Ag-based organic coordination nanoparticles, their preparation method, photoresist compositions, and their applications

Abstract

This invention relates to Ag-based organic coordination nanoparticles and their preparation method, photoresist compositions and their applications, wherein the Ag-based organic coordination nanoparticles have the general formula: [Ag m (R) n (Q) x ] y The preparation method involves adding silver salt and the first organic ligand to a sample vial, dissolving them in an organic solvent, stirring for a certain time under a certain temperature, filtering, concentrating, cooling and crystallizing or evaporating and crystallizing, and finally recrystallizing in an organic solvent to obtain Ag-based organic coordination nanoparticles. This nanoparticle composition can be used as an electron beam, mid-ultraviolet, deep ultraviolet, and EUV photoresist.

Description

Technical Field

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

[0002] Photoresist is a corrosion-resistant thin film material whose solubility changes upon exposure to ultraviolet light, electron beams, ion 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 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 constantly evolving, from I-line, G-line, and deep ultraviolet (DUV) lithography (including 248nm KrF lithography and 193nm ArF lithography) to finer processing methods such as EUV 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 very important evaluation indicator for photoresists. 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 etched products.

[0003] 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, extremely fine patterns (e.g., less than or equal to approximately 20 nanometers) can be formed during the exposure process in semiconductor device manufacturing. For EUV exposure, the absorptivity of the photoresist itself, the reaction mechanism of solubility changes after exposure, and the size distribution of the photoresist components have a significant impact on the overall performance of the photoresist. Since metal elements have a higher absorptivity to EUV radiation, metal-containing photoresist materials have attracted considerable interest, with metal oxide nanoparticle photoresists being a hot research area. The Ober research group at Cornell University first introduced the concept of metal oxide nanoparticles as a next-generation EUV photoresist material. The synthesis of these nanoparticles generally involves controlled hydrolysis of Zr or Hf in an excess of carboxylic acid, followed by precipitation to obtain ZrO2 or HfO2 nanoparticle photoresists with organic ligands. The size of these nanoparticles is controlled to 2-5 nm, which is advantageous for photolithography below 20 nm. To further explore more efficient metal-organic nanophotoresists, this invention focuses on Ag-based organic ligand nanoparticle photoresists and has prepared photoresists with excellent photolithographic performance. Summary of the Invention

[0004] This invention proposes a novel Ag-based organic coordination nanoparticle, its preparation method, a photoresist composition containing the nanoparticle, and its applications.

[0005] This invention provides Ag-based organic coordination nanoparticles with the general formula: [Ag m (R) n (Q) x ] y ,

[0006] R can be selected from bis(diphenylphosphine)methane (dppm), bis(dicyclohexylphosphine)methane (abbreviated dcpm), bis(diphenylamino)methane, N,N-bis(diphenylphosphine)amine (abbreviated dppa), N,N,N',N'-tetramethyldiaminomethane, N,N,N',N'-tetraethyldiaminomethane, etc.

[0007] Q can be selected from CH3COO, C2H5COO, C3H7COO, i-C3H7COO, C4H9COO, C6H 13 COO, C9H 19 COO, C6H5COO, CF3COO, C2F5COO, C3F7COO, i-C3F7COO, C4F9COO, C6F 13 COO, C9F 19COO, C6H5COO, etc.

[0008] Where m, n, x, and y all range from 1 to 4.

[0009] Furthermore, Ag-based organic coordination nanoparticles can have the following structure:

[0010] Ag2(dppm)2(CH3COO)2;

[0011] Ag4(dppm)2(CH3COO)4;

[0012] Ag4(dppm)2(CF3COO)4;

[0013] Ag2(dppm)2(C2H5COO)2;

[0014] Ag4(dppm)2(C2F5COO)4;

[0015] Ag4(dppm)2(C4F9COO)4;

[0016] Ag2(dcpm)2(CH3COO)2;

[0017] Ag4(dppa)2(CH3COO)4

[0018] The size of the Ag-based organic coordination nanoparticle crystal is 1nm-4nm, preferably 1nm-2nm.

