Ni-based organic coordination nanoparticles and methods for producing the same, as well as photoresist compositions containing the nanoparticles and their applications.

Abstract

This invention provides Ni-based organic coordination nanoparticles, a method for producing the same, and a photoresist composition containing the nanoparticles and its applications. The Ni-based organic coordination nanoparticles are obtained by mixing and stirring a nickel-containing compound, metatoluic acid, and a nitrogen-containing organic ligand in an organic solvent, followed by post-treatment. Furthermore, the general formula is Ni m X n (CH3COO) t Y p H q Nanoparticles are obtained as follows: In the formula, X represents the metatoluyl ion, CH3COO represents the acetate ion, and Y represents the nitrogen-containing organic ligand. m, n, p, and q are each independently selected from any integer between 1 and 20, and t is selected from any integer between 0 and 20. By using Ni-based organic coordination nanoparticles as a photoresist component, superior lithography performance such as high resolution, high sensitivity, and low linewidth roughness can be achieved.

Description

[Technical Field]

[0001] The present invention relates to the technical field of photoresists, and more particularly to Ni-based organic coordination nanoparticles and methods for producing the same, as well as photoresist compositions and their applications. [Background technology]

[0002] Lithography is a technique that transfers a mask pattern onto a substrate using photoresist under the action of a specific energy, and it is a core technology in chip manufacturing. In the integrated circuit manufacturing process, the cost of lithography accounts for more than one-third of the total cost. The size and quality of the lithography have a significant impact on chip performance. With the continuous development of lithography technology, the line width of light sources is constantly shrinking, and exposure technology using 13.5nm extreme ultraviolet light sources is becoming the main option for lithography nodes of 7nm and below.

[0003] Photoresist refers to an etching-resistant thin film material whose solubility changes upon irradiation with ultraviolet light, electron beams, particle beams, extreme ultraviolet (EUV), or soft X-rays. It is widely applied to pattern transfer in the manufacturing processes of advanced micro-nanostructures, including in fields such as semiconductor integrated circuits, liquid crystal panel processing, and the manufacture of advanced optical devices. With the continuous advancement of semiconductor technology and the development of Moore's Law, semiconductor processes are constantly becoming smaller, and the demand for reductions in characteristic dimensions during processing is increasing. To meet the needs of more advanced semiconductor processes and achieve smaller characteristic dimensions, lithography technology is also continuously developing, progressing from i-line, G-line, deep ultraviolet (DUV), 193nm, and immersion 193nm to precision processing methods such as extreme ultraviolet lithography and electron beam lithography. The photoresist film forms a resist pattern by exposure and development, and then dry etching or wet etching is performed. The substrate material in areas not covered by the resist film is etched directly, while the substrate surface covered by the resist film is not etched due to the protection of the photoresist film. Etching resistance is a very important evaluation indicator for photoresists. Excellent etching resistance ensures that the photoresist protects the substrate surface from damage during the etching process, effectively simplifying the etching process and significantly improving the yield of etched products.

[0004] Conventional photoresists have complex compositions, containing photoresist resin, photosensitive agents, leveling agents, stabilizers, dispersants, thickeners, and solvents, resulting in a complicated manufacturing process and extremely high process requirements for controlling the mixing ratio and purity. Conventional photoresists are mostly high-molecular-weight polymers containing various functional additives, and their complex composition leads to a wide size distribution of photoresists, with components of various sizes present. The size conformation of some components can reach 10nm to 20nm, making it difficult to control the dimensions of photoresist patterns and potentially causing many defects. Furthermore, the applicability range of conventional photoresists is greatly affected by the wavelength of the light source, requiring different photoresists to be matched for different light sources.

[0005] Extreme ultraviolet (EUV) lithography is attracting attention as a fundamental technology used in the manufacturing of next-generation semiconductor devices. EUV lithography is a pattern formation technique that uses EUV rays with a wavelength of approximately 13.5 nm as the exposure light source. According to EUV lithography, it is possible to form extremely fine patterns (for example, approximately 20 nm or less) in the exposure process of semiconductor device manufacturing.

