Ni-based organic coordination nanoparticles, a preparation method thereof, a photoresist composition containing the same, and applications thereof

Abstract

The present application relates to a kind of Ni-based organic coordination nanoparticles and its preparation method, the photoresist composition comprising it and its application.The Ni-based organic coordination nanoparticles are obtained by mixing, stirring and post-processing in organic solvent using nickel-containing compound, m-toluic acid and nitrogen-containing organic ligand, and nanoparticles with chemical formula Ni m X n (CH3COO) t Y p H q Are obtained, wherein X is m-toluic acid root, CH3COO indicates acetate, Y is nitrogen-containing organic ligand, m, n, p, q are each independently selected from any integer from 1 to 20, t is selected from any integer from 0 to 20.The Ni-based organic coordination nanoparticles as photoresist component can realize more excellent photoetching performance such as high resolution, high sensitivity and low line roughness.

Description

Technical Field

[0001] This invention relates to the field of photoresist technology, and in particular to a Ni-based organic coordination nanoparticle and its preparation method, a photoresist composition and its application. Background Technology

[0002] Photolithography, also known as photoresist, is a technique that transfers patterns from a photomask onto a substrate using photoresist under certain energy conditions. It is the core of chip manufacturing. In integrated circuit manufacturing, photolithography costs account for one-third or more of the total cost; the size and quality of the photolithography significantly affect chip performance. With the continuous development of photolithography technology and the decreasing linewidth of light sources, extreme ultraviolet (EUV) light source exposure technology at 13.5nm has gradually become the main choice for photolithography nodes below 7nm.

[0003] Photoresist is a corrosion-resistant thin film material whose solubility changes upon exposure to ultraviolet light, electron beams, particle beams, extreme ultraviolet (EUV), or soft X-rays. It is widely used for pattern transfer in high-end micro / nano structure manufacturing processes, including semiconductor integrated circuits, LCD panel processing, and high-end optical device manufacturing. With the continuous advancement of semiconductor technology and the development of Moore's Law, semiconductor processes are constantly shrinking, placing higher demands on minimizing feature sizes. To meet the needs of more advanced semiconductor processes and achieve smaller feature sizes, photolithography technology is also constantly evolving, from i-line, G-line, deep ultraviolet (DUV), 193nm, immersion 193nm to finer processing methods such as extreme ultraviolet lithography and electron beam lithography. After the photoresist film is exposed and developed to form a photolithographic pattern, it undergoes dry or wet etching. The substrate material not covered by the photoresist film is directly etched, while the substrate surface covered by the photoresist film is protected from etching. Etching resistance is a crucial evaluation metric for photoresists. Excellent etch resistance ensures that the photoresist protects the substrate surface from damage during the etching process, effectively simplifies the etching process, and significantly improves the yield of etched products.

[0004] Traditional photoresists have a complex composition, including photoresist resin, photosensitizer, leveling agent, stabilizer, dispersant, thickener, and solvent. The manufacturing process is cumbersome, requiring extremely high precision in controlling the proportions and purity. Because traditional photoresists are mostly macromolecular polymers and contain numerous functionalized additives, their complex composition results in a wide size distribution, with components of various sizes, some reaching 10nm to 20nm. This makes it difficult to control the size of the photoresist pattern and can potentially introduce numerous defects. Furthermore, the application range of traditional photoresists is greatly affected by the wavelength of the light source; 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 rays with a wavelength of approximately 13.5 nanometers as the exposure source. According to EUV lithography, it is known that extremely fine patterns (e.g., less than or equal to approximately 20 nanometers) can be formed in the exposure process during the fabrication of semiconductor devices.

[0006] However, in the existing technology, the patterns obtained by photolithography have large edge roughness and low resolution, which is not conducive to the application of photolithography technology. It is necessary to improve this. Summary of the Invention

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

[0008] In one aspect, this invention provides Ni-based organic coordination nanoparticles, the general chemical formula of which is Ni. m X n (CH3COO) t Y p H q Where X is m-methylbenzoate, CH3COO represents acetate, Y is 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: the nickel-containing compound, m-methylbenzoic acid and 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 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, imidazoles and their derivatives; nickel-containing compounds include nickel-containing soluble salts, such as nickel acetate, nickel acetate tetrahydrate, and nickel chloride.

