A fluorine-containing aromatic acid ligand modified zirconium metal oxide nanocluster photoresist material, a preparation method and application thereof

Abstract

The application provides a fluorine-containing aromatic acid ligand modified zirconium metal oxide nanocluster photoresist material and a preparation method and application thereof. The preparation method of the fluorine-containing aromatic acid ligand modified zirconium metal oxide nanocluster photoresist material comprises the following steps: mixing a Zr6O4(OH)4(MAA) 12 solution and a fluorine-containing aromatic acid ligand compound solution, reacting, rotary evaporation and drying to obtain the fluorine-containing aromatic acid ligand modified zirconium metal oxide nanocluster photoresist material. The preparation method is simple, raw materials are cheap and easy to obtain, and the cost is low, and the method is suitable for industrial production. The fluorine-containing aromatic acid ligand modified zirconium metal oxide nanocluster photoresist material can be applied to ultraviolet lithography, electron beam lithography and extreme ultraviolet lithography, and the formed lithography pattern has the advantages of low line edge roughness and high resolution, and has a wide application prospect.

Description

Technical Field

[0001] This invention belongs to the field of photoresist technology materials, specifically relating to a zirconium metal oxide nanocluster photoresist material modified with fluorinated aromatic acid ligands, its preparation method and application. Background Technology

[0002] As the world enters the digital age, computers, smart electronic products, and the Internet are increasingly becoming the center of life and production. This has led to ever-increasing demands on the performance of digital processors and memory, which means that the integration of electronic components is becoming higher and higher.

[0003] The linewidth limits and precision of photolithography directly determine the integration density, reliability, and cost of integrated circuits. Photoresist is the most critical material in the photolithography process. By coating a silicon wafer with photoresist and then irradiating it with light of a specific wavelength, the photoresist undergoes chemical changes according to the light exposure, ultimately forming the desired pattern through development. The resolution of the photoresist determines the minimum feature size of the chip that can be manufactured; high-resolution photoresist can achieve finer patterns, thereby improving chip integration density and performance.

[0004] Extreme ultraviolet lithography (EUVL) is currently the most advanced photolithography technology internationally. However, the low photon utilization efficiency of its light source severely limits the production capacity of EUVL systems. Therefore, developing EUV resists with higher sensitivity has become an urgent need in the semiconductor industry. In recent years, various novel metal-containing photoresists have been developed. Among them, metal oxide clusters have been favored by researchers due to their advantages such as small and uniform molecular size and high EUV absorption cross-section.

[0005] The development of EUV photoresists has been limited by three factors: resolution, line edge roughness, and photosensitivity, which are interdependent. Current research on metal oxide nanoclusters mainly focuses on single carboxylic acid ligands, with methacrylic acid ligands being the predominant type. While these methacrylic acid ligand-based metal oxide nanoclusters exhibit high sensitivity in forming lithographic patterns, their pattern resolution is low, preventing the formation of higher-resolution patterns.

[0006] Chinese patent document CN 111948904 A discloses a photoresist composition and its preparation method, comprising: a metal oxide nanocluster, wherein the metal oxide nanocluster includes a metal oxide core and an organic ligand coordinated with the metal oxide core, and its general molecular formula is M. x O y (OH) m L nM is a metallic element, L is the organic ligand, and is an organic group containing a double bond, 4≤x≤8, 2≤y≤8, 0≤m<4, 12≤n≤16; L is a photoacid generator; a free radical quencher; and a solvent. M can be selected from zirconium, titanium, and hafnium, preferably zirconium. The metal oxide nanoclusters can be zirconium oxide, titanium oxide, or hafnium oxide. The metal oxide nanoclusters have a high light absorption rate, which can effectively improve energy utilization, resulting in higher energy absorption in the photoresist, more effectively initiating free radical reactions, and improving photosensitivity. However, the minimum linewidth feature size of the photolithographic pattern obtained by this invention is 26nm, the pattern quality is poor, and it is impossible to form a higher quality, higher resolution pattern.

[0007] Therefore, how to form higher quality and higher resolution lithographic patterns with minimal impact on the sensitivity of metal oxide clusters is the most pressing problem to be solved. Summary of the Invention

[0008] To address the shortcomings of existing technologies, this invention provides a zirconium metal oxide nanocluster photoresist material modified with fluorinated aromatic acid ligands, its preparation method, and its applications. This invention introduces partially fluorinated aromatic acid ligands into zirconium-based metal oxide nanoclusters via ligand exchange, resulting in zirconium metal oxide nanoclusters with mixed ligands. The preparation method is simple, uses inexpensive and readily available raw materials, and is low-cost, making it suitable for industrial production. The zirconium metal oxide nanocluster photoresist material modified with fluorinated aromatic acid ligands of this invention is applicable to ultraviolet lithography, electron beam lithography, and extreme ultraviolet lithography. The resulting photolithographic patterns exhibit advantages such as low edge roughness and high resolution, demonstrating broad application prospects.