[0006] However, conventional lithography techniques produce patterns with high edge roughness and low pattern resolution, which hinders the application of lithography technology and necessitates improvement. [Overview of the project] [Problems that the invention aims to solve]

[0007] In view of the above, the present invention addresses the problem of high edge roughness and low resolution of patterns obtained by conventional lithography using photoresists by providing novel Ni-based organic coordination nanoparticles, a method for producing the same, a photoresist composition containing the nanoparticles, and its applications. [Means for solving the problem]

[0008] In one embodiment, the present invention provides Ni-based organic coordination nanoparticles. The general formula of the nanoparticles is Ni m X n (CH3COO) t Y p H q The formula is as follows: where X is the metatoluyl ion, CH3COO is the acetate ion, and Y is the nitrogen-containing organic ligand. m, n, p, and q are each independently selected from any integer between 1 and 20, and t is selected from any integer between 0 and 20. The nanoparticles are produced by the following method: that is, they are obtained by mixing and stirring a nickel-containing compound, metatoluyl acid, and a nitrogen-containing organic ligand in an organic solvent, followed by post-treatment. Here, the molar ratio of nickel-containing compound:metatoluyl acid:nitrogen-containing organic ligand is (2-10):(4-10):(2-10).

[0009] Furthermore, the nitrogen-containing organic ligand is one or more selected from organoliphatic amines and their derivatives, imidazoles and their derivatives. The nickel-containing compound is a nickel-containing soluble salt, such as nickel acetate, nickel acetate tetrahydrate, or nickel chloride.

[0010] Furthermore, the organoaliphatic amines are one or more selected from benzylamine and triamylamine. The imidazole and its derivatives are one or more selected from N-methylimidazole and N-butylimidazole.

[0011] Furthermore, the nitrogen-containing organic ligand is selected from benzylamine, triamylamine, N-methylimidazole, and N-butylimidazole.

[0012] Furthermore, the size of the Ni-based organic coordination nanoparticles is 2 nm to 5 nm.

[0013] Furthermore, the post-treatment includes stirring at 45°C to 80°C for 5 hours to 24 hours, then performing rotary evaporation at 35°C to 50°C for 20 minutes to 80 minutes using a rotary evaporator, and subsequently evacuating in a vacuum oven at 65°C to 90°C for 2 hours.

[0014] Furthermore, the general structural formula of the nanoparticles is any of the following. Ni 12 (C8H7COO)6(CH3COO) 18 (CH3C2N2H3)6(H2O)6; Ni 12 (C8H7COO)6(CH3COO) 18 (C7H9N)6(H2O)6; Ni 12 (C8H7COO)6(CH3COO) 18 (C7H 12 N2)6(H2O)6; Ni 12 (C8H7COO)6(CH3COO) 18 (C 15 H 33 (CHN)6(H2O)6.

[0015] Furthermore, the above photoresist composition further includes a photoacid generator and an organic dispersion solvent. The photoacid generator preferably occupies 5 wt% to 10 wt% of the composition. The nanoparticles preferably occupy 3 wt% to 20 wt% of the composition.

[0016] Furthermore, the photoacid generator is any one or more selected from N-hydroxynaphthalimide trifluoromethanesulfonate, 1,4-aminonaphthalenesulfonic acid, 2-amino-5,7-naphthalenedisulfonic acid, tert-butylphenyliodonium perfluorooctanesulfonate, triphenylsulfonium perfluorobutanesulfonate, triphenylsulfonium perfluorobutylsulfonate, triphenylsulfonium trifluoromethanesulfonate.

[0017] Furthermore, the organic dispersion solvent is one or more selected from ethyl acetate, butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol methyl ether acetate, 1-ethoxy-2-propanol, methanol, ethanol, and propanol. Propylene glycol methyl ether acetate is preferred as the solvent.

