Ni-based organic coordination nanoparticles and preparation method therefor, photoresist composition comprising ni-based organic coordination nanoparticles, and use of photoresist composition

Abstract

Provided are Ni-based organic coordination nanoparticles and a preparation method therefor, a photoresist composition comprising the Ni-based organic coordination nanoparticles, and a use of the photoresist composition. The Ni-based organic coordination nanoparticles are obtained by mixing and stirring a nickel-containing compound, m-methylbenzoic acid, and a nitrogen-containing organic ligand in an organic solvent, and then carrying out post-treatment. In addition, nanoparticles represented by the chemical general formula NimXn(CH3COO)tYpHq are obtained, wherein X is m-methylbenzoate, CH3COO represents acetate, Y is the nitrogen-containing organic ligand, m, n, p and q are each any integer independently selected from 1-20, and t is any integer selected from 1-20. The Ni-based organic coordination nanoparticles are used as a photoresist component and can achieve more excellent photoetching performance such as high resolution, high sensitivity, and low line roughness.

Description

Ni-based organic coordination nanoparticles and preparation method thereof, photoresist composition containing same and application thereof Technical Field

[0001] The present invention relates to the technical field of photoresists, in particular to Ni-based organic coordination nanoparticles and a preparation method thereof, a photoresist composition and application thereof. Background Art

[0002] Photolithography, the technique of transferring a pattern from a mask onto a substrate through a photoresist under a certain amount of energy, is the core of chip manufacturing. In the integrated circuit manufacturing process, photolithography costs account for one-third or more of the total cost; the size and quality of the lithography significantly impact chip performance. With the continuous advancement of photolithography technology and the continuous reduction of light source linewidth, 13.5nm extreme ultraviolet light exposure technology has gradually become the main choice for lithography nodes below 7nm.

[0003] Photoresist refers to a corrosion-resistant thin film material whose solubility is altered by exposure to ultraviolet light, electron beams, particle beams, extreme ultraviolet (EUV), or soft x-rays. It is widely used for pattern transfer in the fabrication of high-end micro- and nanostructures, including semiconductor integrated circuits, liquid crystal display panels, and high-end optical devices. With the continuous advancement of semiconductor technology and the growth of Moore's Law, semiconductor process sizes have continued to shrink, placing higher demands on the reduction of feature sizes. To meet the needs of more advanced semiconductor processes and achieve smaller feature sizes, photolithography technology has continued to evolve, from i-line, G-line, deep ultraviolet (DUV), 193nm, and immersion 193nm to EUV and electron beam lithography, among other precision fabrication methods. After the photoresist film is exposed and developed to form the lithographic pattern, it is then etched using either dry or wet methods. The portions of the substrate material not covered by the photoresist film are directly etched, while the covered substrate surface is protected from etching by the photoresist film. Etching resistance is a very important evaluation index of photoresist. Excellent etching resistance can ensure that the photoresist can protect the substrate surface from damage during the etching process, effectively simplify the etching process, and greatly improve the yield of the etched product.

[0004] Traditional photoresists have complex components, including photoresist resin, photosensitizer, leveling agent, stabilizer, dispersant, thickener and solvent, etc. The production process is cumbersome and requires extremely high control process for proportion and purity. Because traditional photoresists are mostly large molecular polymers and contain many functional additives, their complex composition leads to a wide size distribution of photoresists, with components of various sizes. Some size conformations can reach 10nm to 20nm, making the size of the photoresist pattern difficult to control and may also cause numerous defects. In addition, for traditional photoresists, their scope of use is greatly affected by the wavelength of the light source, and different photoresists are required to match different light sources.

[0005] Extreme ultraviolet (EUV) lithography has attracted attention as a fundamental technology for manufacturing next-generation semiconductor devices. EUV lithography is a patterning technique that uses EUV radiation, which has a wavelength of approximately 13.5 nanometers, as an exposure light source. EUV lithography is known to enable the formation of extremely fine patterns (e.g., approximately 20 nanometers or less) during the exposure process during semiconductor device manufacturing.