[0009] The technical solution of the present invention is as follows:

[0010] A zirconium metal oxide nanocluster photoresist material modified with fluorinated aromatic acid ligands, having the general structural formula Zr6O4(OH)4(MAA). x (L) 12-x Where x takes values ​​from 0 to 11, MAA is a methacrylic acid ligand, and L is a fluorinated aromatic acid ligand.

[0011] According to a preferred embodiment of the present invention, the fluorinated aromatic acid ligand is a ligand formed from one or two of the following coordination compounds:

[0012]

[0013] According to a preferred embodiment of the present invention, x takes the value of 7-11.

[0014] The preparation method of the above-mentioned zirconium metal oxide nanocluster photoresist material modified with fluorinated aromatic acid ligands includes the following steps:

[0015] Zr6O4(OH)4(MAA) 12 The solution and the fluorinated aromatic acid ligand compound solution are mixed, reacted, and then rotary evaporated and dried to obtain a zirconium metal oxide nanocluster photoresist material modified with fluorinated aromatic acid ligands.

[0016] According to a preferred embodiment of the present invention, Zr6O4(OH)4(MAA) 12 The solvent used in the solution is one or a combination of two or more of the following: propylene glycol methyl ether, propylene glycol methyl ether acetate, ethyl lactate, acetone, methanol, ethanol, cyclohexanone, cyclopentanone, tetrahydrofuran, chloroform, n-butanol, dichloromethane, or toluene; Zr6O4(OH)4(MAA) 12 The concentration of the solution is 0.01-1 mol / L.

[0017] According to a preferred embodiment of the present invention, the solvent used for the fluorinated aromatic acid ligand compound solution is one or a combination of two or more of propylene glycol methyl ether, propylene glycol methyl ether acetate, ethyl lactate, acetone, methanol, ethanol, cyclohexanone, cyclopentanone, tetrahydrofuran, chloroform, n-butanol, dichloromethane, or toluene; and the concentration of the fluorinated aromatic acid ligand compound solution is 0.01-1 mol / L.

[0018] According to a preferred embodiment of the present invention, Zr6O4(OH)4(MAA) 12 The molar ratio of the compound to the fluorinated aromatic acid ligand is 1:1-5, preferably 1:3-4.2, and more preferably 1:3.

[0019] According to a preferred embodiment of the present invention, the fluorinated aromatic acid ligand compound is selected from one or two of the following:

[0020]

[0021] According to a preferred embodiment of the present invention, the reaction temperature is room temperature, the reaction time is 5-15 min, and the reaction is carried out under stirring conditions.

[0022] According to a preferred embodiment of the present invention, the rotary evaporation temperature is 35-45°C, the rotary evaporation time is 10-20 min, and the drying is performed under vacuum at room temperature.

[0023] According to the present invention, Zr6O4(OH)4(MAA) 12 It can be prepared using existing methods. Preferably, it is Zr6O4(OH)4(MAA). 12 The preparation method includes the following steps: thoroughly mixing a zirconium n-propanol solution in n-propanol and methacrylic acid, reacting, allowing to stand for crystallization, separating, and drying to obtain Zr6O4(OH)4(MAA). 12 .

[0024] Preferably, the concentration of the n-propanol solution of zirconium propoxide is 60-80 wt%; the molar ratio of zirconium propoxide to methacrylic acid is 0.1-0.5:1; the reaction temperature is 60-80℃, the reaction time is 15-20 h, the reaction is carried out under stirring conditions; the crystallization temperature is room temperature, and the crystallization time is 1-3 days.

[0025] A photoresist composition comprising, by weight, the following components: 1-3 parts solvent, 0.01-0.5 parts zirconium metal oxide nanocluster photoresist material modified with fluorinated aromatic acid ligands, and 0.005-0.05 parts photoacid generator.

[0026] According to a preferred embodiment of the present invention, the solvent is selected from one or more combinations of propylene glycol methyl ether, propylene glycol methyl ether acetate, ethyl lactate, acetone, methanol, ethanol, cyclohexanone, cyclopentanone, tetrahydrofuran, chloroform, n-butanol, dichloromethane, butyl acetate, n-hexane, N-methylpyrrolidone, carbon tetrachloride, γ-butyrolactone, ethylene glycol ethyl ether, isopropanol, or toluene.

[0027] According to a preferred embodiment of the present invention, the photoacid generator is selected from one or more combinations of 2-(2-((((propylsulfonyl)oxy)imino)thiophene-3(2H)-ylidene)-2-(o-tolyl)acetonitrile (acid generator PAG 103), 2-(2-((((octylsulfonyl)oxy)imino)thiophene-3(2H)-ylidene)-2-(o-tolyl)acetonitrile (acid generator PAG 108), N-hydroxynaphthalimide trifluoromethanesulfonic acid, N-hydroxysulfonic acid succinimide, or N-hydroxyphthalimide p-toluenesulfonate.