[0018] Furthermore, the present invention provides a lithography method that employs the photoresist composition, drops the photoresist composition onto a substrate, performs spin coating and heating, then exposes it with an electron beam, medium ultraviolet light, deep ultraviolet light, or extreme ultraviolet light, and develops it using a developer.

[0019] The amount of exposure agent used in the aforementioned exposure procedure is 50 mJ / cm³. 2 ~500mJ / cm 2 Therefore, the amount of exposure agent must be controlled within an appropriate range. If the amount of exposure agent is too low, the energy will be too low, and polymerization of photoresist particles in the exposed area will not be sufficiently promoted, resulting in insufficient formation of a solubility difference between the exposed and unexposed areas, and a poor development effect. Compared to bare metal nanoparticles, nanoparticles containing organic ligands undergo polymerization reactions more easily. If the amount of exposure agent is too high, the organic ligands may detach directly from the metal oxide to form fragments, preventing the photoresist particles from undergoing the exchange reaction of organic ligands, and reducing the degree of polymerization in the exposed area.

[0020] Furthermore, the developer is a mixture of one or more substances selected from toluene, mesitylene, orthoxylene, metaxylene, paraxylene, tetralin, decalin, cyclohexane, and n-propanol, and the development temperature is room temperature or 20°C to 50°C.

[0021] The thickness of the pre-coating layer after removing the organic dispersion solvent can be 10 nm to 100 nm. Specifically, the thickness of the pre-coating layer can be 10 nm to 20 nm, 20 nm to 30 nm, 30 nm to 40 nm, 40 nm to 50 nm, 50 nm to 60 nm, 60 nm to 70 nm, 70 nm to 80 nm, 80 nm to 90 nm, or 90 nm to 100 nm.

[0022] Furthermore, the above nanoparticles are applicable to the field of photoresists, particularly electron beam, mid-ultraviolet, deep ultraviolet, and / or extreme ultraviolet photoresists.

[0023] The exposure conditions are selected from one of the following: medium ultraviolet, deep ultraviolet, electron beam, or extreme ultraviolet. The photoresist composition of the present invention is applicable to any of these exposure conditions.

[0024] The substrate is selected from silicon substrates. Alternatively, other substrates insoluble in the developer can be selected depending on the specific needs.

[0025] For masks, a transmission mask is used for deep ultraviolet and longer wavelength light sources, a reflection mask is used for extreme ultraviolet light, and exposure to electron beams is performed according to a pattern set in the software.

[0026] Compared to the conventional technology, the beneficial effects of the present invention are as follows: The Ni-based organic coordination nanoparticles obtained in this invention have a special structure and, under light irradiation conditions, interact with a photoacid generator, changing the polarity of the material and causing aggregation, thus changing the solubility of the Ni-based organic coordination nanoparticles before and after light irradiation. Due to these properties, when these Ni-based organic coordination nanoparticles are used as a photoresist component, a difference in solubility in the developer occurs between the photosensitive and light-shielding portions of the photoresist. The photosensitive portion aggregates and its solubility in the developer decreases, while the light-shielding portion does not aggregate and dissolves in the developer, allowing for the removal of unexposed areas after development to obtain a pattern of the desired shape. In particular, because these Ni-based organic coordination nanoparticles have a special structure, using these Ni-based organic coordination nanoparticles as a photoresist component compared to conventional polymer-type photoresists and molecular glass-type photoresists enables superior lithography performance, such as high resolution, high sensitivity, and low linewidth roughness. This invention has shown that by introducing a benzoic acid ligand to Ni-based organic coordination nanoparticles, the crystallinity of the complex can be effectively reduced, improving the solubility of the material in organic solvents and facilitating storage and application. [Brief explanation of the drawing]