[0010] Furthermore, the organic fatty amine is selected from any one or more of benzylamine and triammonium amine; the imidazole and its derivatives are selected from any one or more of N-methylimidazolium and N-butylimidazolium.

[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-processing includes: stirring at 45℃-80℃ for 5h-24h, then rotary evaporating at 35℃-50℃ for 20min-80min, and then vacuum drying at 65℃-90℃ for 2h in a vacuum oven.

[0014] Furthermore, the general structural formula of 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] The Ni-based organic coordination nanoparticles obtained in this invention possess a unique structure. Under illumination, they can interact with photoacid-generating agents (photoacidifiers), causing a change in material polarity and aggregation. This results in a change in the solubility of the Ni-based organic coordination nanoparticles before and after illumination. Due to these characteristics, using these Ni-based organic coordination nanoparticles as a photoresist component can create a difference in the solubility of the photosensitive and light-shielding portions of the photoresist in the developer. The photosensitive portion aggregates and its solubility in the developer decreases, while the light-shielding portion does not aggregate and dissolves in the developer. This allows for the removal of unexposed areas after development, thereby obtaining a pattern of the desired shape. In particular, due to the unique structure of these Ni-based organic coordination nanoparticles, compared to traditional polymer-based photoresists and molecular glass photoresists, using these Ni-based organic coordination nanoparticles as a photoresist component can achieve superior photolithographic performance, including high resolution, high sensitivity, and low line roughness. This invention discovers 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.

[0020] Furthermore, the above-mentioned photoresist composition also includes a photoacid and an organic dispersing solvent, wherein the photoacid preferably accounts for 5 wt%-10 wt% of the composition, and the nanoparticles preferably account for 3 wt%-20 wt% of the composition.

[0021] Furthermore, the photoacid 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.

[0022] 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. Propylene glycol methyl ether acetate is preferred as the solvent.

[0023] The present invention also provides a photolithography method, which uses the above-mentioned photoresist composition, drops the photoresist composition onto a substrate, rotates it, heats it, and then exposes it with an electron beam, mid-ultraviolet, deep ultraviolet or extreme ultraviolet light, and develops it with a developer.

[0024] The exposure dose for the exposure operation is 50 mJ / cm². 2 ~500mJ / cm 2 The exposure dose should be controlled within a suitable range. Too low an exposure dose results in insufficient energy, which is detrimental to the polymerization of photoresist particles in the exposed area, hindering the formation of a solubility difference between the exposed and unexposed areas, leading to poor development. Compared to bare metal nanoparticles, nanoparticles containing organic ligands polymerize more easily. Excessive exposure dose may cause the organic ligands to detach directly from the metal oxide, forming fragments. This prevents the photoresist particles from undergoing the organic ligand exchange reaction, reducing the degree of polymerization in the exposed area.

[0025] Furthermore, the developer is selected from any one or a mixture of toluene, mesitylene, o-xylene, m-xylene, p-xylene, tetrahydronaphthalene, decahydronaphthalene, cyclohexane, and n-propanol, and the developing temperature is room temperature or 20°C to 50°C.

[0026] The thickness of the pre-formed film after removing the organic dispersion solvent can be 10 nm to 100 nm. Specifically, the thickness of the pre-formed film 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.

[0027] Furthermore, the aforementioned nanoparticles are used in the field of photoresists, particularly electron beam, mid-ultraviolet, deep ultraviolet, and / or extreme ultraviolet photoresists.

[0028] 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 under any exposure condition.

[0029] The substrate is selected from silicon substrates. Other substrates that are insoluble in developer can also be selected according to actual needs.

[0030] Regarding masks, deep ultraviolet and longer wavelength light sources are used as transmission masks, while extreme ultraviolet light is used as a reflection mask. The electron beam is exposed according to the pattern set in the software. Attached Figure Description

[0031] Figure 1 The cluster structure of the Ni-based organic coordination nanoparticles single crystal was analyzed in Example 1 of this invention;

[0032] Figure 2 This is a dynamic light scattering diagram of the Ni-based organic coordination nanoparticles of Example 1 of the present invention;

[0033] Figure 3 The infrared spectrum of the Ni-based organic coordination nanoparticles of Example 1 of this invention;

[0034] Figure 4 The XPS spectrum of the Ni-based organic coordination nanoparticles of Example 1 of this invention is shown below.