[0019] The Ag-based organic coordination nanoparticles described above were prepared by the following method:

[0020] Silver salt and the first organic ligand were added to sample vials, dissolved in organic solvent, stirred for a certain time under a certain temperature, filtered, concentrated, cooled to crystallize or evaporated to crystallize, and finally recrystallized in organic solvent to obtain Ag-based organic coordination nanoparticles.

[0021] Furthermore, the ratio of the silver salt to the first organic ligand is 1:(0.5-1);

[0022] The organic 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, tetrahydrofuran, methanol, ethanol, propanol, dichloromethane, and trichloromethane.

[0023] The stirring temperature is controlled at 0-120℃, preferably 15-80℃, and more preferably 20-40℃.

[0024] The present invention also provides a photoresist composition comprising the above-mentioned nanoparticles.

[0025] Furthermore, the above-mentioned photoresist composition also includes a photoinitiator and an organic dispersing solvent, wherein the photoinitiator preferably accounts for 0.1 wt% to 10 wt% of the composition, and the nanoparticles preferably account for 1 wt% to 20 wt% of the composition.

[0026] Furthermore, the photoinitiator 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.

[0027] 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-methoxy-2-propanol, propylene glycol mono-n-propyl ether, propylene glycol butyl ether, 1-ethoxy-2-propanol, methanol, ethanol, and propanol. The solvent is preferably 1-ethoxy-2-propanol.

[0028] [Metal-Organic Coordination Nanoparticle Photoresist Patterning Method]

[0029] The present invention also provides a method for forming a photolithographic pattern, which uses the above-mentioned photoresist composition, drops the photoresist composition onto a substrate, spin-coates it into a film, heats it on a hot stage, and then exposes it with an electron beam or medium ultraviolet, deep ultraviolet, or extreme ultraviolet light, and develops it with a developer.

[0030] Furthermore, the spin coating speed is 1000-6000 rpm; the heating temperature of the hot table is controlled at 50-110℃, and the heating time is controlled at 30-900s.

[0031] Furthermore, the exposure dose is 50–8000 mJ / cm². 2 .

[0032] Furthermore, the developer is selected from any one or more mixtures of decahydronaphthalene, tetrahydronaphthalene, indene, indene, quinoline, 1-methylnaphthalene, toluene, o-xylene, m-xylene, p-xylene, ethyl acetate, butyl acetate, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, propylene glycol mono-n-propyl ether, propylene glycol butyl ether, n-hexane, and cyclohexane, and the developing temperature is room temperature or 20°C to 50°C.

[0033] 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.

[0034] The substrate is selected from silicon substrates. Other substrates that are insoluble in developer can also be selected according to actual needs.

[0035] Furthermore, the aforementioned nanoparticles are used in the field of photoresists, particularly electron beam, mid-ultraviolet, deep ultraviolet, and EUV photoresists. Regarding masks, deep ultraviolet and longer wavelength light sources serve as transmission masks, extreme ultraviolet light as reflection masks, and electron beams expose according to patterns set in the software.

[0036] The Ag-based organic coordination nanoparticles provided in this invention have a unique structure. When the photoacid-generating agent is irradiated with ultraviolet light, it generates photoacid, which can interact with the Ag-based organic coordination nanoparticles, thereby altering the polarity of the nanoparticles and causing them to aggregate. Therefore, the solubility of the Ag-based organic coordination nanoparticles changes before and after exposure. Due to these characteristics, using these Ag-based organic coordination nanoparticles as a photoresist component can create a difference in solubility between the photosensitive and light-shielding portions of the photoresist in the developer. The photosensitive portion aggregates, resulting in reduced solubility in the developer, while the light-shielding portion does not aggregate and dissolves in the developer. This allows for the removal of unexposed areas after development, thus obtaining a pattern of the desired shape. Using the Ag-based organic coordination nanoparticles of this invention as a photoresist component can achieve superior photolithography performance, including high resolution, high sensitivity, and low line roughness. Attached Figure Description

[0037] Figure 1 The structural formula of the crystalline compound prepared in Example 1 of this invention is shown below.