[0027] [Figure 1] This is a cluster structure diagram obtained from single-crystal analysis of Ni-based organic coordination nanoparticles according to Example 1 of the present invention. [Figure 2] This is a dynamic light scattering diagram of the Ni-based organic coordination nanoparticles of Example 1 of the present invention. [Figure 3] This is the infrared absorption spectrum of the Ni-based organic coordination nanoparticles of Example 1 of the present invention. [Figures 4a-4d] This is the XPS spectrum of the Ni-based organic coordination nanoparticles of Example 1 of the present invention. [Figure 5] This is a cluster structure diagram obtained from single-crystal analysis of Ni-based organic coordination nanoparticles according to Example 3 of the present invention. [Figure 6] This is a dynamic light scattering diagram of the Ni-based organic coordination nanoparticles of Example 3 of the present invention. [Figure 7] These are the powder XRD spectra of Ni-based organic coordination nanoparticles of Examples 1, 2, and 4 of the present invention. [Figure 8]This is a dynamic light scattering diagram of the Ni-based organic coordination nanoparticles of Example 2 of the present invention. [Figure 9] This is a dynamic light scattering diagram of the Ni-based organic coordination nanoparticles of Example 4 of the present invention. [Figure 10-19] This is a micrograph of a lithographic image of Ni-based organic coordination nanoparticles according to Example 1 of the present invention. [Figures 20a-20c] This is a micrograph of a lithographic image of Ni-based organic coordination nanoparticles according to Example 2 of the present invention. [Figure 21] This is a micrograph of a lithographic image of Ni-based organic coordination nanoparticles according to Example 2 of the present invention. [Figures 22a-22c] This is a micrograph of a lithographic image of Ni-based organic coordination nanoparticles according to Example 3 of the present invention. [Figures 23a-23c] This is a micrograph of a lithographic image of Ni-based organic coordination nanoparticles according to Example 4 of the present invention. [Modes for carrying out the invention]

[0028] Example 1 5.44 g (40 mmol) of m-toluic acid and 4.98 g (20 mmol) of nickel acetate tetrahydrate were placed in a 150 mL flask, dissolved in 45 mL of THF, heated and stirred at 65°C for 5 minutes, then 1.67 g of methylimidazole was added, and the mixture was heated and stirred at 65°C overnight. After a green solution was obtained, the solution was allowed to stand at a low temperature for 15 days to obtain crystals. The structure of the nanoparticles was obtained by single-crystal analysis. The molecular structure shown in Figure 1 is Ni 12 (C8H7COO)6(CH3COO) 18 We analyzed it as (CH3C2N2H3)6(H2O)6 and named it Ni-mTA-MI. This is a cyclic polynuclear complex containing 12 Ni atoms, with metatoluic acid, N-methylimidazole, acetate ions, and water as ligands.

[0029] Furthermore, the green solution was rotary evaporated at 100 mbar for 2 hours using a rotary evaporator to obtain a green, viscous fluid. This fluid was then placed in a vacuum oven and held at 80°C for 4 hours to obtain the photoresist product. The photoresist product was dissolved in a 5% PGMEA solution, and DLS particle size measurement was performed on the solution, with the results shown in Figure 2. In addition, infrared absorption spectroscopy and XPS measurements were performed, yielding the results shown in Figures 3 and 4a-4d. From these results, it was confirmed that the material produced by the method of this example is a metal-organic ligand nanoparticle.

[0030] Example 2 5.44 g (40 mmol) of m-toluic acid and 4.98 g (20 mmol) of nickel acetate tetrahydrate were placed in a 150 mL flask, dissolved in 45 mL of THF, heated and stirred at 65°C for 5 minutes, then 2.16 g of benzylamine was added, and the mixture was heated and stirred at 65°C overnight. After a green solution was obtained, the solution was allowed to stand at a low temperature for 15 days to obtain crystals. Powder XRD analysis was performed, and the results are shown in Figure 7. The XRD results of this example are basically the same as those of Example 1, and it is presumed that in this example, the methylimidazole in Example 1 is substituted with benzylamine, and the molecular structure is Ni 12 (C8H7COO)6(CH3COO) 18 The compound is (C7H9N)6(H2O)6, which we named Ni-mTA-BA.