[0028] The preparation method of the above photoresist composition includes the following steps: fully dispersing the zirconium metal oxide nanocluster photoresist material modified with fluorinated aromatic acid ligands and the photoacid generator in a solvent to obtain the photoresist composition.

[0029] Application of the above-mentioned zirconium metal oxide nanocluster photoresist materials or photoresist compositions modified with fluorinated aromatic acid ligands in photolithography technology.

[0030] Taking 4-fluoro-2-methylbenzoic acid organic ligand as an example, the preparation route of zirconium metal oxide nanocluster photoresist material modified with fluorinated aromatic acid ligand is as follows:

[0031]

[0032] The technical features and beneficial effects of this invention are as follows:

[0033] 1. This invention relates to zirconium-based metal oxide nanoclusters Zr6O4(OH)4(MAA) 12This invention introduces fluorinated aromatic acid ligands into the organic shell of zirconium-based metal oxide nanoclusters, which initially consisted only of methacrylic acid ligands. Fluorinated aromatic acid ligand-modified zirconium metal oxide nanoclusters are obtained through ligand exchange. The acid ligand exchange method of this invention is simple, operates under mild conditions, requires no heating or gas introduction, has simple steps, uses readily available and inexpensive raw materials, and has low cost. The exchanged metal oxide clusters exhibit good stability and high yield, making it suitable for industrial production.

[0034] 2. This invention introduces fluorinated aromatic acid ligands, which stabilize the free radical cations generated after ionization, preventing rapid decarboxylation and cross-linking reactions. This significantly improves the contrast of the developed image, which is beneficial for reducing the roughness of the line edges and generating high-resolution patterns, enabling finer lines. Because fluorine has strong absorption of extreme ultraviolet light, the problem of reduced reactivity due to the introduction of aromatic ligands is mitigated, and the sensitivity of fluorine-free aromatic ligand metal-oxygen clusters is improved.

[0035] 3. There are a wide variety of fluorinated aromatic acid ligands, and the metal oxide nanoclusters synthesized from different ligands have different physical and chemical properties. This invention screened specific fluorinated aromatic ligands through a large number of experiments, and the resulting photoresist material has the advantages of good solubility, film formation and storage stability. While maintaining high sensitivity, it has significantly improved resolution compared with zirconium metal oxide clusters with methacrylic acid ligands currently being studied, and has the advantage of low line edge roughness. It is suitable for ultraviolet lithography, electron beam lithography and extreme ultraviolet lithography, and has broad application prospects.

[0036] 4. In the preparation method of this invention, the selection of solvent type, the selection of fluorinated aromatic acid ligand, and Zr6O4(OH)4(MAA) are all important considerations. 12 The selection of the ratio of fluorinated aromatic acid ligands and the type of photoacid generator will affect the quality of subsequent photolithography patterns. If the above conditions are not suitable, high-resolution patterns cannot be obtained. Attached Figure Description

[0037] Figure 1 The 1H NMR spectrum of the zirconium-based metal oxide nanoclusters prepared in Comparative Example 1 is shown.

[0038] Figure 2 The 1H NMR spectrum of the zirconium metal oxide nanocluster photoresist material modified with fluorine-free aromatic acid ligands prepared in Comparative Example 3 is shown.

[0039] Figure 3 The image shows the 1H NMR spectrum of the zirconium metal oxide nanocluster photoresist material modified with fluorinated aromatic acid ligands prepared in Example 1.

[0040] Figure 4The image shows the 1H NMR spectrum of the zirconium metal oxide nanocluster photoresist material modified with fluorinated aromatic acid ligands prepared in Example 3.

[0041] Figure 5 Thermogravimetric spectra of the zirconium metal oxide nanocluster photoresist materials prepared in Comparative Examples 1, 3 and 1 in air atmosphere.

[0042] Figure 6 This is a morphology image of the zirconium metal oxide nanocluster photoresist film modified with fluorinated aromatic acid ligands prepared in Example 5 under an atomic force microscope.

[0043] Figure 7 This is a diagram showing the solubility of the zirconium metal oxide nanocluster photoresist material modified with fluorinated aromatic acid ligands prepared in Example 1 in different solvents.

[0044] Figure 8 The electron beam lithography pattern of the photoresist film prepared in Comparative Example 2 is shown.

[0045] Figure 9 The electron beam lithography pattern of the photoresist film prepared in Comparative Example 4 is shown.

[0046] Figure 10 This is the electron beam lithography pattern of the photoresist film prepared in Example 5.

[0047] Figure 11 This is the electron beam lithography pattern of the photoresist film prepared in Example 5.

[0048] Figure 12 This is the electron beam lithography pattern of the photoresist film prepared in Example 6.