[0038] Figure 2 The 1H NMR spectrum of the crystalline compound prepared in Example 1 of this invention;

[0039] Figure 3 The results of dynamic light scattering particle size test in Example 1 of this invention;

[0040] Figure 4 This is the exposure pattern of Embodiment 1 of the present invention;

[0041] Figure 5 This is the structural formula of Embodiment 2 of the present invention;

[0042] Figure 6 This is the hydrogen NMR spectrum of Example 2 of the present invention;

[0043] Figure 7 The results of dynamic light scattering particle size test in Example 2 of this invention;

[0044] Figure 8 This is the exposure pattern of Embodiment 2 of the present invention;

[0045] Figure 9This is the structure of Embodiment 3 of the present invention;

[0046] Figure 10 This is the hydrogen NMR spectrum of Example 3 of the present invention;

[0047] Figure 11 The results of dynamic light scattering particle size test in Example 3 of this invention;

[0048] Figure 12 This is the exposure pattern of Embodiment 3 of the present invention. Detailed Implementation

[0049] To facilitate understanding of the present invention, a more complete description will be given below with reference to the accompanying drawings. Preferred embodiments of the invention are shown in the drawings. However, the invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a thorough and complete understanding of the disclosure of the invention.

[0050] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

[0051] This invention provides Ag-based organic coordination nanoparticles with the general formula: [Ag m (R) n (Q) x ] y

[0052] R can be selected from bis(diphenylphosphine)methane (dppm), bis(dicyclohexylphosphine)methane (abbreviated dcpm), bis(diphenylamino)methane, N,N-bis(diphenylphosphine)amine (abbreviated dppa), N,N,N',N'-tetramethyldiaminomethane, N,N,N',N'-tetraethyldiaminomethane, etc.

[0053] Q can be selected from CH3COO, C2H5COO, C3H7COO, i-C3H7COO, C4H9COO, C6H 13 COO, C9H 19 COO, C6H5COO, CF3COO, C2F5COO, C3F7COO, i-C3F7COO, C4F9COO, C6F 13 COO, C9F 19 COO, C6H5COO, etc.

[0054] Where m, n, x, and y all range from 1 to 4;

[0055] Furthermore, Ag-based organic coordination nanoparticles can have the following structure:

[0056] Ag2(dppm)2(CH3COO)2;

[0057] Ag4(dppm)2(CH3COO)4;

[0058] Ag4(dppm)2(CF3COO)4;

[0059] Ag2(dppm)2(C2H5COO)2;

[0060] Ag4(dppm)2(C2F5COO)4;

[0061] Ag4(dppm)2(C4F9COO)4;

[0062] Ag2(dcpm)2(CH3COO)2;

[0063] Ag4(dppa)2(CH3COO)4.

[0064] The size of the Ag-based organic coordination nanoparticle crystal is 1nm-4nm, preferably 1nm-2nm.

[0065] The Ag-based organic coordination nanoparticles provided in this invention have a unique structure. When the photoacid-generating agent is irradiated with ultraviolet light, it generates photoacid, which can interact with the Ag-based organic coordination nanoparticles, thereby altering the polarity of the nanoparticles and causing them to aggregate. Therefore, the solubility of the Ag-based organic coordination nanoparticles changes before and after exposure. Due to these characteristics, using these Ag-based organic coordination nanoparticles as a photoresist component can create a difference in solubility between the photosensitive and light-shielding portions of the photoresist in the developer. The photosensitive portion aggregates, resulting in reduced solubility in the developer, 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. Using the Ag-based organic coordination nanoparticles of this invention as a photoresist component can achieve superior photolithography performance, including high resolution, high sensitivity, and low line roughness.

[0066] The Ag-based organic coordination nanoparticles described above were prepared by the following method:

[0067] Silver salt and the first organic ligand were added to sample vials, dissolved in an organic solvent, stirred for a certain time under a certain temperature, filtered, concentrated, cooled to crystallize or evaporated to crystallize, and finally recrystallized in an organic solvent to obtain Ag-based organic coordination nanoparticles.