[0031] Furthermore, the green solution was subjected to rotary evaporation at 100 mbar for 2 hours using a rotary evaporator to obtain a green, viscous fluid. This fluid was then placed in a vacuum oven and held at 80°C for 4 hours to obtain the photoresist product. The photoresist product was dissolved in a 5% PGMEA solution, and DLS particle size measurement was performed on the solution. The results are shown in Figure 8. From these results, it was confirmed that the material produced by the method of this example is a metal-organic ligand nanoparticle.

[0032] Example 3 5.44 g (40 mmol) of m-toluic acid and 4.98 g (20 mmol) of nickel acetate tetrahydrate were placed in a 150 mL flask, dissolved in 45 mL of THF, heated and stirred at 65°C for 5 minutes, then 2.51 g of 1-Butylimidazole was added, and the mixture was heated and stirred at 65°C overnight. After a green solution was obtained, the solution was allowed to stand at a low temperature for 15 days to obtain crystals. The structure of the nanoparticles was confirmed by single-crystal analysis, and the molecular structure shown in Figure 5 is Ni 12 (C8H7COO)6(CH3COO) 18 (C7H 12 We analyzed it to be N2)6(H2O)6 and named it Ni-mTA-BI. This is a cyclic polynuclear complex containing 12 Ni atoms, with metatoluic acid, N-butylimidazole, acetate ions, and water as ligands.

[0033] Furthermore, the green solution was subjected to rotary evaporation at 100 mbar for 2 hours using a rotary evaporator to obtain a green, viscous fluid. This fluid was then placed in a vacuum oven and held at 80°C for 4 hours to obtain the photoresist product. The photoresist product was dissolved in a 5% PGMEA solution, and DLS particle size measurement was performed on the solution. The results are shown in Figure 6. From these results, it was confirmed that the material produced by the method of this example is a metal-organic ligand nanoparticle.

[0034] Example 4 5.44 g (40 mmol) of m-toluic acid and 4.98 g (20 mmol) of nickel acetate tetrahydrate were placed in a 150 mL flask, dissolved in 45 mL of THF, heated and stirred at 65 °C for 5 minutes, then 4.59 g of triamylamine was added, and the mixture was heated and stirred at 65 °C overnight. After a green solution was obtained, the solution was allowed to stand at a low temperature for 15 days to obtain crystals. Analytical measurements were performed, and the results are shown in Figure 7. The molecular structure is Ni 12 (C8H7COO)6(CH3COO) 18 (C 15 H33 It was hypothesized that it was N)6(H2O)6. This was named Ni-mTA-TAA.

[0035] Furthermore, the green solution was subjected to rotary evaporation at 100 mbar for 2 hours using a rotary evaporator to obtain a green, viscous fluid. This fluid was then placed in a vacuum oven and held at 80°C for 4 hours to obtain the photoresist product. The photoresist product was dissolved in a 5% PGMEA solution, and DLS particle size measurement was performed on the solution. The results are shown in Figure 9. From these results, it was confirmed that the material produced by the method of this example is a metal-organic ligand nanoparticle.

[0036] Examples 5-8 0.5 wt% PAG-1 (N-hydroxynaphthalimide trifluoromethanesulfonate) was added to the Ni-mTA-MI solution (5.0 wt%) prepared in Example 1. The solvent was propylene glycol monoethyl ether acetate (PGMEA), and the mixture was stirred for 5 minutes until all of it was dissolved to obtain a photoresist mixed solution.

[0037] After filtering the photoresist mixture twice using a filter head, the silicon wafer was placed on a spin coater, the photoresist was dropped onto the silicon wafer, and the wafer was spin-coated for 1 minute at a rotation speed of 2000 r / min. Next, it was heated on a hot plate at 90°C for 1 minute. Medium ultraviolet exposure and development were performed. The specific conditions were as follows: The thin film was exposed to 254 nm ultraviolet irradiation, and the exposure agent amount was 150 mJ / cm². 2 A contact exposure mask was used. Metaxylene was used as the developer, and development was performed for 5 seconds, 10 seconds, and 15 seconds, respectively, to obtain line exposure patterns with a half-pitch of 1 to 10 μm. The results are shown in Figures 10 to 12. Further electron beam exposure and development were performed with an exposure agent amount of 400 μC / cm². 2 When the beam current density was set to 1.0-3.0 A and the image was developed for 15 seconds using orthoxylene as the developer, a line with a half-pitch of 100 nm was obtained. The pattern obtained from the measurement is shown in Figure 13.

