Method for realizing patterning by controlling hydrolysis of titanium-containing oxygen cluster material with ligand exchange characteristic

Abstract

The invention discloses a method for realizing patterning by controlling hydrolysis of a titanium-containing oxygen cluster material with a ligand exchange characteristic, and the titanium-containing oxygen cluster material and a synthesis method thereof. The invention provides a method and a plurality of embodiments for designing and synthesizing a titanium-containing oxygen cluster material, the general formula of the titanium-containing oxygen cluster material is [Bi4Ti12O18L24], and L comprises but is not limited to any alkoxyalcohol, alcohol containing halogen, S, N and P elements, and alcohol ligand containing unsaturated bonds. The patterning method comprises the following steps: dissolving and filtering a titanium-containing oxygen cluster material, spin-coating the titanium-containing oxygen cluster material on a substrate, after radiation of a light source, accelerating hydrolytic polymerization of an exposed region, and forming solubility difference with an unexposed region, so that fine lines or complex patterns can be realized after development. The invention provides a novel patterning method based on hydrolysis and condensation polymerization of titanium-containing oxygen clusters, breaks through the limitation that patterns are formed on the basis of cross-linking, bond breaking or hydrophilic and hydrophobic changes of traditional photoresist, and has great application prospects in the fields of photoetching, photocatalysis, electrocatalysis and solar cells.

Description

Technical Field

[0001] The present invention relates to the technical fields of crystal material preparation and photoresist preparation, specifically: a synthesis method of a class of titanium-oxo cluster materials with ligand exchange characteristics; a method for patterning by radiation-induced regulation of the hydrolysis process of titanium-oxo clusters. Background Art

[0002] Metal-oxide clusters (MOCs) are crystalline molecular clusters formed by connecting multiple metals with multiple oxygen atoms, having uniform particle size, atomically precise structure, and modifiable surface modification. Constructing oxo-cluster materials with definite composition and novel structure and exploring their physical and chemical properties and potential performance in the fields of applied chemistry and materials science have become the focus and research hotspot of scientific researchers in recent years. Among them, titanium-oxo clusters are the structural models of titanium dioxide materials, not only having novel and unique structures, but also showing great potential in the fields of lithography, photocatalysis, electrocatalysis, and solar cells. Conducting research on titanium-oxo cluster materials can not only enrich the structural diversity of heterometallic oxo clusters, but also broaden the application of oxo-cluster-based functional materials. However, the reported titanium-oxo cluster materials currently have problems such as poor solution stability, limited ligand modifiability, and insufficient application research. Therefore, it is particularly important and necessary to develop new synthesis strategies to prepare titanium-oxo cluster materials with ligand exchange characteristics after synthesis and deeply study their applications in the fields of lithography, photocatalysis, electrocatalysis, solar cells, etc.

[0003] A photoresist, also known as a photo-resist, is an anti-etching photosensitive thin film material whose solubility changes due to cross-linking, bond-breaking, or hydrophilic-hydrophobic changes caused by radiation or irradiation with electron beams, ultraviolet light, X-rays, or ion beam light sources. In the development process of positive photoresists, the exposed parts are removed, and in the development process of negative photoresists, the unexposed parts are removed. The currently reported negative photoresists are mainly prepared by a cross-linking mechanism, that is, small molecules break bonds and cross-link and polymerize after irradiation, making them insoluble in the developer. Summary of the Invention

[0004] One of the purposes of the present invention is to provide a method for patterning by controlling the hydrolysis of titanium-oxo cluster materials with ligand exchange characteristics, that is, a method for patterning of alkoxy-modified titanium-oxo clusters by radiation-induced hydrolysis, which broadens the field of photoresist materials and is of great significance for the development of fine line patterning. Another purpose of the present invention is to provide a class of titanium-oxo cluster materials with high solution stability and ligand exchange characteristics and their synthesis methods, which are used to solve the problems of poor solution stability, limited ligand modifiability, and lack of application research of titanium-oxo cluster materials.

[0005] Titanium-oxo clusters are sensitive to moisture and unstable, and are extremely prone to hydrolysis, resulting in changes in structure and properties. The soluble titanium-oxo clusters become insoluble materials after hydrolysis and polycondensation, which may exhibit the application potential of negative photoresists. Compared with the crosslinking, bond-breaking, and hydrophilic-hydrophobic transition mechanisms relied on by traditional photoresists, solubility regulation driven by hydrolysis reactions can be used as an innovative patterning method.