[0068] Furthermore, the ratio of the silver salt to the first organic ligand is 1:(0.5-1);

[0069] The organic 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, tetrahydrofuran, methanol, ethanol, propanol, dichloromethane, and trichloromethane.

[0070] The stirring temperature is controlled between 0 and 120°C, preferably between 15 and 80°C, and more preferably between 20 and 40°C.

[0071] Some embodiments of the present invention provide Ag organic coordination nanoparticle photoresist compositions, comprising the above-mentioned nanoparticles, and further comprising a photoinitiator and an organic dispersing solvent, wherein the photoinitiator preferably accounts for 0.1 wt%-10 wt% of the composition, and the nanoparticles preferably account for 1 wt%-20% of the composition.

[0072] Furthermore, the photoinitiator 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.

[0073] 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-methoxy-2-propanol, propylene glycol mono-n-propyl ether, propylene glycol butyl ether, 1-ethoxy-2-propanol, methanol, ethanol, and propanol. The solvent is preferably 1-ethoxy-2-propanol.

[0074] Some embodiments of the present invention provide a method for patterning Ag organic coordination nanoparticle photoresist. Using the above-mentioned photoresist composition, the photoresist composition is spin-coated onto a substrate, heated on a hot stage, and then exposed with an electron beam or mid-ultraviolet, deep ultraviolet, or extreme ultraviolet light, and developed with a developer.

[0075] Furthermore, the spin coating speed is 1000-6000 rpm; the heating temperature of the hot table is controlled at 50-110℃, and the heating time is controlled at 30-900s.

[0076] Furthermore, the exposure dose is 50–8000 mJ / cm². 2 .

[0077] Furthermore, the developer is selected from any one or more mixtures of decahydronaphthalene, tetrahydronaphthalene, indene, indane, quinoline, 1-methylnaphthalene, toluene, o-xylene, m-xylene, ethyl acetate, butyl acetate, ethanol, n-propanol, isopropanol, n-butanol, n-hexane, and cyclohexane, and the developing temperature is room temperature or 20°C to 50°C.

[0078] 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.

[0079] The substrate is selected from silicon substrates. Other substrates that are insoluble in developer can also be selected according to actual needs.

[0080] Furthermore, the aforementioned nanoparticles are used in the field of photoresists, particularly electron beam, mid-ultraviolet, deep ultraviolet, extreme ultraviolet, and / or EUV photoresists. Regarding masks, deep ultraviolet and longer wavelength light sources serve as transmission masks, extreme ultraviolet as reflection masks, and electron beams expose according to patterns set in the software.

[0081] Example 1

[0082] 0.769 g of bis(diphenylphosphine)methane was dissolved in 20 mL of dichloromethane, and 0.884 g of silver trifluoroacetate was added. The mixture was stirred for 12 h, filtered, and the solvent was evaporated to obtain a white solid product. The product was recrystallized in dichloromethane, dried under vacuum at room temperature, and a sample was taken for 1H NMR spectroscopy (see Appendix). Figure 2 Among them, δ3.26 (CH2), δ7.26, 7.40 (C6H5), the crystal structure is shown in the attached figure. Figure 1 As shown, the molecular formula is Ag4(dppm)2(CF3COO)4.

[0083] Weigh 0.5 g Ag4(dppm)2(CF3COO)4 and 0.05 g N-hydroxynaphthalimide trifluoromethanesulfonate, dissolve them in 0.945 g propylene glycol monomethyl ether acetate, and filter the solution three times through a 0.22 μm filter to obtain a photoresist composition. Dynamic light scattering particle size analysis showed an average particle size of 1.7 nm (see appendix). Figure 3 The spin coater was set to 2000 rpm for 1 minute to spin-coat a uniform photoresist film onto a silicon wafer. The wafer was then heated on an 80°C hot stage for 1 minute. The wafer was then exposed to a 254nm mercury lamp at a dose of 1260 mJ / cm². 2 Using m-xylene as the developer, development for 10 seconds yielded a line pattern with a half-pitch of 10 μm (see appendix). Figure 4 ).