[0038] Examples 9-11 0.5 wt% PAG-1 (N-hydroxynaphthalimide trifluoromethanesulfonate) was added to the Ni-mTA-MI solution (5.0 wt%) prepared in Example 1. The solvent was propylene glycol monoethyl ether acetate (PGMEA), and the mixture was stirred for 5 minutes until all of it was dissolved to obtain a photoresist mixed solution.

[0039] After filtering the photoresist mixture twice using a filter head, the silicon wafer was placed on a spin coater, the photoresist was dropped onto the silicon wafer, and the wafer was spin-coated for 1 minute at a rotation speed of 2000 r / min. Next, it was heated on a hot plate at 100°C for 1 minute. Medium ultraviolet exposure and development were performed. The specific conditions were as follows: The thin film was exposed to 254 nm ultraviolet irradiation, and the exposure agent amount was 150 mJ / cm². 2 A contact exposure mask was used. Metaxylene was used as the developer, and development was performed for 5 seconds, 10 seconds, and 15 seconds, respectively, to obtain line exposure patterns with a half-pitch of 1 to 10 μm. The results are shown in Figures 14 to 16.

[0040] Examples 12-14 0.5 wt% PAG-1 (N-hydroxynaphthalimide trifluoromethanesulfonate) was added to the Ni-mTA-MI solution (5.0 wt%) prepared in Example 1. The solvent was propylene glycol monoethyl ether acetate (PGMEA), and the mixture was stirred for 5 minutes until all of it was dissolved to obtain a photoresist mixed solution.

[0041] After filtering the photoresist mixture twice using a filter head, the silicon wafer was placed on a spin coater, the photoresist was dropped onto the silicon wafer, and the wafer was spin-coated for 1 minute at a rotation speed of 2000 r / min. Next, it was heated on a hot plate at 110°C for 1 minute. Medium ultraviolet exposure and development were performed. The specific conditions were as follows: The thin film was exposed to 254 nm ultraviolet irradiation, and the exposure agent amount was 150 mJ / cm². 2A contact exposure mask was used. Metaxylene was used as the developer, and development was performed for 5 seconds, 10 seconds, and 15 seconds, respectively, to obtain line exposure patterns with a half-pitch of 1 to 10 μm. The results are shown in Figures 17 to 19.

[0042] Examples 15-16 0.5 wt% PAG-1 (N-hydroxynaphthalimide trifluoromethanesulfonate) was added to the Ni-mTA-BA solution (5.0 wt%) prepared in Example 2. The solvent was propylene glycol monoethyl ether acetate (PGMEA), and the mixture was stirred for 5 minutes until all of it was dissolved to obtain a photoresist mixed solution.

[0043] After filtering the photoresist mixture twice using a filter head, the silicon wafer was placed on a spin coater, the photoresist was dropped onto the silicon wafer, and the wafer was spin-coated for 1 minute at a rotation speed of 2000 r / min. Next, the wafers were heated on a hot plate at 90°C, 100°C, and 110°C for 1 minute each. Medium ultraviolet exposure and development were then performed. The specific conditions were as follows: The thin film was exposed to 254 nm ultraviolet irradiation, and the exposure agent amount was 150 mJ / cm². 2 A contact exposure mask was used. When developed for 10 seconds using metaxylene as the developer, a line exposure pattern with a half-pitch of 1-10 μm was obtained. The results are shown in Figures 20a to 20c. Note that A in Figure 20a, B in Figure 20b, and C in Figure 20c correspond to 90°C, 100°C, and 110°C, respectively. Electron beam exposure and development were performed with a exposure agent amount of 400 μC / cm². 2 With a beam current density of 1.0 to 3.0 A, development was performed using mesitylene as the developer for 15 seconds, resulting in a line with a half-pitch of 100 nm. The pattern obtained from the measurement is shown in Figure 21.

