrate the characteristics of In₂Ti₈(SA)₉O₇(OCH₃). 10 The (H₂O)₂·MeOH compound exhibits excellent photolithographic properties, achieving extremely low linewidths below 20 nm while maintaining excellent patterning. Based on the minimum linewidth data, it can be seen that the In₂Ti₈(SA)₉O₇(OCH₃) compound of this invention... 10 The (H2O)2·MeOH compound can achieve extremely low linewidth (15 nm) and excellent resolution. Therefore, the compound of the present invention has excellent photolithography performance.

[0107] 5. Etching Test The photoresist to be tested was spin-coated onto a silicon substrate, and after EBL exposure and development, a pattern (linewidth 300 nm, spacing 600 nm) was formed. Etching tests were performed using the following etching parameters: SF6 flow rate 50 sccm; pressure 2.5 × 10⁻⁶. -3 Torr, RIE power 15 W, ICP power 400 W, time 120 s. The photoresist data can be calculated by comparing the AFM data of the patterns before and after etching, using the compound In2Ti8(SA)9O7(OCH3). 10 Etching tests were performed using (H₂O)₂·MeOH, and the AFM data before etching were as follows: Figure 28 The AFM data shown and after etching are as follows: Figure 29 As shown, the compound In2Ti8(SA)9O7(OCH3) was calculated using the following formula. 10 The etching rate of the photoresist prepared by (H2O)2·MeOH was 0.385 nm / s.

[0108] V si =H Si / t0=170.657 nm / 120 s=1.422 nm / s; t1 = h si / V si =111.202 nm / 1.422 nm / s=78.2 s; Compound In2Ti8(SA)9O7(OCH3) 10 The etching rate V of the photoresist prepared by (H2O)2·MeOH In2Ti8 =H Si / t0= 30.182 nm / 78.2 s=0.385 nm / s; V si : Silicon wafer etching rate; H si : Height difference between etched and unetched portions of the silicon wafer (170.657 nm). h si The height difference of the pattern after photoresist over-etching; t0: Total etching time set in the etching process; t1: Duration of over-etching of the photoresist.

[0109] The above experimental results demonstrate that the titanium oxide heterometallic cluster compound In2Ti8(SA)9O7(OCH3) synthesized by the preparation method in Example 1 of this invention... 10 (H2O)2·MeOH can achieve a linewidth resolution of 15nm, and the linewidth ratio can reach 1:2, which means that it can etch finer, denser and more precise circuit patterns on silicon wafers, solving the problem of insufficient photolithography precision of traditional photoresists.

[0110] The titanium oxide heterometallic cluster compounds of this invention avoid the traditional complex synthesis route of Ti clusters and the instability of synthesis. They are small in size and uniformly distributed, and the surface roughness Rq after film formation can be less than 1 nm, which is beneficial to the formation of photolithographic patterns. The In element has a high extreme ultraviolet light (EUV) absorption cross section to reduce the exposure dose required for patterning applications. At the same time, these rigid benzoic acid ligands can improve the etching resistance of their photolithographic patterns.

[0111] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A titanium oxide heterometallic cluster compound, characterized in that, The molecular formula of the titanium oxide heterometallic cluster compound is In a Ti b (R') c (O) d (OCH3) e (CH3OH) f (H2O) g (H3O) h , where R' is the structure obtained by salicylic acid and its derivatives after losing hydrogen from the carboxyl group and / or hydroxyl group; 2≤a≤4; 8≤b≤12; 4≤c≤12; 7≤d≤14; 8≤e≤14; 0≤f≤4; 1≤g≤3; 0≤h≤3.

2. The titanium oxide heterometallic cluster compound according to claim 1, characterized in that, The derivatives of salicylic acid include 4-fluoro-2-hydroxybenzoic acid, 2-hydroxy-4-methylbenzoic acid, 2-hydroxy-4-(trifluoromethyl)benzoic acid, 3,5-di-tert-butylsalicylic acid, and 4... At least one of ethylene-2-hydroxybenzoic acid, 3,4-difluoro-2-hydroxybenzoic acid, 2-fluoro-6-hydroxybenzoic acid, 2,3-difluoro-6-hydroxybenzoic acid, 2-chloro-6-hydroxybenzoic acid, and 2-bromo-6-hydroxybenzoic acid.

3. The titanium oxide heterometallic cluster compound according to claim 1, characterized in that, The molecular formula of the titanium oxide heterometallic cluster compound includes at least one of the following: In2Ti8(SA)9O7(OCH3) 10 (H2O)2·MeOH;In2Ti 10 (SA)7O 10 (OCH3) 14 (CH3OH)(H2O)·MeOH; In4Ti 12 (SA)8(SA-F)4O 14 (OCH3)8(CH3OH)4(H2O)2(H3O)3·MeOH; In4Ti 12 (SA-F) 12 O 14 (OCH3)8(CH3OH)2(H2O)2·MeOH; In4Ti 12 (SA-2F) 12 O 14 (OCH3)8(CH3OH)4(H2O)3(H3O)2·MeOH。 4. A patterned composition, characterized in that, The patterned composition comprises the titanium oxide heterometallic cluster compound according to any one of claims 1-3.

5. The method for preparing the titanium oxide heterometallic cluster compound according to any one of claims 1-3, characterized in that, The preparation method includes the following steps: Dissolve salicylic acid and / or its derivatives, indium salt hydrate in an organic solvent, add titanate ester and mix evenly, heat at 50-100℃ for 1-7 days, and crystallize to obtain the titanium oxide heterometallic cluster compound. The indium salt hydrate includes at least one of indium chloride hydrate, indium nitrate hydrate, indium sulfate hydrate, indium acetate hydrate, and indium perchlorate hydrate; The titanate includes at least one of tetrabutyl titanate, tetraisopropyl titanate, and tetraethyl titanate.

6. The preparation method according to claim 5, characterized in that, The molar ratio of the indium salt hydrate, salicylic acid, salicylic acid derivative and titanate is (1-3):(0-3):(0-3):(1-3).

7. A patterning method, characterized in that, The method includes the following steps: The titanium oxide heterometallic cluster compound of any one of claims 1-3 is dissolved in an organic solvent, coated onto a substrate to form a coating, and the coating is subjected to radiation exposure and development to obtain a patterned coating.

8. The patterning method according to claim 7, characterized in that, The development includes developing with at least one of isopropanol, methyl isobutyl ketone, ethylene glycol monoethyl ether, 2-heptanone, and 5-nonanone.

9. The use of the titanium oxide heterometallic cluster compound according to any one of claims 1-3 in the preparation of photoresists.

10. The application according to claim 9, characterized in that, The photoresist includes at least one of electron beam photoresist, UV photoresist, DUV photoresist, and EUV photoresist.

Images