[0084] Example 2

[0085] Dissolve 0.157 g of bis(diphenylphosphine)methane in 16 mL of dichloromethane, add 0.136 g of silver acetate, and stir until a clear solution is obtained. Filter, concentrate the solution, and cool to allow a white precipitate to form. Separate the precipitate, recrystallize it in dichloromethane / n-hexane, and perform 1H NMR spectroscopy on a sample of the crystals (see Appendix). Figure 6 The 1H NMR spectrum shows δ2.02 (CH3), δ3.31 (CH2), and δ7.0–7.5 (C6H5). The crystal structure is shown in the attached figure. Figure 5 As shown, the molecular formula is Ag4(dppm)2(CH3COO)4, which is vacuum dried at room temperature.

[0086] Weigh 0.5 g Ag₄(dppm)₂(CH₃COO)₄ and 0.05 g N-hydroxynaphthalimide trifluoromethanesulfonate, dissolve them in 0.945 g propylene glycol monomethyl ether acetate, and filter the solution three times through a 0.22 μm filter. Dynamic light scattering particle size analysis showed an average particle size of 1.7 nm (see Appendix). Figure 7 The spin coater was set to 2000 rpm for 1 minute to spin-coat a uniform photoresist film onto a silicon wafer. The wafer was then heated on an 80°C hot stage for 1 minute. The wafer was then exposed to a 254nm mercury lamp at a dose of 2000 mJ / cm². 2 Using o-xylene as the developer, development for 15 seconds yielded a line pattern with a half-pitch of 10 μm (see appendix). Figure 8 ).

[0087] Example 3

[0088] Dissolve 0.104 g of Ag₄(dppm)₂(CH₃COO)₄ crystals in 30 mL of methanol, add 0.056 g of bis(diphenylphosphine)methane, and stir until a clear solution is obtained. Filter, concentrate the solution, and cool to allow precipitation to form. Separate the precipitate, recrystallize it in dichloromethane / n-hexane, separate the precipitate again, and perform 1H NMR spectroscopy on a sample of the crystals (see Appendix). Figure 10 The 1H NMR spectra are δ2.12 (CH3), δ3.36 (CH2), and δ6.95-7.45 (C6H5). The crystal structure is shown in the attached figure. Figure 9 As shown, the molecular formula is Ag2(dppm)2(CH3COO)2, which is vacuum dried at room temperature.

[0089] Weigh 0.5 g Ag₂(dppm)₂(OAc)₂ and 0.05 g N-hydroxynaphthalimide trifluoromethanesulfonate, dissolve them in 0.945 g propylene glycol monomethyl ether acetate, and filter the solution three times using a 0.22 μm filter. Dynamic light scattering particle size analysis showed an average particle size of 1.3 nm (see Appendix). Figure 11The spin coater was set to 2000 rpm for 1 minute to spin-coat a uniform photoresist film onto a silicon wafer. The wafer was then heated on an 80°C hot stage for 1 minute. The wafer was then exposed to a 254nm mercury lamp at a dose of 270 mJ / cm². 2 Using m-xylene as the developer, development for 30 seconds yielded a line pattern with a half-pitch of 10 μm (see appendix). Figure 12 ).

[0090] In summary, this invention has yielded a variety of effective nanoparticles and corresponding compositions, verifying that the structures possess excellent photolithography performance under medium ultraviolet and electron beam conditions, enabling superior photolithography performance such as high resolution, high sensitivity, and low line roughness.

Claims

1. An Ag-based organic coordination nanoparticle, characterized in that, The general formula is: [Ag m (R) n (Q) x ] y The ranges of m, n, x, and y are all 1-4; Wherein, R is selected from bis(diphenylphosphine)methane (dppm), bis(dicyclohexylphosphine)methane (abbreviated dcpm), bis(diphenylamino)methane, N,N-bis(diphenylphosphine)amine (abbreviated dppa), N,N,N',N'-tetramethyldiaminomethane, N,N,N',N'-tetraethyldiaminomethane; Q is selected from CH3COO, C2H5COO, C3H7COO, i-C3H7COO, C4H9COO, C6H 13 COO, C9H 19 COO, C6H5COO, CF3COO, C2F5COO, C3F7COO, i-C3F7COO, C4F9COO, C6F 13 COO, C9F 19 COO, C6H5COO.