[0044] Examples 17-19 0.5 wt% PAG-1 (N-hydroxynaphthalimide trifluoromethanesulfonate) was added to the Ni-mTA-BI solution (5.0 wt%) prepared in Example 3. The solvent was propylene glycol monoethyl ether acetate (PGMEA), and the mixture was stirred for 5 minutes until all of it was dissolved to obtain a photoresist mixed solution.

[0045] After filtering the photoresist mixture twice using a filter head, the silicon wafer was placed on a spin coater, the photoresist was dropped onto the silicon wafer, and the wafer was spin-coated for 1 minute at a rotation speed of 2000 r / min. Next, the wafers were heated on a hot plate at 90°C, 100°C, and 110°C for 1 minute each. Medium ultraviolet exposure and development were then performed. The specific conditions were as follows: The thin film was exposed to 254 nm ultraviolet irradiation, and the exposure agent amount was 1000 mJ / cm². 2 A contact exposure mask was used. When developed for 10 seconds using metaxylene as the developer, a line exposure pattern with a half-pitch of 1 to 10 μm was obtained. The results are shown in Figures 22a to 22c. Note that A in Figure 22a, B in Figure 22b, and C in Figure 22c correspond to 90°C, 100°C, and 110°C, respectively.

[0046] Examples 20-22 0.5 wt% PAG-1 (N-hydroxynaphthalimide trifluoromethanesulfonate) was added to the Ni-mTA-TAA solution (5.0 wt%) prepared in Example 4. The solvent was propylene glycol monoethyl ether acetate (PGMEA), and the mixture was stirred for 5 minutes until all of it was dissolved to obtain a photoresist mixed solution.

[0047] After filtering the photoresist mixture twice using a filter head, the silicon wafer was placed on a spin coater, the photoresist was dropped onto the silicon wafer, and the wafer was spin-coated for 1 minute at a rotation speed of 2000 r / min. Next, the wafers were heated on a hot plate at 90°C, 100°C, and 110°C for 1 minute each. Medium ultraviolet exposure and development were then performed. The specific conditions were as follows: The thin film was exposed to 254 nm ultraviolet irradiation, and the exposure agent amount was 2000 mJ / cm². 2 A contact exposure mask was used. When developed for 10 seconds using metaxylene as the developer, a line exposure pattern with a half-pitch of 1 to 10 μm was obtained. The results are shown in Figures 23a to 23c. Note that A in Figure 23a, B in Figure 23b, and C in Figure 23c correspond to 90°C, 100°C, and 110°C, respectively.

[0048] In summary, the present invention yielded several types of effective nanoparticles and corresponding compositions. Their structures and good lithography performance under medium ultraviolet and EBL conditions were verified. Excellent photoresist performance, including high resolution, high sensitivity, and low line roughness, can be achieved.

Claims

1. Ni-based organic coordination nanoparticles, wherein the general formula of the nanoparticles is Ni ｍ X ｎ (CH ３ COO) ｔ Y ｐ H ｑ In the formula, X is the metatoluyl ion, CH ３ COO represents an acetate ion, Y represents a nitrogen-containing organic ligand, m, n, p, and q are each independently selected from any integer between 1 and 20, and t is selected from any integer between 0 and 20. The nanoparticles are produced by the following method, namely by mixing and stirring a nickel-containing compound, metatoluic acid, and a nitrogen-containing organic ligand in an organic solvent, followed by post-treatment, wherein the molar ratio of nickel-containing compound:metatoluic acid:nitrogen-containing organic ligand is (2-10):(4-10):(2-10), characterized in that these are Ni-based organic coordination nanoparticles.