[0006] The technical solution of the present invention

[0007] A method for patterning by controlling the hydrolysis of a titanium-oxo cluster material with ligand exchange properties, comprising:

[0008] (1) Dissolve a hydrolyzable titanium-oxo cluster material in a solvent, filter, and spin-coat it on a substrate to form a patterned coating;

[0009] (2) Irradiate and expose a predetermined position of the coating in step (1) to induce the accelerated hydrolysis and polycondensation reactions in the exposed area to generate an organic solvent-insoluble substance, making the exposed area different from the unexposed area;

[0010] (3) Develop the coating to wash away the unexposed area to achieve fine lines or complex patterns.

[0011] In some embodiments, the substrate may be a silicon wafer or a silicon dioxide wafer;

[0012] The solvent is a solvent that can completely dissolve the titanium-oxo cluster material, including but not limited to ethyl lactate, propylene glycol monomethyl ether, cyclohexanone, or methyl isobutyl carbinol;

[0013] The radiation exposure source is one of deep ultraviolet light, extreme ultraviolet light, ultraviolet light, or an electron beam;

[0014] The developer is a solvent that can completely dissolve the exposed area and make the unexposed area insoluble, including but not limited to one or a mixed solvent of n-hexane, cyclohexane, DMF, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, cyclohexanone, acetonitrile, diethyl ether, acetone, methyl ethyl ketone, ethyl acetate, ethyl lactate, and propylene glycol monomethyl ether.

[0015] The present invention also provides a class of high-solution-stability titanium-oxo cluster materials with ligand exchange properties for implementing the above patterning method, and the general composition formula is: [Bi4Ti 12 O 18 L 24 , where L includes but is not limited to any one of alkoxy alcohols, alcohols containing halogen, S, N, P elements, and alcohol ligands containing unsaturated bonds.

[0016] In some embodiments, the titanium-oxo cluster material includes but is not limited to any one of the following:

[0017] (1) [Bi4Ti 12 O 18 L 24 , L = ethanol;

[0018] The molecular formula is C 48 H 120 O 42 Bi4Ti 12 , Mr = 2779.7668; The space group is P42 / n, and the unit cell parameters are α = 90°, β = 90°, γ = 90°,

[0019] (2) [Bi4Ti 12 O 18 L 24 , L = n-propanol;

[0020] The molecular formula is C 72 H 168 O 42 Bi4Ti 12 , Mr = 3116.4047; The space group is Pcca, and the unit cell parameters are α = 90°, β = 90°, γ = 90°,

[0021] (3) [Bi4Ti 12 O 18 L 24 , L = methanol;

[0022] The molecular formula is C 24 H 72 O 42 Bi4Ti 12 , Mr = 2443.1289; The space group is P21 / c, and the unit cell parameters are α = 90°, β = 107.9251(17)°, γ = 90°,

[0023]

[0024] (4) [Bi4Ti 12 O 18 L 24 , L = isopropanol;

[0025] The molecular formula is C 72 H 168 O 42 Bi4Ti 12, Mr = 3116.4047; The space group is Cmcm, and the unit cell parameters are α = 90°, β = 90°, γ = 90°,

[0026] (5)[Bi4Ti 12 O 18 L 24 , L = phenol;

[0027] The molecular formula is C 144 H 120 O 42 Bi4Ti 12 , Mr = 3932.7940; The space group is Pcca, and the unit cell parameters are α = 90°, β = 90°, γ = 90°,

[0028] (6)[Bi4Ti 12 O 18 L 24 , L = 2-fluoroethanol;

[0029] The molecular formula is C 48 H 96 F 24 O 42 Bi4Ti 12 , Mr = 3211.5379; The space group is P42 / n, and the unit cell parameters are α = 90°, β = 90°, γ = 90°,

[0030] The present invention also provides a synthesis method of the titanium-oxo cluster material with ligand exchange properties, which can be synthesized by a solvothermal method, including:

[0031] 1) Mix the titanium source, bismuth source, and solvent evenly, heat after ultrasonic treatment, and cool to room temperature to obtain a mixture;

[0032] 2) Wash the obtained mixture with an alcohol solvent multiple times and dry it to obtain a high-purity titanium-oxo cluster material.