[0035] Figure 5 The cluster structure of the Ni-based organic coordination nanoparticles single crystal was analyzed in Example 3 of this invention;

[0036] Figure 6 The image shows the dynamic light scattering pattern of the Ni-based organic coordination nanoparticles in Example 3 of this invention.

[0037] Figure 7 The powder XRD patterns of Ni-based organic coordination nanoparticles in Examples 1, 2, and 4 of this invention are shown below.

[0038] Figure 8 This is a dynamic light scattering diagram of the Ni-based organic coordination nanoparticles of Example 2 of the present invention;

[0039] Figure 9 This is a dynamic light scattering diagram of the Ni-based organic coordination nanoparticles of Example 4 of the present invention;

[0040] Figures 10-19 This is a photolithographic imaging microscope image of Ni-based organic coordination nanoparticles from Example 1 of the present invention;

[0041] Figure 20 and Figure 21 This is a photolithographic imaging microscope image of Ni-based organic coordination nanoparticles from Example 2 of the present invention;

[0042] Figure 22 This is a photolithographic imaging microscope image of Ni-based organic coordination nanoparticles in Example 3 of the present invention;

[0043] Figure 23 This is a photolithographic imaging microscope image of the Ni-based organic coordination nanoparticles in Example 4 of the present invention. Detailed Implementation

[0044] Example 1

[0045] 5.44 g (40 mmol) m-toluic acid and 4.98 g (20 mmol) Nickel acetate tetrahydrate were added to a 150 mL flask and dissolved in 45 mL THF. The mixture was heated and stirred at 65 °C for 5 minutes. Then, 1.67 g methylimidazole was added, and the mixture was heated and stirred at 65 °C 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 obtained by single-crystal analysis, and the crystals were analyzed to reveal the structure of the nanoparticles. Figure 1 The molecular structure shown is Ni 12 (C8H7COO)6(CH3COO) 18 (CH3C2N2H3)6(H2O)6, named Ni-mTA-MI, is a polynuclear complex containing 12 Ni rings with m-methylbenzoic acid, N-methylimidazolium, acetate, and water as ligands.

[0046] Furthermore, the green solution was 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 the photoresist product. The photoresist product was dissolved in a 5% PGMEA solution, and the solution was subjected to DLS particle size analysis. The results are as follows: Figure 2 As shown. Infrared spectroscopy and XPS tests were performed on it, yielding the following results. Figures 3-4 The test results shown indicate that the substance prepared by the method in this embodiment is a metal-organic ligand nanoparticle.

[0047] Example 2

[0048] 5.44 g (40 mmol) m-toluic acid and 4.98 g (20 mmol) Nickel acetate tetrahydrate were added to a 150 mL flask and dissolved in 45 mL THF. The solution was heated and stirred at 65 °C for 5 minutes. Then, 2.16 g Benzylamine was added, and the mixture was heated and stirred overnight at 65 °C. After obtaining a green solution, the solution was allowed to stand at low temperature for 15 days to obtain crystals. The crystals were analyzed by powder XRD. 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 methylimidazole in Example 1, and the molecular structure is Ni. 12 (C8H7COO)6(CH3COO) 18 (C7H9N)6(H2O)6, named Ni-mTA-BA.

[0049] Furthermore, the green solution was 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 the photoresist product. The photoresist product was dissolved in a 5% PGMEA solution, and the solution was subjected to DLS particle size analysis. The results are as follows: Figure 8 As shown, the substance prepared by the method in this embodiment is a metal-organic ligand nanoparticle.

[0050] Example 3

[0051] 5.44 g (40 mmol) m-toluic acid and 4.98 g (20 mmol) Nickel acetate tetrahydrate were added to a 150 mL flask and dissolved in 45 mL THF. The mixture was heated and stirred at 65 °C for 5 minutes. Then, 2.51 g 1-Butylimidazole (N-butylimidazole) was added, and the mixture was heated and stirred overnight at 65 °C. 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 could be obtained by single-crystal analysis. Figure 5 The molecular structure shown is Ni 12 (C8H7COO)6(CH3COO) 18 (C7H 12 N2)6(H2O)6, named Ni-mTA-BI, is a polynuclear complex containing 12 Ni rings with m-methylbenzoic acid, N-butylimidazole, acetate, and water as ligands.