[0049] Figure 13 This is the electron beam lithography pattern of the photoresist film prepared in Example 7. Detailed Implementation

[0050] The present invention will be further illustrated below with specific embodiments, but is not limited thereto. Unless otherwise specified, the experimental methods described in the embodiments are conventional methods; the reagents and materials used are commercially available unless otherwise specified.

[0051] Comparative Example 1

[0052] A zirconium-based metal oxide nanocluster Zr6O4(OH)4(MAA) consisting entirely of methacrylic acid ligands. 12 The preparation method includes the following steps:

[0053] 20 g of a 70 wt% zirconium propoxide (0.043 mol) solution in n-propanol was added to a three-necked flask, followed by 20 g (0.23 mol) of methacrylic acid solution. The mixture was stirred in air for 5 min, then heated to 70 °C and reacted for 18 h. After the reaction was complete, the mixture was allowed to cool naturally to room temperature and allowed to crystallize at room temperature for 2 days to obtain single crystals. Colorless crystals were separated and dried under vacuum at 25 °C for 6 h to obtain the sample Zr-MAA.

[0054] The 1H NMR spectrum of the nanoclusters prepared in this comparative example is shown below. Figure 1 As shown, A1 and A2 are characteristic peaks of the hydrogen on the methylene group in the carbon-carbon double bond of the methacrylic acid ligand, and B is the characteristic peak of the hydrogen on the methyl group in the methacrylic acid, proving the successful synthesis of the target product.

[0055] Comparative Example 2

[0056] A photoresist composition comprising the following components: 2.09 g of solvent propylene glycol methyl ether acetate, 0.1 g of zirconium-based metal oxide nanocluster photoresist material consisting entirely of methacrylic acid ligands prepared by the method of Comparative Example 1, and 0.01 g of photoacid-generating agent N-hydroxynaphthalimide trifluoromethanesulfonic acid.

[0057] The preparation method of the above photoresist composition includes the following steps:

[0058] 0.1 g of zirconium metal oxide nanoclusters Zr6O4(OH)4(MAA), which consist entirely of methacrylic acid ligands and were prepared by the method of Comparative Example 1, was added to 2.09 g of propylene glycol methyl ether acetate. 12 The photoresist material is prepared by adding 0.01g of N-hydroxynaphthalimide trifluoromethanesulfonic acid, stirring evenly at room temperature, and filtering through a 0.22-micron polytetrafluoroethylene filter.

[0059] The obtained photoresist system was spin-coated onto the surface of a two-inch silicon wafer. The specific process flow was spin-coating, pre-baking, electron beam exposure, and development to obtain a patterned silicon wafer. Specific process parameters are shown in Table 1 below.

[0060] Table 1

[0061]

[0062] Comparative Example 3

[0063] A method for preparing a zirconium metal oxide nanocluster photoresist material modified with a fluorine-free aromatic acid ligand includes the following steps:

[0064] 1.01 g (0.000595 mol) of zirconium metal oxide nanoclusters (Zr-MAA) consisting entirely of methacrylic acid ligands, prepared according to the method of Comparative Example 1, and 0.218 g (0.00178 mol) of benzoic acid were dissolved in 10 ml of chloroform. The two solutions were then mixed and stirred at room temperature for ten minutes. The mixture was then rotary evaporated at 40 °C for 15 min. The resulting sample was then vacuum-pumped at room temperature for 30 min to obtain a white solid powder. The yield was 95.31%. The 1H NMR spectrum of the nanoclusters prepared in this comparative example is shown below. Figure 2 As shown, this demonstrates the successful introduction of benzoic acid ligands.

[0065] Comparative Example 4

[0066] A photoresist composition comprising the following components: 2.09 g of solvent propylene glycol methyl ether, 0.1 g of zirconium metal oxide nanocluster photoresist material modified with fluorine-free aromatic acid ligands prepared by the method of Comparative Example 3, and 0.01 g of photoacid-generating agent N-hydroxynaphthalimide trifluoromethanesulfonic acid.

[0067] The preparation method of the above photoresist composition includes the following steps:

[0068] Add 0.1g of the fluorine-free aromatic acid ligand-modified zirconium metal oxide nanocluster photoresist material prepared by the method of Comparative Example 3 to 2.09g of propylene glycol methyl ether, add 0.01g of N-hydroxynaphthalimide trifluoromethanesulfonic acid, stir evenly at room temperature, and filter with a 0.22-micron polytetrafluoroethylene filter to obtain the final product.

[0069] The obtained photoresist system was spin-coated onto the surface of a two-inch silicon wafer. The specific process flow was spin-coating, pre-baking, electron beam exposure, and development to obtain a patterned silicon wafer. Specific process parameters are shown in Table 2 below.