[0033] In some embodiments, the titanium source is preferably one or a combination of two of isopropyl titanate and isobutyl titanate;

[0034] The bismuth source is preferably bismuth subnitrate;

[0035] In step 1), the solvent is a mixed solvent of DMF, acetonitrile, and alcohol, and the dosage ratio is preferably 1:1 - 6:2 - 4;

[0036] The dosage ratio of the titanium source to the bismuth source is preferably 1:1 to 2;

[0037] The ultrasonic time is 5 to 40 minutes;

[0038] The temperature of the solvothermal reaction is 60 to 100 °C;

[0039] The time of the solvothermal reaction is 3 to 10 days.

[0040] In some embodiments, the present invention further includes a post-modification synthesis step, and the full ligand exchange property of the titanium-containing oxo cluster material is revealed in the post-modification synthesis step. The specific operation steps are as follows:

[0041] 1) Place the titanium-containing oxo cluster material prepared by the above method in a glass bottle, add other alcohol solvents, ultrasonicate, and filter 1 to 4 times using a 0.22 μm needle filter;

[0042] 2) Let the filtered solution stand, and the titanium-containing oxo cluster material with completely modified surface slowly precipitates.

[0043] In some embodiments, the concentration of the titanium-containing oxo cluster material dissolved in the alcohol solution is 2 mg / ml to 10 mg / ml;

[0044] The alcohol solvents include, but are not limited to, any alkoxy alcohol, alcohol containing halogen, S, N, P elements, and alcohol containing unsaturated bonds, preferably any one of methanol, ethanol, n-propanol, isopropanol, phenol, 2-fluoroethanol;

[0045] The ultrasonic time is 30 to 60 minutes, preferably 20 to 40 minutes;

[0046] The number of filtration times is 1 to 4 times, preferably 2 to 3 times.

[0047] The principle of the present invention is that the alkoxy-modified titanium-containing oxo cluster is extremely easy to hydrolyze, and the hydrolysis causes irreversible changes in its structure and properties. Electron beam radiation can accelerate the hydrolysis and polycondensation processes in the exposed area, and the exposed area can be retained after development to achieve patterning.

[0048] The present invention provides other uses of the titanium-containing oxo cluster material. Based on the full ligand exchange property, the surface of the oxo cluster can be completely modified, which is extremely beneficial to the performance optimization and regulation of the titanium-containing oxo cluster material in the fields of photocatalysis, electrocatalysis, and solar cells.

[0049] The advantages and beneficial effects of the present invention:

[0050] The present invention provides a novel class of titanium-oxo cluster materials with high solution stability, which have stable cluster cores and ligands that are easily exchangeable. Dissolving the titanium-oxo cluster materials in alcohol solvents enables full ligand exchange, and the physical and chemical properties of the entire cluster can be altered, which is very important for performance regulation in the fields of lithography, photocatalysis, electrocatalysis, and solar cells. In addition, a method for patterning titanium-oxo cluster materials through radiation-induced hydrolysis is also provided. Under irradiation, hydrolysis and polycondensation occur, and after development, there is a contrast difference between the exposed area and the unexposed area, allowing for the preparation of fine lines or complex patterns. BRIEF DESCRIPTION OF THE DRAWINGS

[0051] Figure 1 Schematic diagram of patterning achieved by hydrolysis of titanium-oxo cluster materials with ligand exchange properties in the present invention;

[0052] Figure 2 For [Bi4Ti 12 O 18 L 24 cluster core schematic diagram;

[0053] Figure 3 For [Bi4Ti 12 O 18 L 24 , L = ethanol structural schematic diagram, hydrogen atoms are omitted for clearer structure;

[0054] Figure 4 For [Bi4Ti 12 O 18 L 24 , L = ethanol X-ray powder diffraction pattern, the upper line represents the spectrum of the synthesized crystal, and the lower line represents the spectrum simulated by single crystal structure analysis;

[0055] Figure 5 For [Bi4Ti 12 O 18 L 24 , L = ethanol thermogravimetric spectrum;

[0056] Figure 6 For [Bi4Ti 12 O 18 L 24 , L = ethanol infrared spectrum;

[0057] Figure 7 For [Bi4Ti 12 O 18 L 24 , L = ethanol ultraviolet-visible spectrum;

[0058] Figure 8 For [Bi4Ti12 O 18 L 24 , where L = ethanol, is the high-resolution mass spectrum in a methanol solution;

[0059] Figure 9 is [Bi4Ti 12 O 18 L 24 , where L = ethanol, is the high-resolution mass spectrum in a n-propanol solution;