2. The Ni-based organic coordination nanoparticle according to claim 1, characterized in that the nitrogen-containing organic ligand is one or more selected from organic aliphatic amines and their derivatives, imidazoles and their derivatives, and the nickel-containing compound is selected from nickel acetate and nickel acetate tetrahydrate.

3. The Ni-based organic coordination nanoparticle according to claim 2, characterized in that the organoaliphatic amines are one or more selected from benzylamine and triamylamine, and the imidazole and its derivatives are one or more selected from N-methylimidazole and N-butylimidazole.

4. The Ni-based organic coordination nanoparticle according to claim 3, characterized in that the nitrogen-containing organic ligand is selected from benzylamine, triamylamine, N-methylimidazole, and N-butylimidazole.

5. The Ni-based organic coordination nanoparticles according to any one of claims 1 to 4, characterized in that the size of the Ni-based organic coordination nanoparticles is 2 nm to 5 nm.

6. The Ni-based organic coordination nanoparticles according to any one of claims 1 to 4, characterized in that the post-treatment includes stirring at 45°C to 80°C for 5 to 24 hours, followed by rotary evaporation using a rotary evaporator at 35°C to 50°C for 20 to 80 minutes, and then vacuuming in a vacuum oven at 65°C to 90°C for 2 hours.

7. The general structural formula for nanoparticles is as follows: Ni １２ (C ８ H ７ COO) ６ (CH ３ COO) １８ (CH ３ C ２ N ２ H ３ ) ６ (H ２ O) ６ ; Ni １２ (C ８ H ７ COO) ６ (CH ３ COO) １８ (C ７ H ９ N) ６ (H ２ O) ６ ; Ni １２ (C ８ H ７ COO) ６ (CH ３ COO) １８ (C ７ H １２ N ２ ) ６ (H ２ O) ６ ; Ni １２ (C ８ H ７ COO) ６ (CH ３ COO) １８ (C １５ H ３３ N) ６ (H ２ O) ６ A Ni-based organic coordination nanoparticle according to any one of claims 1 to 4, characterized in that it is one of any of the above.

8. A photoresist composition characterized by comprising Ni-based organic coordination nanoparticles according to any one of claims 1 to 7.

9. The photoresist composition according to claim 8, further comprising a photoacid generator and an organic dispersion solvent, wherein the photoacid generator accounts for 5 wt% to 10 wt% of the composition, and the nanoparticles account for 3 wt% to 20 wt% of the composition.

10. The photoresist composition according to claim 9, characterized in that the photoacid generator is one or more selected from N-hydroxynaphthalimide trifluoromethanesulfonate, 1,4-aminonaphthalenesulfonic acid, 2-amino-5,7-naphthalenedisulfonic acid, tert-butylphenyliodonium perfluorooctanesulfonate, triphenylsulfonium perfluorobutanesulfonate, triphenylsulfonium perfluorobutylsulfonate, and triphenylsulfonium trifluorosulfonate.

11. The photoresist composition according to claim 9, characterized in that the organic dispersion solvent is one or more selected from ethyl acetate, butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol methyl ether acetate, 1-ethoxy-2-propanol, methanol, ethanol, and propanol.

12. A lithography method characterized by employing a photoresist composition according to any one of claims 8 to 11, dropping the photoresist composition onto a substrate, performing spin coating and heating, exposing it to electron beam, medium ultraviolet, deep ultraviolet or extreme ultraviolet light, and developing it using a developer.

13. The exposure agent dose is 50 mJ / cm². ２ ~500 mJ / cm ２ The lithography method according to claim 12, characterized in that...

14. The lithography method according to claim 13, characterized in that the developer is a mixture of one or more selected from toluene, mesitylene, orthoxylene, metaxylene, paraxylene, tetralin, decalin, cyclohexane, and n-propanol, and the development temperature is 20°C to 50°C.

15. The use of Ni-based organic coordination nanoparticles according to any one of claims 1 to 7, characterized in that it is applied to the field of photoresists, particularly electron beam, medium ultraviolet, deep ultraviolet and / or extreme ultraviolet photoresists.

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