[0070] Table 2

[0071]

[0072] Example 1

[0073] A method for preparing a zirconium metal oxide nanocluster photoresist material modified with fluorinated aromatic acid ligands includes the following steps:

[0074] 1.01 g (0.000595 mol) of zirconium metal oxide nanoclusters (Zr-MAA) consisting entirely of methacrylic acid ligands, prepared according to the method of Comparative Example 1, and 0.276 g (0.00179 mol) of 4-fluoro-2-methylbenzoic acid were dissolved in 10 ml of chloroform. The two solutions were then mixed and stirred at room temperature for ten minutes, followed by rotary evaporation at 40 °C for 15 minutes. The resulting sample was then vacuum-pumped at room temperature for 30 minutes to obtain a white solid powder. The yield of the obtained sample was 97.88%.

[0075] The 1H NMR spectrum of the zirconium metal oxide nanocluster photoresist material modified with fluorinated aromatic acid ligands prepared in this embodiment is shown below. Figure 3 As shown in the figure, the 4-fluoro-2-methylbenzoic acid ligand was successfully introduced.

[0076] Example 2

[0077] A method for preparing a zirconium metal oxide nanocluster photoresist material modified with fluorinated aromatic acid ligands includes the following steps:

[0078] 1.01 g (0.000595 mol) of zirconium metal oxide nanoclusters Zr-MAA, which consisted entirely of methacrylic acid ligands, prepared according to the method of Comparative Example 1, and 0.384 g (0.00249 mol) of 4-fluoro-2-methylbenzoic acid were dissolved in 10 ml of chloroform. The two solutions were then mixed and stirred at room temperature for 10 minutes, and then rotary evaporated at 40 °C for 15 min. The resulting sample was then vacuumed at room temperature for 30 min to obtain a white solid powder.

[0079] Example 3

[0080] A method for preparing a zirconium metal oxide nanocluster photoresist material modified with fluorinated aromatic acid ligands includes the following steps:

[0081] 1.01 g (0.000595 mol) of zirconium metal oxide nanoclusters (Zr-MAA) consisting entirely of methacrylic acid ligands, prepared according to the method of Comparative Example 1, and 0.251 g (0.00179 mol) of p-fluorobenzoic acid were dissolved in 10 ml of chloroform. The two solutions were then mixed and stirred at room temperature for ten minutes, followed by rotary evaporation at 40 °C for 15 minutes. The resulting sample was then vacuum-pumped at room temperature for 30 minutes to obtain a white solid powder. The yield of the obtained sample was 94.02%.

[0082] The 1H NMR spectrum of the zirconium metal oxide nanocluster photoresist material modified with fluorinated aromatic acid ligands prepared in this embodiment is shown below. Figure 4 As shown in the figure, the p-fluorobenzoic acid ligand has been successfully introduced.

[0083] Example 4

[0084] A method for preparing a zirconium metal oxide nanocluster photoresist material modified with fluorinated aromatic acid ligands includes the following steps:

[0085] 1.01 g (0.000595 mol) of zirconium metal oxide nanoclusters (Zr-MAA) consisting entirely of methacrylic acid ligands, prepared according to the method of Comparative Example 1, and 0.251 g (0.00179 mol) of 2-fluorobenzoic acid were dissolved in 10 ml of chloroform. The two solutions were then mixed and stirred at room temperature for ten minutes, followed by rotary evaporation at 40 °C for 15 minutes. The resulting sample was then vacuum-pumped at room temperature for 30 minutes to obtain a white solid powder. The yield of the obtained sample was 93.15%.

[0086] Example 5

[0087] A photoresist composition comprising the following components: 2.09 g of solvent propylene glycol methyl ether, 0.1 g of zirconium metal oxide nanocluster photoresist material modified with fluorinated aromatic acid ligands prepared by the method of Example 1, and 0.01 g of photoacid-generating agent N-hydroxynaphthalimide trifluoromethanesulfonic acid.

[0088] The preparation method of the above photoresist composition includes the following steps:

[0089] Add 0.1g of the zirconium metal oxide nanocluster photoresist material modified with fluorinated aromatic acid ligands prepared in Example 1 to 2.09g of propylene glycol methyl ether, add 0.01g of N-hydroxynaphthalimide trifluoromethanesulfonic acid, stir evenly at room temperature, and filter with a 0.22-micron polytetrafluoroethylene filter to obtain the final product.

[0090] The obtained photoresist system was spin-coated onto the surface of a two-inch silicon wafer. The specific process flow was spin-coating, pre-baking, electron beam exposure, and development to obtain a patterned silicon wafer. Specific process parameters are shown in Table 3 below.

[0091] Table 3

[0092]

[0093] Example 6

[0094] A photoresist composition comprising the following components: 2.09 g of solvent propylene glycol methyl ether, 0.1 g of zirconium metal oxide nanocluster photoresist material modified with fluorinated aromatic acid ligands prepared by the method of Example 2, and 0.01 g of photoacid-generating agent N-hydroxynaphthalimide trifluoromethanesulfonic acid.