[0060] Figure 10 is [Bi4Ti 12 O 18 L 24 , where L = n-propanol, is the upper (non-developed area) and lower (developed area) comparison diagram after 8h of hydrolysis and development of the thin film;

[0061] Figure 11 is [Bi4Ti 12 O 18 L 24 , where L = n-propanol, is the upper (non-developed area) and lower (developed area) comparison diagram after 60h of hydrolysis and development of the thin film;

[0062] Figure 12 is [Bi4Ti 12 O 18 L 24 , where L = n-propanol, is the upper (non-developed area) and lower (developed area) comparison diagram after 132h of hydrolysis and development of the thin film;

[0063] Figure 13 is [Bi4Ti 12 O 18 L 24 , where L = n-propanol, is the upper (non-developed area) and lower (developed area) comparison diagram after 168h of hydrolysis and development of the thin film;

[0064] Figure 14 is [Bi4Ti 12 O 18 L 24 , where L = n-propanol, is the 30nm (L / 2S) line pattern after exposure and development at a dose of 100 μc / cm 2 ;

[0065] Figure 15 is [Bi4Ti 12 O 18 L 24 , where L = n-propanol, is the 20nm (L / 2S) line pattern after exposure and development at a dose of 100 μc / cm 2 ;

[0066] Figure 16 For [Bi4Ti 12 O 18 L 24 , where L = n - propanol, is a complex pattern after exposure and development at a dose of 150 μc / cm 2 dose. Detailed implementation manners

[0067] The general composition formula of the titanium - containing oxo - cluster material with ligand - exchange properties and high solution stability provided by the present invention is: [Bi4Ti 12 O 18 L 24 , where L includes but is not limited to alkoxy alcohols, alcohols containing halogen, S, N, P elements, and alcohol ligands containing unsaturated bonds. The following further describes the present invention, but the protection scope of the present invention is not limited thereto.

[0068] In the implementation manner of the present invention, it is essential that the alcohol solvent participates in coordination during the structure synthesis process, and the dosage of other solvents can further optimize the reaction kinetics process, so as to obtain a titanium - containing oxo - cluster material with higher yield and higher purity. In addition, the ultrasonic process is also indispensable in the present invention, which can ensure that the added metal source is evenly mixed with the solution, facilitating the formation of the titanium - containing oxo - cluster material.

[0069] The solvothermal preparation method of the titanium - containing oxo - cluster material provided by the present invention specifically comprises the following steps:

[0070] S1: At room temperature, weigh bismuth subnitrate (1 - 2 mmol) and add it to a 20 - ml glass bottle. Then, add 1 - 6 mL of acetonitrile, 1 mL of DMF, and a mixed solution of 2 - 4 ml of alcohol solvent according to the molar volume ratio. Subsequently, slowly dropwise add 1 mmol of isopropyl titanate or isobutyl titanate, and cover the bottle cap;

[0071] S2: Ultrasonic the glass bottle containing the raw materials in an ultrasonic machine for 5 - 40 minutes, heat at 60 - 100 °C for 3 - 10 days, and then cool to room temperature to precipitate titanium - containing oxo - cluster crystals;

[0072] S3: Wash the mixture multiple times with the alcohol solvent used in the synthesis, and dry it to obtain a high - purity titanium - containing oxo - cluster material.

[0073] The alcohol solvent includes but is not limited to any one of alkoxy alcohols, alcohols containing halogen, S, N, P elements, and alcohol ligands containing unsaturated bonds. Preferably, the alcohol solvent in step S1 is one of ethanol, n - propanol, and tert - butanol;

[0074] The present invention also provides a post - modification synthesis method of the titanium - containing oxo - cluster material, including the following steps:

[0075] S4: Weigh 2 - 10 mg of the titanium oxo cluster material prepared in step S3 into a glass bottle, and then add 1 ml of an alcohol solvent according to the corresponding mass - volume ratio.

[0076] S5: Sonicate for 30 - 60 minutes, and filter 1 - 4 times using a 0.22 μm needle - type filter.

[0077] S6: Let it stand, and the novel titanium oxo cluster material with all surfaces modified will slowly precipitate.

[0078] It should be noted that the alcohol solvents added in step S4 include, but are not limited to, alkoxy alcohols, alcohols containing halogens, S, N, P elements, and alcohols containing unsaturated bonds. Preferably, it is any one of methanol, ethanol, n - propanol, isopropanol, phenol, 2 - fluoroethanol.