[0052] Furthermore, the green solution was 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 the photoresist product. The photoresist product was dissolved in a 5% PGMEA solution, and the solution was subjected to DLS particle size analysis. The results are as follows: Figure 6 As shown, the substance prepared by the method in this embodiment is a metal-organic ligand nanoparticle.

[0053] Example 4

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

[0055] Furthermore, the green solution was 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 the photoresist product. The photoresist product was dissolved in a 5% PGMEA solution, and the solution was subjected to DLS particle size analysis. The results are as follows: Figure 9 As shown, the substance prepared by the method in this embodiment is a metal-organic ligand nanoparticle.

[0056] Examples 5-8

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

[0058] The photoresist mixture was filtered twice using a filter head. The silicon wafer was then placed on a spin coater, and the photoresist was dropped onto the wafer at a speed of 2000 rpm for 1 minute. It was then heated at 90°C on a hot plate for 1 minute. Intra-ultraviolet exposure-development was then performed: the film was exposed to 254 nm ultraviolet radiation at an exposure dose of 150 mJ / cm². 2A contact exposure mask was used. The developer was m-m-xylene, and development was performed for 5s, 10s, and 15s respectively, resulting in line exposure patterns with a half-pitch of 1-10μm. See [the table below for details]. Figures 10-12 Electron beam exposure and development were performed at an exposure dose of 400 μC / cm². 2 With a beam current of 1.0–3.0 A, o-xylene was used as the developer, and the development time was 15 s. A line with a half-pitch of 100 nm was obtained. The test pattern is shown below. Figure 13 .

[0059] Examples 9-11

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

[0061] The photoresist mixture was filtered twice using a filter head. The silicon wafer was then placed on a spin coater, and the photoresist was dropped onto the wafer at a speed of 2000 rpm for 1 minute. It was then heated at 100°C on a hot plate for 1 minute. Intra-ultraviolet exposure-development was then performed: the film was exposed to 254 nm ultraviolet radiation at an exposure dose of 150 mJ / cm². 2 A contact exposure mask was used. The developer was m-m-xylene, and development was performed for 5s, 10s, and 15s respectively, resulting in line exposure patterns with a half-pitch of 1-10μm. See [the table below for details]. Figures 14-16 .

[0062] Examples 12-14

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

[0064] The photoresist mixture was filtered twice using a filter head. The silicon wafer was then placed on a spin coater, and the photoresist was dropped onto the wafer at a speed of 2000 rpm for 1 minute. It was then heated at 110°C on a hot plate for 1 minute. Intra-ultraviolet exposure-development was then performed: the film was exposed to 254 nm ultraviolet radiation at an exposure dose of 150 mJ / cm². 2 A contact exposure mask was used. The developer was m-m-xylene, and development was performed for 5s, 10s, and 15s respectively, resulting in line exposure patterns with a half-pitch of 1-10μm. See [the table below for details]. Figures 17-19 .

[0065] Examples 13-16

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

[0067] The photoresist mixture was filtered twice using a filter head. The silicon wafer was then placed on a spin coater, and the photoresist was dropped onto the wafer at a speed of 2000 rpm for 1 minute. The wafer was then heated on a hot plate at 90°C, 100°C, and 110°C for 1 minute each. Intra-ultraviolet exposure-development was then performed: the film was exposed to 254 nm ultraviolet radiation at an exposure dose of 150 mJ / cm². 2 A contact exposure mask was used. The developer was m-m-xylene, and development was performed for 10 seconds, resulting in a line exposure pattern with a half-pitch of 1-10 μm. (See attached image.) Figure 20 , Figure 20 Figures A, B, and C correspond to 90℃, 100℃, and 110℃, respectively. Electron beam exposure-development was performed at an exposure dose of 400 μC / cm². 2 With a beam current of 1.0–3.0 A, using trimethylbenzene as the developer and a development time of 15 s, a line with a half-pitch of 100 nm was obtained. The test pattern is shown below. Figure 21 .