[0095] The preparation method of the above photoresist composition includes the following steps:

[0096] Add 0.1g of the zirconium metal oxide nanocluster photoresist material modified with fluorinated aromatic acid ligands prepared in Example 2 to 2.09g of propylene glycol methyl ether, add 0.01g of N-hydroxynaphthalimide trifluoromethanesulfonic acid, stir evenly at room temperature, and filter with a 0.22-micron polytetrafluoroethylene filter to obtain the final product.

[0097] The obtained photoresist system was spin-coated onto the surface of a two-inch silicon wafer. The specific process flow was spin-coating, pre-baking, electron beam exposure, and development to obtain a patterned silicon wafer. Specific process parameters are shown in Table 4 below.

[0098] Table 4

[0099]

[0100] Example 7

[0101] A photoresist composition comprising the following components: 2.09 g of solvent propylene glycol methyl ether, 0.1 g of zirconium metal oxide nanocluster photoresist material modified with fluorinated aromatic acid ligands prepared by the method of Example 3, and 0.01 g of photoacid-generating agent N-hydroxynaphthalimide trifluoromethanesulfonic acid.

[0102] The preparation method of the above photoresist composition includes the following steps:

[0103] Add 0.1g of the zirconium metal oxide nanocluster photoresist material modified with fluorinated aromatic acid ligands prepared in Example 3 to 2.09g of propylene glycol methyl ether, add 0.01g of N-hydroxynaphthalimide trifluoromethanesulfonic acid, stir evenly at room temperature, and filter with a 0.22-micron polytetrafluoroethylene filter to obtain the final product.

[0104] The obtained photoresist system was spin-coated onto the surface of a two-inch silicon wafer. The specific process flow was spin-coating, pre-baking, electron beam exposure, and development to obtain a patterned silicon wafer. Specific process parameters are shown in Table 5 below.

[0105] Table 5

[0106]

[0107] Example 8

[0108] A photoresist composition comprising the following components: 2.09 g of solvent propylene glycol methyl ether, 0.1 g of zirconium metal oxide nanocluster photoresist material modified with fluorinated aromatic acid ligands prepared by the method of Example 4, and 0.01 g of photoacid-generating agent N-hydroxynaphthalimide trifluoromethanesulfonic acid.

[0109] The preparation method of the above photoresist composition includes the following steps:

[0110] Add 0.1g of the zirconium metal oxide nanocluster photoresist material modified with fluorinated aromatic acid ligands prepared in Example 4 to 2.09g of propylene glycol methyl ether, add 0.01g of N-hydroxynaphthalimide trifluoromethanesulfonic acid, stir evenly at room temperature, and filter with a 0.22-micron polytetrafluoroethylene filter to obtain the final product.

[0111] The obtained photoresist system was spin-coated onto the surface of a two-inch silicon wafer. The specific process flow was spin-coating, pre-baking, electron beam exposure, and development to obtain a patterned silicon wafer. Specific process parameters are shown in Table 6 below.

[0112] Table 6

[0113]

[0114] Experimental Example 1

[0115] Thermal analysis was performed on the products of Comparative Example 1, Comparative Example 3 and Example 1.

[0116] Thermal analysis (NETZSCH, model STA449F3): The temperature was increased from room temperature to 800°C at a rate of 10°C / min in air. The obtained thermal analysis curves are as follows... Figure 5 As shown in the figure, all three samples have good thermal stability, and the thermal stability curves remain unchanged after two months of storage.

[0117] Experimental Example 2

[0118] To evaluate the quality of the spin-coated photoresist film in Example 5, the surface morphology of the photoresist film was acquired using a non-contact atomic force microscope (AFM) (Shimadzu, model: SPM-9700HT), with the acquisition area set to 10 μm * 10 μm. The surface morphology image of the photoresist film of Example 1 observed by AFM is shown below. Figure 6 As shown, the root mean square roughness (Rq) of the film was measured to be 0.466 nm, indicating that its surface is smooth and the film quality is good.

[0119] Experimental Example 3

[0120] To evaluate the solubility of the fluorinated aromatic acid ligand-modified zirconium metal oxide nanoclusters photoresist material synthesized in Example 1, it was dissolved in various solvents, including propylene glycol methyl ether acetate, with a solid content of 5%. The solubility results are as follows: Figure 7 As shown, the metal-oxygen clusters of fluorinated aromatic acid ligands can be completely dissolved in a variety of solvents, which indicates that the metal-oxygen clusters of fluorinated aromatic acid ligands have good solubility.