[0006] However, in the prior art, the pattern edges obtained by photolithography have large roughness and low pattern resolution, which is not conducive to the application of photolithography technology. It is necessary to improve this. Technical issues

[0007] Based on this, it is necessary to propose a new Ni-based organic coordination nanoparticle and its preparation method, a photoresist composition containing the same and its application to address the problems of large edge roughness and low resolution of the pattern obtained by traditional photoresist lithography. Technical Solutions

[0008] In one aspect of the present invention, a Ni-based organic coordination nanoparticle is provided. The general chemical formula of the nanoparticle is Ni m X n (CH3COO) t Y p H q , wherein X represents m-methylbenzoate, CH3COO represents acetate, Y represents a nitrogen-containing organic ligand, m, n, p, and q are each independently selected from any integer from 1 to 20, and t is selected from any integer from 0 to 20; the nanoparticles are prepared by the following method: a nickel-containing compound, m-methylbenzoic acid, and a nitrogen-containing organic ligand are mixed and stirred in an organic solvent and then post-treated, wherein the molar ratio of the nickel-containing compound:m-methylbenzoic acid:and the nitrogen-containing organic ligand is (2-10):(4-10):(2-10).

[0009] Furthermore, the nitrogen-containing organic ligand is selected from any one or more of organic fatty amines and their derivatives, imidazole and its derivatives; nickel-containing compounds such as soluble nickel salts, such as nickel acetate, nickel acetate tetrahydrate, and nickel chloride.

[0010] Furthermore, the organic fatty amines are selected from any one or more of benzylamine and tripentylamine; the imidazole and its derivatives are selected from any one or more of N-methylimidazole and N-butylimidazole.

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

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

[0013] Furthermore, the post-treatment includes: stirring at 45°C-80°C for 5h-24h, then rotary evaporating at 35°C-50°C for 20min-80min using a rotary evaporator, and then vacuum drying at 65°C-90°C for 2h in a vacuum oven.

[0014] Furthermore, the general structural formula of the nanoparticles is one of the following:

[0015] Ni 12 (C8H7COO)6(CH3COO) 18 (CH3C2N2H3)6(H2O)6;

[0016] Ni 12 (C8H7COO)6(CH3COO) 18 (C7H9N)6(H2O)6;

[0017] Ni 12 (C8H7COO)6(CH3COO) 18 (C7H 12 N2)6(H2O)6;

[0018] Ni 12 (C8H7COO)6(CH3COO) 18 (C 15 H 33 N)6(H2O)6.

[0019] Furthermore, the above-mentioned photoresist composition further includes a photoacid and an organic dispersing solvent. The photoacid preferably accounts for 5wt%-10wt% of the composition, and the nanoparticles preferably account for 3wt%-20wt% of the composition.

[0020] Furthermore, the photoacid agent is selected from any one or more of N-hydroxynaphthalimide trifluoromethanesulfonic acid, 1,4-aminonaphthalenesulfonic acid, 2-amino-5,7-naphthalenedisulfonic acid, tert-butylphenyliodonium salt perfluorooctanesulfonic acid, triphenylsulfonium perfluorobutanesulfonic acid, triphenylsulfonium perfluorobutyl and triphenylsulfonium trifluorosulfonic acid.

[0021] Furthermore, the organic dispersing solvent is selected from any one or more of ethyl acetate, butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol methyl ether acetate, 1-ethoxy-2-propanol, methanol, ethanol, and propanol. The solvent is preferably propylene glycol methyl ether acetate.

[0022] The present invention also provides a photolithography method, which uses the above-mentioned photoresist composition, drops the photoresist composition onto a substrate, rotates, heats, then exposes it with an electron beam, mid-ultraviolet, deep ultraviolet or extreme ultraviolet, and develops it with a developer.