[0079] As time goes by, the yield of the titanium oxo cluster material increases, and the purity is extremely high. The prepared titanium oxo cluster material does not need to be washed.

[0080] After the titanium oxo cluster photoresist film is exposed under deep ultraviolet light, extreme ultraviolet light, ultraviolet light or electron beam, the exposed area accelerates hydrolysis polymerization into an oxide nanostructure containing Bi, Ti, C, O, and H. There is a difference in solubility between the unexposed area and the exposed area. Using an organic solvent for development, the exposed area is insoluble in the developer, while the unexposed area is soluble in the developer. Specifically, the developer is used to elute the unhydrolyzed and polycondensed oxo cluster molecules. Subsequently, lines or complex patterns can be photographed by a scanning electron microscope or an atomic force microscope.

[0081] In the present invention, the development time and the solvent used have a great influence on the development effect. Specifically, the development time generally does not exceed 30 minutes; the developer can be one or a mixed solvent of n - hexane, cyclohexane, DMF, methanol, ethanol, n - propanol, isopropanol, n - butanol, isobutanol, tert - butanol, cyclohexanone, acetonitrile, ether, acetone, butanone, ethyl acetate, ethyl lactate, propylene glycol methyl ether.

[0082] In the present invention, the dose of the exposure operation has a significant influence on the patterning effect. When the dose is small, the hydrolysis polycondensation reaction of the exposed part is incomplete, and the photoreactivity is weak, resulting in an unclear difference between the exposed area and the non - exposed area, which is not conducive to the preparation of fine patterns. On the contrary, when the dose is too large, although the hydrolysis polycondensation reaction of the exposed part is complete, the electron diffusion phenomenon is serious, and the difference between the exposed area and the non - exposed area is also unclear, which is not conducive to the preparation of fine patterns. Specifically, the exposure operation dose in the present invention is controlled within the range of 100 - 200 μC / cm 2 range.

[0083] In the following solvothermal synthesis examples, the chemicals and reagents used are all purchased from Aladdin Company and are not further processed.

[0084] Example 1

[0085] Weigh 1.5 mmol of bismuth subnitrate and add it to a 20 mL glass bottle. Then add a mixed solution of 5 mL of acetonitrile (CH3CN), 1 mL of N,N-dimethylformamide (DMF), and 2 mL of ethanol. Subsequently, slowly add dropwise 1 mmol of isopropyl titanate or isobutyl titanate, and cover the bottle cap. Place the glass bottle containing the raw materials in an ultrasonic machine and ultrasonically treat for 20 minutes. Then heat at 80 °C for 7 days and cool to room temperature. Use ethanol solvent to wash the precipitated mixture multiple times, and after drying, high-purity [Bi4Ti 12 O 18 L 24 (L = ethanol) can be obtained.

[0086] Example 2

[0087] Weigh 1 mmol of bismuth subnitrate and add it to a 20 mL glass bottle. Then add a mixed solution of 6 mL of acetonitrile, 1 mL of N,N-dimethylformamide, and 3 mL of n-propanol. Subsequently, slowly add dropwise 1 mmol of isopropyl titanate or isobutyl titanate, and cover the bottle cap. Place the glass bottle containing the raw materials in an ultrasonic machine and ultrasonically treat for 10 minutes. Then heat at 70 °C for 6 days and cool to room temperature. Use n-propanol solvent to wash the mixture multiple times, and after drying, high-purity [Bi4Ti 12 O 18 L 24 (L = n-propanol) can be obtained.

[0088] In the following post-modification synthesis examples, all reagents used are purchased from Aladdin Company and are not further treated; all titanium-oxo cluster materials used are prepared by the solvothermal method.

[0089] Example 3

[0090] Weigh 5 mg of the titanium-oxo cluster material prepared in Example 2 and add it to a glass bottle. Then add 1.5 mL of ethanol solvent and ultrasonically treat for 30 minutes. Filter the mixture twice with a 0.22 μm needle-type filter, let the filtrate stand at room temperature, and colorless crystals of surface-modified [Bi4Ti 12 O 18 L 24 (L = ethanol) slowly precipitate at the bottom of the vial.