[0121] Test Example 4

[0122] To demonstrate that fluorinated aromatic acid ligands improve the imaging quality of photoresists, line exposure of the photoresist films in Comparative Example 2 and Example 5 was performed using electron beam lithography (EBL) (Pioneer Two, Raith GmbH, Germany). A voltage of 30 kV and an aperture stop of 10 mm were used. The exposed silicon wafers were immediately developed in toluene for 20 seconds and then dried with nitrogen. Other suitable developers include cyclopentanone, ethyl lactate, ethyl acetate, propylene glycol acetate, and propylene glycol methyl ether, with a designed linewidth of less than 50 nm.

[0123] The above photolithographic pattern was characterized using the scanning electron microscope imaging function of an electron beam exposure system, such as... Figure 8 , 10 As shown in Figure 11, the lowest linewidth achievable in Comparative Example 2 is 36 nm, with a linewidth period (spacing between adjacent lines) of 100 nm. In Example 5, the fluorinated oxygen cluster photoresist can achieve a minimum linewidth of 22 nm under a linewidth period of 90 nm, and also a linewidth of 27 nm under a 90 nm condition. The fluorinated aromatic acid ligand oxygen cluster photoresist can achieve patterns with even lower linewidths under a smaller linewidth period, with good pattern quality. This demonstrates that the fluorinated aromatic acid ligand improves the imaging quality of the zirconia nanoparticle photoresist and exhibits superior photolithographic performance.

[0124] Experimental Example 5

[0125] To demonstrate that fluorinated aromatic acid ligands can improve the low reactivity of non-fluorinated aromatic acid ligands, line exposure of the photoresist films in Comparative Example 4 and Example 5 was performed using electron beam lithography (EBL) (Pioneer Two, Raith GmbH, Germany). The voltage was 30 kV and the aperture stop was 10 mm. The exposed silicon wafers were immediately developed in toluene for 20 seconds and then dried with nitrogen. Other suitable developers include cyclopentanone, ethyl lactate, ethyl acetate, propylene glycol acetate, and propylene glycol methyl ether, with a designed linewidth of less than 50 nm.

[0126] The above photolithographic pattern was characterized using the scanning electron microscope imaging function of an electron beam exposure system, such as... Figure 9 and Figure 10 As shown, when the metal-oxide clusters of both ligands have a pattern linewidth of 27 nm and a linewidth period of 90 nm, the required exposure dose for the zirconium metal-oxide cluster photoresist with non-fluorinated aromatic acid ligands is 940 μC / cm. 2 The required exposure dose for fluorinated aromatic acid ligands is 430 μC / cm. 2The required exposure dose for fluorinated ligands is greatly reduced, proving that fluorinated aromatic acid ligands can improve the low reactivity of non-fluorinated aromatic acid ligands and increase the sensitivity of non-fluorinated aromatic ligand metal-oxygen clusters.

[0127] Experimental Example 6

[0128] To demonstrate the effect of the choice of the ratio of the same fluorinated aromatic acid ligand compound on the photolithographic pattern, line exposure of the photoresist films in Examples 5 and 6 was performed using electron beam lithography (EBL) (Pioneer Two, Raith GmbH, Germany). A voltage of 30 kV and an aperture stop of 10 mm were used. The exposed silicon wafers were immediately developed in toluene for 20 seconds and then dried with nitrogen. Other suitable developers include cyclopentanone, ethyl lactate, ethyl acetate, propylene glycol acetate, and propylene glycol methyl ether, with a designed linewidth of less than 50 nm.

[0129] The above photolithographic pattern was characterized using the scanning electron microscope imaging function of an electron beam exposure system, such as... Figure 10 and Figure 12 As shown, compared to Example 5, Example 6 requires a higher exposure dose, has lower sensitivity, and produces a worse pattern quality when obtaining a straight line of the same linewidth under electron beam exposure. This demonstrates that the choice of the ratio of the same fluorinated aromatic acid ligand compound has a significant impact on the photolithographic pattern.

[0130] Experimental Example 7

[0131] To demonstrate the influence of the type of fluorinated aromatic acid ligand compound on the photolithographic pattern, line exposure of the photoresist films in Examples 5 and 7 was performed using electron beam lithography (EBL) (Pioneer Two, Raith GmbH, Germany). A voltage of 30 kV and an aperture stop of 10 mm were used. The exposed silicon wafers were immediately developed in toluene for 20 seconds and then dried with nitrogen. Other suitable developers include cyclopentanone, ethyl lactate, ethyl acetate, propylene glycol methyl ether acetate, and propylene glycol methyl ether, with a designed linewidth of less than 50 nm.

[0132] The above photolithographic pattern was characterized using the scanning electron microscope imaging function of an electron beam exposure system, such as... Figure 10 and Figure 13 As shown, compared to Example 5, Example 7 requires a lower exposure dose and has higher sensitivity to obtain a straight line with the same linewidth under electron beam exposure, but the resulting pattern quality is worse. This demonstrates that the choice of the same fluorinated aromatic acid ligand compound has a significant impact on the photolithographic pattern.