[0023] The exposure dose of the exposure operation is 50mJ / cm 2 ~500mJ / cm 2 The exposure dose should be controlled within an appropriate range. If the exposure dose is too small, the energy is too low, which is not conducive to the polymerization of the photoresist particles in the exposed area, and is not conducive to the formation of solubility differences between the exposed area and the non-exposed area, resulting in poor development effect. Compared with bare metal nanoparticles, nanoparticles containing organic ligands are more easily polymerized. If the exposure dose is too large, the organic ligands may fall off directly from the metal oxide to form fragments. The photoresist particles can no longer undergo organic ligand exchange reactions, reducing the degree of polymerization in the exposed area.

[0024] Furthermore, the developer is selected from a mixture of any one or more of toluene, mesitylene, o-xylene, m-xylene, p-xylene, tetralin, decalin, cyclohexane, and n-propanol, and the developing temperature is room temperature or 20°C to 50°C. The thickness of the pre-film layer after removing the organic dispersing solvent can be 10nm to 100nm. Specifically, the thickness of the pre-film layer can be 10nm to 20nm, 20nm to 30nm, 30nm to 40nm, 40nm to 50nm, 50nm to 60nm, 60nm to 70nm, 70nm to 80nm, 80nm to 90nm, or 90nm to 100nm.

[0025] Furthermore, the above-mentioned nanoparticles are used in the field of photoresists, especially electron beam, mid-ultraviolet, deep ultraviolet and / or extreme ultraviolet photoresists.

[0026] The exposure conditions are selected from any one of mid-ultraviolet, deep ultraviolet, electron beam, and extreme ultraviolet. The photoresist composition of the present invention can be used in any exposure condition.

[0027] The substrate is selected from a silicon plate. Other substrates that are insoluble in developer can also be selected according to actual needs.

[0028] Regarding masks, deep ultraviolet and longer wavelength light sources are transmissive masks, extreme ultraviolet is a reflective mask, and the electron beam exposes according to the pattern set by the software. Beneficial effects

[0029] Compared with the prior art, the present invention has the following beneficial effects:

[0030] The Ni-based organic coordination nanoparticles obtained by the present invention have a special structure. Under illumination conditions, they can interact with a photoacid generator (photoacid agent), causing material polarity to change and agglomerate, resulting in a change in the solubility of the Ni-based organic coordination nanoparticles before and after illumination. Due to these characteristics, the Ni-based organic coordination nanoparticles can be used as a photoresist component to make the solubility of the photosensitive portion and the light-shielding portion of the photoresist in the developer produce a difference. The photosensitive portion agglomerates in the developer and the solubility is reduced, while the light-shielding portion does not agglomerate and dissolves in the developer, thereby enabling the non-exposed area to be removed after development to obtain a pattern of the desired shape. In particular, due to the special structure of the Ni-based organic coordination nanoparticles, compared to traditional polymer-type photoresists and molecular glass photoresists, the Ni-based organic coordination nanoparticles of the present invention can be used as a photoresist component to achieve more excellent lithographic performance such as high resolution, high sensitivity, and low line roughness. The present invention finds that introducing benzoic acid ligands into Ni-based organic coordination nanoparticles can effectively reduce the crystallinity of the complex, improve the solubility of the material in organic reagents, and facilitate storage and application. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] FIG1 is a cluster structure of a Ni-based organic coordination nanoparticle single crystal analyzed in Example 1 of the present invention;

[0032] FIG2 is a dynamic light scattering diagram of Ni-based organic coordination nanoparticles according to Example 1 of the present invention;

[0033] FIG3 is an infrared spectrum of Ni-based organic coordination nanoparticles according to Example 1 of the present invention;

[0034] 4a-4d are XPS spectra of Ni-based organic coordination nanoparticles according to Example 1 of the present invention;

[0035] FIG5 is a cluster structure of a Ni-based organic coordination nanoparticle single crystal analyzed in Example 3 of the present invention;

[0036] FIG6 is a dynamic light scattering diagram of Ni-based organic coordination nanoparticles according to Example 3 of the present invention;

[0037] FIG7 is a powder XRD spectrum of Ni-based organic coordination nanoparticles of Examples 1, 2, and 4 of the present invention;