[0091] Example 4

[0092] Weigh 3 mg of the titanium-oxo cluster material prepared in Example 1 and add it to a glass bottle. Then add 1 mL of n-propanol solvent and ultrasonically treat for 40 minutes. Filter the mixture twice with a 0.22 μm needle-type filter, let the filtrate stand at room temperature, and colorless crystals of surface-modified [Bi4Ti12 O 18 L 24 (L = n - propanol) precipitates slowly.

[0093] Example 5

[0094] Weigh 8 mg of the titanium - containing oxo - cluster material prepared in Example 1 or Example 2, add it to a glass bottle, then add 2 mL of methanol solvent, and ultrasonically treat for 35 minutes. Filter the mixture 3 times with a 0.22 - μm syringe filter, let the filtrate stand at room temperature, and colorless crystals of surface - modified [Bi4Ti 12 O 18 L 24 (L = methanol) precipitate slowly.

[0095] Example 6

[0096] Weigh 6 mg of the titanium - containing oxo - cluster material prepared in Example 1 or Example 2, add it to a glass bottle, then add 1 mL of isopropanol solvent, and ultrasonically treat for 40 minutes. Filter the mixture 2 times with a 0.22 - μm syringe filter, let the filtrate stand at room temperature, and colorless crystals of surface - modified [Bi4Ti 12 O 18 L 24 (L = isopropanol) precipitate slowly.

[0097] Example 7

[0098] Weigh 10 mg of the titanium - containing oxo - cluster material prepared in Example 1 or Example 2, add it to a glass bottle, then add 1 ml of phenol solvent. Let the filtrate stand at 60 °C, and red crystals of surface - modified [Bi4Ti 12 O 18 L 24 (L = phenol) precipitate slowly.

[0099] Example 8

[0100] Weigh 5 mg of the titanium - containing oxo - cluster material prepared in Example 1 or Example 2, add it to a glass bottle, then add 1 mL of 2 - fluoroethanol solvent, and ultrasonically treat for 45 minutes. Filter the mixture 2 times with a 0.22 - μm syringe filter, let the filtrate stand at room temperature, and surface - modified [Bi4Ti 12 O 18 L 24 (L = 2 - fluoroethanol) precipitate slowly.

[0101] The above alkoxy - modified titanium - containing oxo - cluster materials have good solubility in common organic solvents and are suitable for the preparation of photoresist films.

[0102] In the preparation of the photoresist film, all the reagents used were purchased from Aladdin and were not further treated; all the titanium-oxo cluster materials used were prepared through Examples 1 to 8.

[0103] Example 9

[0104] Dissolve 20 mg of [Bi4Ti 12 O 18 L 24 (L = n-propanol) in 1 mL of one of the solvents of ethyl lactate, propylene glycol monomethyl ether, cyclohexanone or methyl isobutyl carbinol, and ultrasonically treat for 40 minutes. Filter the mixture twice with a 0.22 μm needle-type filter and set aside. Use a vacuum rotary coating machine to spin-coat it on a silicon or silica substrate, and pre-bake at 50 - 70 °C for 10 - 60 seconds to obtain the photoresist film.

[0105] Example 10

[0106] Dissolve 20 mg of [Bi4Ti 12 O 18 L 24 (L = ethanol) in 1 mL of one of the solvents of ethyl lactate, propylene glycol monomethyl ether, cyclohexanone or methyl isobutyl carbinol, and ultrasonically treat for 40 minutes. Filter the mixture twice with a 0.22 μm needle-type filter and set aside. Use a vacuum rotary coating machine to spin-coat it on a silicon or silica substrate, and pre-bake at 50 - 70 °C for 10 - 60 seconds to obtain the photoresist film.

[0107] Experimental Example 1

[0108] Use an X-ray single crystal diffractometer to test the structure of the obtained titanium-oxo cluster material, and the results are shown in Figure 2 and Figure 3 .

[0109] Experimental Example 2

[0110] Perform PXRD, thermogravimetry, infrared and ultraviolet tests on [Bi4Ti 12 O 18 L 24 (L = ethanol), and the results are shown in Figures 4 to 7 .

[0111] Experimental Example 3

[0112] Perform tests on the high-resolution mass spectra of [Bi4Ti 12 O 18 L 24 (L = ethanol) in methanol or n-propanol solutions, and the results are shown in Figure 8 and Figure 9 .