[0068] Examples 17-19

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

[0070] The photoresist mixture was filtered twice using a filter head. The silicon wafer was then placed on a spin coater, and the photoresist was dropped onto the wafer at a speed of 2000 rpm for 1 minute. The wafer was then heated on a hot plate at 90°C, 100°C, and 110°C for 1 minute each. Intra-ultraviolet exposure-development was then performed: the film was exposed to 254 nm ultraviolet radiation at an exposure dose of 1000 mJ / cm². 2 A contact exposure mask was used. The developer was m-m-xylene, and development was performed for 10 seconds, resulting in a line exposure pattern with a half-pitch of 1-10 μm. (See attached image.) Figure 22 ,in, Figure 22Figures A, B, and C correspond to 90℃, 100℃, and 110℃, respectively.

[0071] Examples 20-22

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

[0073] The photoresist mixture was filtered twice using a filter head. The silicon wafer was then placed on a spin coater, and the photoresist was dropped onto the wafer at a speed of 2000 rpm for 1 minute. The wafer was then heated on a hot plate at 90°C, 100°C, and 110°C for 1 minute each. Intra-ultraviolet exposure-development was then performed: the film was exposed to 254 nm ultraviolet radiation at an exposure dose of 2000 mJ / cm². 2 A contact exposure mask was used. The developer was m-m-xylene, and development was performed for 10 seconds, resulting in a line exposure pattern with a half-pitch of 1-10 μm. (See attached image.) Figure 23 ,in, Figure 23 Figures A, B, and C correspond to 90℃, 100℃, and 110℃, respectively.

[0074] In summary, this invention has yielded a variety of effective nanoparticles and corresponding compositions, verifying that the structure and the nanoparticles exhibit excellent photolithography performance under medium ultraviolet and EBL conditions, enabling superior photolithography 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 nanoparticles is Ni m X n (CH3COO) t Y p H q O r Where X is m-methylbenzoate, CH3COO represents acetate, Y is 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); The nitrogen-containing organic ligand is selected from benzylamine, tripentylamine, N-methylimidazolium, and N-butylimidazolium; The nickel-containing compound is selected from nickel acetate and nickel acetate tetrahydrate; The nanoparticles have one of the following general structural formulas: 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; It’s 12 (C8H7COO)6(CH3COO) 18 (C 15 H 33 N)6(H2O)6。 2. The Ni-based organic coordination nanoparticles according to claim 1, characterized in that, The size of the Ni-based organic coordination nanoparticles is 2nm-5nm.

3. The Ni-based organic coordination nanoparticles according to claim 1, characterized in that, The post-treatment includes: stirring at 45℃-80℃ for 5h-24h, then evaporating at 35℃-50℃ for 20min-80min in a rotary evaporator, and then vacuum drying at 65℃-90℃ for 2h in a vacuum oven.

4. A photoresist composition, characterized in that, Including the Ni-based organic coordination nanoparticles as described in any one of claims 1-3.

5. The photoresist composition according to claim 4, characterized in that, It also includes a photoacid and an organic dispersing solvent, wherein the photoacid accounts for 5 wt%-10 wt% of the composition and the nanoparticles account for 3 wt%-20 wt% of the composition.

6. The photoresist composition according to claim 5, characterized in that, The photoacid 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.

7. The photoresist composition according to claim 5, characterized in that, The organic dispersion 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.

8. A photolithography method, characterized in that, Using the photoresist composition according to any one of claims 4-7, the photoresist composition is dropped onto a substrate, rotated, heated, and then exposed with an electron beam, mid-ultraviolet, deep ultraviolet, or extreme ultraviolet light, and developed with a developer.

9. The photolithography method according to claim 8, characterized in that, Exposure dose is 50 mJ / cm 2 ~500 mJ / cm 2 .

10. The photolithography method according to claim 9, characterized in that, The developer is selected from any one or a mixture of toluene, mesitylene, o-xylene, m-xylene, p-xylene, tetrahydronaphthalene, decahydronaphthalene, cyclohexane, and n-propanol, and the developing temperature is 20℃~50℃.

11. The use of the Ni-based organic coordination nanoparticles according to any one of claims 1-3, characterized in that, Used in the field of photoresist, the photoresist is an electron beam, mid-ultraviolet, deep ultraviolet and / or extreme ultraviolet photoresist.

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