[0038] FIG8 is a dynamic light scattering diagram of Ni-based organic coordination nanoparticles according to Example 2 of the present invention;

[0039] FIG9 is a dynamic light scattering diagram of Ni-based organic coordination nanoparticles according to Example 4 of the present invention;

[0040] Figures 10 to 19 are photolithography imaging microscope photos of Ni-based organic coordination nanoparticles according to Example 1 of the present invention;

[0041] Figures 20a-20c and Figure 21 are photolithography imaging microscope photos of Ni-based organic coordination nanoparticles according to Example 2 of the present invention;

[0042] Figures 22a-22c are photolithography imaging microscope photos of Ni-based organic coordination nanoparticles according to Example 3 of the present invention;

[0043] 23a-23c are photolithography imaging microscope photos of Ni-based organic coordination nanoparticles according to Example 4 of the present invention. Modes for Carrying Out the Invention

[0044] Example 1

[0045] 5.44g (40mmol) m-toluic acid and 4.98g (20mmol) Nickel acetate tetrahydrate were added to a 150ml flask, dissolved in 45mL THF, and heated at 65°C with stirring for 5 minutes. 1.67g methylimidazole was then added and heated at 65°C with stirring overnight. After obtaining a green solution, the solution was allowed to stand at low temperature for 15 days to obtain crystals. The structure of the nanoparticles was determined by single crystal analysis, and the molecular structure shown in Figure 1 was Ni 12 (C8H7COO)6(CH3COO) 18 (CH3C2N2H3)6(H2O)6, named Ni-mTA-MI, is a multinuclear complex with m-toluic acid, N-methylimidazole, acetate and water as ligands and containing 12 Ni rings.

[0046] The green solution was then rotary evaporated at 100 mbar for 2 hours to obtain a green viscous fluid. This was then placed in a vacuum oven at 80°C for 4 hours to obtain a photoresist product. The photoresist product was then dissolved in a 5% PGMEA solution, and the solution was subjected to DLS particle size analysis, with the results shown in Figure 2. Infrared spectroscopy and XPS analysis were performed on the solution, yielding the results shown in Figures 3 and 4a-4d. This demonstrates that the substance prepared by the method of this example is metal-organic ligand nanoparticles.

[0047] Example 2

[0048] 5.44 g (40 mmol) of m-toluic acid and 4.98 g (20 mmol) of nickel acetate tetrahydrate were added to a 150 ml flask, dissolved in 45 mL of THF, and heated at 65°C with stirring for 5 minutes. 2.16 g of benzylamine was then added, and the mixture was heated at 65°C with stirring overnight. After obtaining a green solution, the solution was allowed to stand at low temperature for 15 days to obtain crystals. The powder XRD analysis test results are shown in Figure 7. The XRD results of this embodiment are basically consistent with those of Example 1. It is speculated that in this embodiment, benzylamine replaces the methylimidazole in Example 1, and the molecular structure is Ni. 12 (C8H7COO)6(CH3COO) 18 (C7H9N)6(H2O)6, named Ni-mTA-BA.

[0049] The green solution was then rotary evaporated at 100 mbar for 2 hours to obtain a green viscous fluid. This was then placed in a vacuum oven at 80°C for 4 hours to obtain a photoresist product. The photoresist product was then dissolved in a 5% PGMEA solution, and the solution was subjected to a DLS particle size analysis. The results are shown in Figure 8. This indicates that the substance prepared by the method of this example is metal-organic ligand nanoparticles.

[0050] Example 3

[0051] 5.44g (40mmol) m-toluic acid (m-toluic acid) + 4.98g (20mmol) Nickel acetate tetrahydrate (nickel acetate tetrahydrate) were added to a 150ml flask, dissolved in 45mL THF, heated and stirred at 65℃ for 5 minutes, and then 2.51g 1-Butylimidazole (N-butylimidazole) was added and heated and stirred at 65℃ overnight. After obtaining a green solution, the solution was allowed to stand at low temperature for 15 days to obtain crystals. The structure of the nanoparticles can be obtained through single crystal analysis test. The molecular structure shown in Figure 5 is Ni 12 (C8H7COO)6(CH3COO) 18 (C7H 12 N2)6(H2O)6, named Ni-mTA-BI, is a multinuclear complex containing 12 Ni rings with m-methylbenzoic acid, N-butylimidazole, acetate and water as ligands.