[0113] Experimental Example 4

[0114] Take the photoresist film with a thickness of 30nm prepared in Example 9 and place it in a clean room with a humidity of 20% for 8h, 60h, 132h and 168h respectively. The experiment adopts a partitioned development strategy: the lower half of the film is immersed in isopropanol developer for 40s development, while the upper half remains untreated as a reference. Hydrolysis comparison photos are taken under a metallographic microscope. The results are shown in Figures 10 to 13 As the film placement time, that is, the oxygen cluster hydrolysis time, increases, the insoluble matter gradually increases, causing the development effect to gradually deteriorate, and the color contrast between the two parts gradually weakens. At 132 hours, development can still be achieved, but at 168 hours, there is no color difference between the developed and undeveloped parts, indicating that the titanium oxygen cluster film is completely hydrolyzed and condensed to form insoluble products.

[0115] Experimental Example 5

[0116] The photoresist film prepared in Example 9 was exposed to electron beam and post-baked at 100°C for 30 seconds. After the film was cooled to room temperature, it was developed with isopropanol for 40 seconds. The photolithography line results were photographed using a scanning electron microscope. Figure 14 and Figure 15 ; Use atomic force microscopy to observe complex patterns, see Figure 16 .

[0117] Finally, it should be pointed out that the embodiments described in the present invention are only preferred embodiments and are not intended to limit the present invention. Although the present invention has been described in detail through specific embodiments, those skilled in the art may still modify or partially replace the technical solutions in the embodiments without departing from the spirit and principles of the present invention. Any modification, equivalent replacement or improvement made on the basis of the present invention shall be included in the protection scope of the present invention. In addition, although the present invention describes the specific implementation methods in conjunction with the accompanying drawings, this does not limit the protection scope of the present invention. Those skilled in the art should understand that any modification or deformation that can be achieved without creative work based on the technical solution of the present invention belongs to the protection scope of the present invention.

Claims

1. A method for controlling the hydrolysis of a titanium-containing oxygen cluster material having ligand exchange properties to achieve patterning, comprising: (1) using an easily hydrolyzable titanium oxygen cluster material dissolved in a solvent, filtering, and spin coating on a substrate to form a patterned coating; (2) by irradiating the predetermined position of the coating layer in step (1), inducing the exposed area to accelerate the hydrolysis and polycondensation reaction to generate organic solvent insoluble substances, so that the exposed area is different from the non-exposed area; (3) Develop the coating and wash away the unexposed areas to achieve fine lines or complex patterns.

2. A method for controlling the hydrolysis of a titanium-containing oxygen cluster material having ligand exchange properties to achieve patterning according to claim 1, characterized in that: The substrate may be a silicon wafer or a silicon dioxide wafer; The solvent is a solvent that can completely dissolve the titanium oxide cluster material, including but not limited to ethyl lactate, propylene glycol methyl ether, cyclohexanone or methyl isobutyl carbinol; The radiation exposure source is one of deep ultraviolet light, extreme ultraviolet light, ultraviolet light or electron beam; The developer is a solvent that can completely dissolve the exposed area and make the non-exposed area insoluble, including but not limited to one of n-hexane, cyclohexane, DMF, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, cyclohexanone, acetonitrile, ether, acetone, butanone, ethyl acetate, ethyl lactate, and propylene glycol methyl ether or a mixed solvent.

3. A titanium-containing oxygen cluster material with ligand exchange properties for implementing the method of claim 1, wherein the material is a titanium-containing oxygen cluster material with high solution stability and ligand exchange properties, and the general composition formula is: [Bi4Ti 12 O 18 L 24 ], wherein L includes but is not limited to any alkoxy alcohol, alcohol containing halogen, S, N, P elements, and alcohol ligand containing unsaturated bonds.