2. The Ag-based organic coordination nanoparticles according to claim 1, characterized in that, Its specific structure is as follows: Ag2(dppm)2(CH3COO)2; Ag4(dppm)2(CH3COO)4; Ag4(dppm)2(CF3COO)4; Ag2(dppm)2(C2H5COO)2; Ag4(dppm)2(C2F5COO)4; Ag4(dppm)2(C4F9COO)4; Ag2(dcpm)2(CH3COO)2; Ag4(dppa)2(CH3COO)4.

3. The Ag-based organic coordination nanoparticles according to claim 1, characterized in that, The size of the Ag-based organic coordination nanoparticle crystals is 1 nm-4 nm.

4. The method for preparing Ag-based organic coordination nanoparticles according to any one of claims 1-3, characterized in that, The process includes the following steps: adding silver salt and the first organic ligand into sample vials respectively, adding organic solvent to dissolve them, stirring for a certain time under a certain temperature, filtering, concentrating, cooling to crystallize or evaporating to crystallize, and finally recrystallizing in an organic solvent to obtain Ag-based organic coordination nanoparticles, wherein the ratio of silver salt to the first organic ligand is 1:(0.5~1). The first ligand is selected from bis(diphenylphosphine)methane (dppm), bis(dicyclohexylphosphine)methane (dcpm), bis(diphenylamino)methane, N,N-bis(diphenylphosphine)amine (dppa), N,N,N',N'-tetramethyldiaminomethane, and N,N,N',N'-tetraethyldiaminomethane.

5. The method for preparing Ag-based organic coordination nanoparticles according to claim 4, characterized in that, The organic 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, tetrahydrofuran, methanol, ethanol, propanol, dichloromethane, and trichloromethane.

6. The method for preparing Ag-based organic coordination nanoparticles according to claim 4, characterized in that, The stirring temperature is controlled between 0 and 120 ℃.

7. A photoresist composition comprising the Ag-based organic coordination nanoparticles according to any one of claims 1-3, further comprising a photoinitiator and an organic dispersion solvent, wherein, The photoinitiator accounts for 0.1wt%-10wt% of the composition, and the Ag-based organic coordination nanoparticles account for 1wt%-20wt% of the composition.

8. The photoresist composition according to claim 7, characterized in that, The photoinitiator 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.

9. The photoresist composition according to claim 7, 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-methoxy-2-propanol, propylene glycol mono-n-propyl ether, propylene glycol butyl ether, 1-ethoxy-2-propanol, methanol, ethanol, and propanol.

10. A method for patterning Ag organic coordination nanoparticle photoresist, comprising using the photoresist composition as described in any one of claims 7-9, wherein the photoresist composition is spin-coated onto a substrate, heated on a hot stage, and then exposed to electron beam or mid-ultraviolet, deep ultraviolet, or extreme ultraviolet light, and developed using a developer; wherein the spin-coating speed is 1000~6000 rpm; the heating temperature of the hot stage is controlled at 50~110 ℃, the heating time is controlled at 30~900 s, and the exposure dose is 50~8000 mJ / cm 2 The developer is selected from any one or more of the following: decahydronaphthalene, tetrahydronaphthalene, indene, indane, quinoline, 1-methylnaphthalene, toluene, o-xylene, m-xylene, ethyl acetate, butyl acetate, ethanol, n-propanol, isopropanol, n-butanol, n-hexane, and cyclohexane. The developing temperature is room temperature or 20℃~50℃. The thickness of the pre-formed film after removing the organic dispersion solvent can be 10 nm~100 nm.

11. Use of the Ag-based organic coordination nanoparticles according to any one of claims 1-3 for use in electron beam, mid-ultraviolet, deep ultraviolet and / or extreme ultraviolet photoresists.

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