[0052] The green solution was then rotary evaporated at 100 mbar for 2 hours to obtain a green viscous fluid. This was then placed in a vacuum oven at 80°C for 4 hours to obtain a photoresist product. The photoresist product was then dissolved in a 5% PGMEA solution, and the solution was subjected to DLS particle size analysis. The results are shown in Figure 6. This indicates that the substance prepared by the method of this example is metal-organic ligand nanoparticles.

[0053] Example 4

[0054] 5.44g (40mmol) m-toluic acid + 4.98g (20mmol) nickel acetate tetrahydrate were added to a 150ml flask and dissolved in 45mL THF. The mixture was heated at 65°C with stirring for 5 minutes. 4.59g triamylamine was then added and the mixture was heated at 65°C with stirring overnight. After obtaining a green solution, the solution was allowed to stand at low temperature for 15 days to obtain crystals. The analytical test results are shown in Figure 7. The molecular structure is presumed to be Ni 12 (C8H7COO)6(CH3COO) 18 (C15H 33 N)6(H2O)6, named Ni-mTA-TAA.

[0055] The green solution was further rotary evaporated at 100 mbar for 2 hours to obtain a green viscous fluid, which was then placed in a vacuum oven at 80°C for 4 hours to obtain a photoresist product. The photoresist product was then dissolved in a 5% PGMEA solution, and the solution was subjected to DLS particle size analysis. The results are shown in Figure 9. This shows that the substance prepared by the method of this example is metal-organic ligand nanoparticles.

[0056] Examples 5-8

[0057] 0.5 wt % PAG-1 (N-hydroxynaphthalimide trifluoromethanesulfonate) was added to the prepared solution of Ni-mTA-MI in Example 1 (5.0 wt %), the solvent was propylene glycol monoethyl ether acetate (PGMEA), and stirred for 5 minutes until completely dissolved to obtain a photoresist mixed solution.

[0058] Filter the photoresist mixture twice with a filter head, then place the silicon wafer on a spreader, add the photoresist to the silicon wafer, set the speed to 2000r / min, and rotate for 1min. Then heat on a hot plate at 90℃ for 1min. In-progress UV exposure-development: The specific conditions are to expose the film to 254nm UV radiation, the exposure dose is 150mJ / cm2, and a contact exposure mask is used. The developer uses meta-xylene, and develops for 5s, 10s, and 15s respectively to obtain a line exposure pattern with a half-pitch of 1-10μm, as shown in Figures 10-12 respectively. Perform electron beam exposure-development with an exposure dose of 400μC / cm 2 , beam intensity 1.0~3.0A, o-xylene is used as developer, development time is 15s, and half-pitch lines of 100nm are obtained. The test pattern is shown in Figure 13.

[0059] Examples 9-11

[0060] 0.5 wt % PAG-1 (N-hydroxynaphthalimide trifluoromethanesulfonate) was added to the prepared solution of Ni-mTA-MI in Example 1 (5.0 wt %), the solvent was propylene glycol monoethyl ether acetate (PGMEA), and stirred for 5 minutes until completely dissolved to obtain a photoresist mixed solution.

[0061] Filter the photoresist mixture twice using a filter head. Then, place the silicon wafer on a spin coater and drip the photoresist onto the wafer. Set the spin coater to 2000 rpm and spin for 1 minute. Then, heat on a hot plate at 100°C for 1 minute. UV exposure-development in progress: The specific conditions are to expose the film to 254nm UV radiation with an exposure dose of 150mJ / cm 2 A contact exposure mask was used. Meta-xylene was used as the developer, and development was performed for 5s, 10s, and 15s, respectively, to obtain line exposure patterns with a half-pitch of 1-10μm, as shown in Figures 14-16.