4. The titanium-containing oxygen cluster material having ligand exchange properties according to claim 3, characterized in that: The titanium-oxygen cluster-containing material is not limited to any one of the following: (1)[Bi4Ti 12 O 18 L 24 ],L=ethanol; The molecular formula is C 48 H 120 O 42 Bi4Ti 12 , Mr = 2779.7668; space group is P42 / n, unit cell parameters are α=90°, β=90°, γ=90°, (2)[Bi4Ti 12 O 18 L 24 ], Ln-propanol; The molecular formula is C 72 H 168 O 42 Bi4Ti 12 , Mr = 3116.4047; space group is Pcca, unit cell parameters are α=90°, β=90°, γ=90°, (3)[Bi4Ti 12 O 18 L 24 ],L=methanol; The molecular formula is C 24 H 72 O 42 Bi4Ti 12 , Mr = 2443.1289; space group is P21 / c, unit cell parameters are α=90°, β=107.9251(17)°, γ=90°, (4)[Bi4Ti 12 O 18 L 24 ],L=isopropanol; The molecular formula is C 72 H 168 O 42 Bi4Ti 12 , Mr = 3116.4047; space group is Cmcm, unit cell parameters are α=90°, β=90°, γ=90°, (5)[Bi4Ti 12 O 18 L 24 ],L=phenol; The molecular formula is C 144 H 120 O 42 Bi4Ti 12 , Mr = 3932.7940; space group is Pcca, unit cell parameters are α=90°, β=90°, γ=90°, (6)[Bi4Ti 12 O 18 L 24 ],L=2-fluoroethanol; The molecular formula is C 48 H 96 F 24 O 42 Bi4Ti 12 , Mr = 3211.5379; space group is P42 / n, unit cell parameters are α=90°, β=90°, γ=90°, 5. The titanium-containing oxygen cluster material having ligand exchange properties according to claim 3 or 4, characterized in that: The titanium oxygen cluster-containing material is a highly symmetrical crystalline compound; The titanium oxygen cluster-containing material has simple synthesis and high yield; The titanium oxygen cluster material exhibits excellent solubility in a variety of solvents including ethyl lactate, propylene glycol methyl ether, cyclohexanone and methyl isobutyl carbinol, and its solubility can be as high as 40 to 80 mg / ml; The titanium oxide cluster material can be used as a precursor for post-modification synthesis, and can undergo a full ligand exchange process in other alcohol solvents to derive a novel titanium oxide cluster material whose peripheral ligands are replaced by these alcohol solvents.

6. The titanium-containing oxygen cluster material having ligand exchange properties according to claim 3 or 4, characterized in that: The titanium-containing oxygen cluster material has a highly stable cluster core, and also has peripheral ligands coordinated by, but not limited to, any alkoxy alcohol, alcohol containing halogen, S, N, P elements, and alcohol containing unsaturated bonds. The peripheral ligands are very active and have full ligand exchange properties, which can modify the entire oxygen cluster surface, thereby achieving performance optimization and improvement of the titanium-containing oxygen cluster material in lithography, photocatalysis, electrocatalysis, and solar cells.

7. The method for synthesizing the titanium-containing oxygen cluster material with ligand exchange properties according to claim 3 or 4 can be synthesized by a solvothermal method, comprising: 1) uniformly mixing a titanium source, a bismuth source and a solvent, heating the mixture after ultrasonic treatment, and cooling the mixture to room temperature to obtain a mixture; 2) The obtained mixture is washed with an alcohol solvent for multiple times and dried to obtain a high-purity titanium oxide cluster-containing material.

8. The synthesis method according to claim 7, characterized in that The titanium source is preferably one or a combination of isopropyl titanate and isobutyl titanate; The bismuth source is preferably bismuth subnitrate; The solvent in step 1) is a mixed solvent of DMF, acetonitrile and alcohol, and the volume ratio is preferably 1:1-6:2-4; The molar ratio of the titanium source to the bismuth source is preferably 1:1 to 2; The ultrasonic time is 5 to 40 minutes; The temperature of the solvent thermal reaction is 60 to 100°C; The solvent thermal reaction time is 3 to 10 days.

9. The synthesis method according to claim 7, characterized in that: Also included is a post-modification synthesis step, in which the full ligand exchange properties of the titanium oxo-cluster-containing material are revealed; 1) placing the titanium oxygen cluster material prepared in claim 7 in a glass bottle, adding other alcohol solvents, ultrasonicating, and filtering 1 to 4 times using a 0.22 μm syringe filter; 2) The filtered solution is allowed to stand, and the titanium oxygen cluster-containing material with all surface modified is slowly precipitated.

10. The synthesis method according to claim 9, characterized in that In the post-modification synthesis of the titanium oxygen cluster-containing material, the concentration of the titanium oxygen cluster-containing material dissolved in the alcohol solvent is 2 mg / ml to 10 mg / ml; The alcohol solvent includes but is not limited to any alkoxy alcohol, alcohol containing halogen, S, N, P elements, and alcohol containing unsaturated bonds, preferably any one of methanol, ethanol, n-propanol, isopropanol, phenol, and 2-fluoroethanol; The ultrasonic time is 30 to 60 minutes; The filtering times are 1 to 4 times.

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