Claims

1. A zirconium metal oxide nanocluster photoresist material modified with fluorinated aromatic acid ligands, characterized in that, The general structural formula is Zr6O4(OH)4(MAA). x (L) 12-x Where x takes values ​​of 7-11, MAA is a methacrylic acid ligand, and L is a fluorinated aromatic acid ligand; Fluorinated aromatic acid ligands are ligands formed by one or two of the following coordination compounds: ； The preparation method of the zirconium metal oxide nanocluster photoresist material modified with fluorinated aromatic acid ligands includes the following steps: Zr6O4(OH)4(MAA) 12 A solution and a solution of fluorinated aromatic acid ligand compound were mixed, reacted, rotary evaporated, and dried to obtain a zirconium metal oxide nanocluster photoresist material modified with fluorinated aromatic acid ligand. Zr6O4(OH)4(MAA) 12 The molar ratio of the compound to the fluorinated aromatic acid ligand is 1:

3.

2. The zirconium metal oxide nanocluster photoresist material modified with fluorinated aromatic acid ligands according to claim 1, characterized in that, Includes one or more of the following conditions: i. Zr6O4(OH)4(MAA) 12 The solvent used in the solution is one or a combination of two or more of the following: propylene glycol methyl ether, propylene glycol methyl ether acetate, ethyl lactate, acetone, methanol, ethanol, cyclohexanone, cyclopentanone, tetrahydrofuran, chloroform, n-butanol, dichloromethane, or toluene; Zr6O4(OH)4(MAA) 12 The concentration of the solution is 0.01-1 mol / L; ii. The solvent used for the fluorinated aromatic acid ligand compound solution is one or a combination of two or more of the following: propylene glycol methyl ether, propylene glycol methyl ether acetate, ethyl lactate, acetone, methanol, ethanol, cyclohexanone, cyclopentanone, tetrahydrofuran, chloroform, n-butanol, dichloromethane, or toluene; the concentration of the fluorinated aromatic acid ligand compound solution is 0.01-1 mol / L. iii. The reaction temperature is room temperature, the reaction time is 5-15 min, and the reaction is carried out under stirring conditions; iv. The rotary evaporation temperature is 35-45℃, and the rotary evaporation time is 10-20 min; the drying is done at room temperature under vacuum.

3. The zirconium metal oxide nanocluster photoresist material modified with fluorinated aromatic acid ligands according to claim 1, characterized in that, Zr6O4(OH)4(MAA) 12 The preparation method includes the following steps: thoroughly mixing a zirconium n-propanol solution in n-propanol and methacrylic acid, reacting, allowing to stand for crystallization, separating, and drying to obtain Zr6O4(OH)4(MAA). 12 ; The concentration of the n-propanol solution of zirconium n-propoxide is 60-80 wt%; the molar ratio of zirconium n-propoxide to methacrylic acid is 0.1-0.5:1; the reaction temperature is 60-80℃, the reaction time is 15-20 h, and the reaction is carried out under stirring conditions; the crystallization temperature is room temperature, and the crystallization time is 1-3 days.

4. A photoresist composition, characterized in that, The composition by weight includes the following components: 1-3 parts solvent, 0.01-0.5 parts zirconium metal oxide nanocluster photoresist material modified with fluorinated aromatic acid ligands, and 0.005-0.05 parts photoacid generator.

5. The photoresist composition according to claim 4, characterized in that, The solvent is selected from one or more combinations of propylene glycol methyl ether, propylene glycol methyl ether acetate, ethyl lactate, acetone, methanol, ethanol, cyclohexanone, cyclopentanone, tetrahydrofuran, chloroform, n-butanol, dichloromethane, butyl acetate, n-hexane, N-methylpyrrolidone, carbon tetrachloride, γ-butyrolactone, ethylene glycol ethyl ether, isopropanol, or toluene; The photoacid-generating agent is selected from one or more combinations of 2-(2-(((propylsulfonyl)oxy)imino)thiophene-3(2H)-ylidene)-2-(o-tolyl)acetonitrile, 2-(2-((((octylsulfonyl)oxy)imino)thiophene-3(2H)-ylidene)-2-(o-tolyl)acetonitrile, N-hydroxynaphthalimide trifluoromethanesulfonic acid, N-hydroxysulfonic acid succinimide, or N-hydroxyphthalimide p-toluenesulfonate.

6. The method for preparing the photoresist composition according to claim 4, comprising the steps of: fully dispersing the zirconium metal oxide nanocluster photoresist material modified with fluorinated aromatic acid ligands and the photoacid generator in a solvent, thereby obtaining the composition.

7. The application of the zirconium metal oxide nanocluster photoresist material modified with fluorinated aromatic acid ligands as described in any one of claims 1-3 or the photoresist composition as described in any one of claims 4-5 in photolithography technology.

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