[0062] Examples 12-14

[0063] 0.5 wt % PAG-1 (N-hydroxynaphthalimide trifluoromethanesulfonate) was added to the prepared solution of Ni-mTA-MI in Example 1 (5.0 wt %), the solvent was propylene glycol monoethyl ether acetate (PGMEA), and stirred for 5 minutes until completely dissolved to obtain a photoresist mixed solution.

[0064] Filter the photoresist mixture twice using a filter head. Then, place the silicon wafer on a spin coater and drip the photoresist onto the wafer. Set the spin coater to 2000 rpm and spin for 1 minute. Then, heat on a hot plate at 110°C for 1 minute. UV exposure-development in progress: The film is exposed to 254nm UV radiation at an exposure dose of 150mJ / cm 2 A contact exposure mask was used. Meta-xylene was used as the developer, and development was performed for 5s, 10s, and 15s, respectively, to obtain line exposure patterns with a half-pitch of 1-10μm, as shown in Figures 17-19.

[0065] Examples 15-16

[0066] 0.5 wt % PAG-1 (N-hydroxynaphthalimide trifluoromethanesulfonate) was added to the prepared solution of Ni-mTA-BA in Example 2 (5.0 wt %), the solvent was propylene glycol monoethyl ether acetate (PGMEA), and stirred for 5 minutes until completely dissolved to obtain a photoresist mixed solution.

[0067] Filter the photoresist mixture twice using a filter head. Then, place the silicon wafer on a spinner and drip the photoresist onto the wafer. Set the spinner to 2000 rpm and spin for 1 minute. Then, heat the film on a hot plate at 90°C, 100°C, and 110°C for 1 minute. UV exposure-development in progress: The film is exposed to 254nm UV radiation with an exposure dose of 150mJ / cm 2 , using a contact exposure mask. Meta-xylene was used as the developer, and development was performed for 10 seconds to obtain a line exposure pattern with a half-pitch of 1-10 μm, as shown in Figures 20a-20c. 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 an exposure dose of 400 μC / cm 2 , beam intensity 1.0 ~ 3.0A, using mesitylene as developer, developing time 15s, to obtain a half-pitch line of 100nm. The test pattern is shown in Figure 21.

[0068] Examples 17-19

[0069] 0.5 wt % PAG-1 (N-hydroxynaphthalimide trifluoromethanesulfonate) was added to the prepared solution of Ni-mTA-BI in Example 3 (5.0 wt %), the solvent was propylene glycol monoethyl ether acetate (PGMEA), and stirred for 5 minutes until completely dissolved to obtain a photoresist mixed solution.

[0070] Filter the photoresist mixture twice using a filter head. Then, place the silicon wafer on a spinner and drip the photoresist onto the wafer. Set the spinner to 2000 rpm and spin for 1 minute. Then, heat the film on a hot plate at 90°C, 100°C, and 110°C for 1 minute. UV exposure-development in progress: The film is exposed to 254nm UV radiation with an exposure dose of 1000mJ / cm 2 A contact exposure mask was used. Meta-xylene was used as the developer for 10 seconds, resulting in a line exposure pattern with a half-pitch of 1-10 μm, as shown in Figures 22a-22c. A in Figure 22a, B in Figure 22b, and C in Figure 22c correspond to temperatures of 90°C, 100°C, and 110°C, respectively.

[0071] Examples 20-22

[0072] 0.5 wt % PAG-1 (N-hydroxynaphthalimide trifluoromethanesulfonate) was added to the prepared solution of Ni-mTA-TAA in Example 4 (5.0 wt %), the solvent was propylene glycol monoethyl ether acetate (PGMEA), and stirred for 5 minutes until completely dissolved to obtain a photoresist mixed solution.

[0073] Filter the photoresist mixture twice using a filter head. Then, place the silicon wafer on a spinner and drip the photoresist onto the wafer. Set the spinner to 2000 rpm and spin for 1 minute. Then, heat the film on a hot plate at 90°C, 100°C, and 110°C for 1 minute. UV exposure-development in progress: The film is exposed to 254nm UV radiation with an exposure dose of 2000mJ / cm 2 A contact exposure mask was used. Meta-xylene was used as the developer for 10 seconds, resulting in a line exposure pattern with a half-pitch of 1-10 μm, as shown in Figures 23a-23c. A in Figure 23a, B in Figure 23b, and C in Figure 23c correspond to temperatures of 90°C, 100°C, and 110°C, respectively.

[0074] In summary, the present invention obtains a variety of effective nanoparticles and corresponding compositions, verifies the structure and has good lithographic performance under mid-ultraviolet and EBL conditions, which can achieve better lithographic performance such as high resolution, high sensitivity, and low line roughness.

Claims

1. A Ni-based organic coordination nanoparticle, characterized in that: The general chemical formula of the nanoparticles is Ni m X n (CH3COO) t Y p H q , wherein X is m-toluate, CH3COO represents acetate, Y is a nitrogen-containing organic ligand, m, n, p, q are each independently selected from any integer from 1 to 20, and t is selected from any integer from 0 to 20; the nanoparticles are prepared by the following method: a nickel-containing compound, m-toluate and a nitrogen-containing organic ligand are mixed and stirred in an organic solvent and then post-treated, wherein the molar ratio of the nickel-containing compound:m-toluate and the nitrogen-containing organic ligand is (2-10):(4-10):(2-10).

2. The Ni-based organic coordination nanoparticles according to claim 1, characterized in that: The nitrogen-containing organic ligand is selected from any one or more of organic fatty amines and their derivatives, imidazole and their derivatives; the nickel-containing compound is selected from nickel acetate and nickel acetate tetrahydrate.

3. The Ni-based organic coordination nanoparticles according to claim 2, characterized in that: The organic fatty amines are selected from any one or more of benzylamine and tripentylamine; the imidazole and its derivatives are selected from any one or more of N-methylimidazole and N-butylimidazole.

4. The Ni-based organic coordination nanoparticles according to claim 3, characterized in that: The nitrogen-containing organic ligand is selected from benzylamine, tripentylamine, 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 2nm-5nm.

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

7. The Ni-based organic coordination nanoparticles according to any one of claims 1 to 4, characterized in that: The general structural formula of the nanoparticles is one 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 N)6(H2O)6.

8. A photoresist composition, characterized in that The invention comprises the Ni-based organic coordination nanoparticles as described in any one of claims 1 to 7.

9. The photoresist composition according to claim 8, characterized in that The composition also includes a photoacid agent and an organic dispersing solvent, wherein the photoacid agent occupies 5wt%-10wt% of the composition, and the nanoparticles occupies 3wt%-20wt% of the composition.

10. The photoresist composition according to claim 9, characterized in that The photoacid agent is selected from any one or more of N-hydroxynaphthaleneimide trifluoromethanesulfonic acid, 1,4-aminonaphthalenesulfonic acid, 2-amino-5,7-naphthalene disulfonic acid, tert-butylphenyl iodonium salt perfluorooctanesulfonic acid, triphenylsulfonium perfluorobutanesulfonic acid, triphenylsulfonium perfluorobutyl and triphenylsulfonium trifluorosulfonic acid.

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

12. A photolithography method, characterized in that: The photoresist composition according to any one of claims 8 to 11 is added dropwise to a substrate, rotated, heated, exposed to electron beam, mid-ultraviolet, deep ultraviolet or extreme ultraviolet light, and developed with a developer.

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

14. The photolithography method according to claim 13, characterized in that: The developer is selected from any one or more mixtures of toluene, mesitylene, o-xylene, m-xylene, p-xylene, tetralin, decalin, cyclohexane, and n-propanol, and the developing temperature is 20° C. to 50° C.

15. The use of the Ni-based organic coordination nanoparticles according to any one of claims 1 to 7, characterized in that: Used in the field of photoresists, especially electron beam, mid-UV, deep UV and / or extreme UV photoresists.

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