Zn-based organic coordination nanoparticle and preparation method therefor, photoresist composition and use thereof

Abstract

Provided are a Zn-based organic coordination nanoparticle and a preparation method therefor, a photoresist composition and the use thereof. The general formula of the Zn-based organic coordination nanoparticles is Znx(M)y(N)z, wherein x, y and z are an integer greater than or equal to 1; M is cinnamic acid and derivatives thereof; and N is any one or more of an organic fatty amine and derivatives thereof, a pyridine and derivatives thereof, a pyrrole and derivatives thereof, a pyrimidine and derivatives thereof, a pyridazine and derivatives thereof, a piperidine and derivatives thereof, and an amide and derivatives thereof. A Zn-based organic coordination nanoparticle photoresist, under the condition that no photoinitiator is present, can absorb photon self-initiation by means of cinnamic acid in the photoresist structure, such that an exposure pattern is directly obtained, thereby improving the exposure efficiency.

Description

Zn-based organic coordination nanoparticles and preparation method thereof, photoresist composition and application thereof Technical Field

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

[0002] Photoresist is a key material for fine patterning in microelectronics. It typically consists of a photoinitiator, photoresist resin, solvent, monomer, and other additives. Photoinitiators are compounds that absorb energy of a certain wavelength in the ultraviolet (250-420 nm) or visible (400-800 nm) region, generating free radicals, cations, and other substances, thereby initiating monomer polymerization or polymer decomposition. Traditional photoresists, and the metal-based photoresists that have been extensively studied in recent years, have historically required the chemical changes caused by photoinitiators to produce changes in solubility.

[0003] However, photons must first be absorbed and decomposed by the photoinitiator, and then the photoinitiator products must react with the photoresist resin. To ensure its solubility in the solvent, the amount of photoinitiator added is limited, resulting in low exposure efficiency and low photoresist sensitivity, significantly affecting production efficiency. Furthermore, photoinitiators are chemically unstable and expensive, adding cost and difficulty to the production process. Technical issues

[0004] Based on this, it is necessary to propose a new Zn-based organic coordination nanoparticle and a preparation method thereof, a photoresist composition containing the same and its application to address the problems of low exposure efficiency and high cost of traditional photoresists. Technical Solutions

[0005] In one aspect of the present invention, a Zn-based organic coordination nanoparticle is provided. The general formula of the Zn-based organic coordination nanoparticle is Zn x (M) y (N) z , x, y, z are integers ≥ 1, M is cinnamic acid and its derivatives, and N is any one or more of organic fatty amines and their derivatives, pyridine and its derivatives, pyrrole and its derivatives, pyrimidine and its derivatives, pyridazine and its derivatives, piperidine and its derivatives, and amides and their derivatives.

[0006] Optionally, M is a compound of formula (I), Wherein, R1, R2, R3, R4, and R5 are independently selected from hydrogen, alkyl, alkoxy, alkyl alcohol, halogenated hydrocarbon, hydroxyl, methoxy, nitro, -F, -Cl, -Br, or -I.

[0007] Optionally, the structural formula of the compound represented by the general formula (I) is

[0008] Optionally, N is diethylamine, and the structural formula of the Zn-based organic coordination nanoparticles is Zn(C6H5CHCHCOO)4(C4H 11 N)2H2.

[0009] Optionally, the size of the Zn-based organic coordination nanoparticle crystals is 1 nm-4 nm.

[0010] In another aspect, the present invention provides a method for preparing Zn-based organic coordination nanoparticles, comprising the following steps:

[0011] The zinc-containing compound, the nitrogen-containing organic ligand and the M compound are mixed and stirred in an organic solvent and then post-treated to obtain the compound. The molar percentage of the M compound to the zinc-containing compound is in the range of 1:1 to 6:1.

[0012] Optionally, the zinc-containing compound is selected from zinc salts such as zinc acetate, zinc acetate dihydrate, zinc chloride or zinc sulfate.

[0013] Optionally, the nitrogen-containing organic ligand is selected from organic amines such as diethylamine, tetrahydropyrrole, piperidine, and diisopropylethylamine.

[0014] Optionally, the post-treatment includes: stirring at 50° C. for 6 h to 24 h, then vacuum evaporating the mixture using a rotary evaporator for 1 h, and then vacuum drying the mixture in a vacuum oven at 50° C. for 5 h.

[0015] In another aspect, the present invention provides a photoresist composition comprising the aforementioned nanoparticles.

[0016] Optionally, the photoresist composition further includes an organic dispersing solvent, which is selected from any one or more of ethyl acetate, butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol methyl ether, propylene glycol ethyl ether, 1-ethoxy-2-propanol, methanol, ethanol, and propanol.

[0017] Another aspect of the present invention provides a photolithography method, which uses the above-mentioned photoresist composition, drips the photoresist composition onto a substrate, rotates, heats, and then exposes it to electron beam, mid-ultraviolet, deep ultraviolet or extreme ultraviolet light, and develops it with a developer. Optionally, the exposure dose under mid-ultraviolet or deep ultraviolet light is 50 mJ / cm 2 ~500mJ / cm 2 .

[0018] Optionally, the developer is selected from a mixture of any one or more of indene, indane, quinoline, 1-methylnaphthalene, toluene, o-xylene, m-xylene, mesitylene, ethyl acetate, butyl acetate, ethanol, n-propanol, tetralin, decalin, isopropanol, n-butanol, n-hexane and cyclohexane, and the developing temperature is 20°C to 50°C.

[0019] Another aspect of the present invention provides a use of Zn-based organic coordination nanoparticles for use in the field of photoresists, including electron beam, mid-ultraviolet, deep ultraviolet or extreme ultraviolet photoresists. Beneficial effects

[0020] Compared with the prior art, the present invention has the following beneficial effects:

[0021] The Zn-based organic coordination nanoparticle photoresist provided by the embodiments of the present invention, on the one hand, can directly obtain an exposure pattern without a photoinitiator through self-initiation by cinnamic acid in the photoresist structure absorbing photons, thereby improving exposure efficiency. On the other hand, the Zn-based organic coordination nanoparticle photoresist provided by the present invention does not contain a photoinitiator, reducing production costs. Furthermore, the Zn-based organic coordination nanoparticle photoresist of the present invention produces zinc-centered crystals, which can improve the storage stability of the photoresist. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] FIG1 is a single crystal image of Zn-based organic coordination nanoparticles according to Example 1 of the present invention;

[0023] FIG2 is a hydrogen NMR spectrum of the Zn-based organic coordination nanoparticles and raw materials of Example 1 of the present invention;

[0024] FIG3 is an exposure sample image of the Zn-based organic coordination nanoparticles of Example 1 of the present invention at 254 nm;

[0025] FIG4 is an exposure sample image of the Zn-based organic coordination nanoparticles of Example 1 of the present invention at 248 nm;

[0026] FIG5 is a sample image of Zn-based organic coordination nanoparticles according to Example 1 of the present invention exposed under an electron beam (E-beam);

[0027] FIG6 is an exposure sample image of Zn-based organic coordination nanoparticles according to Example 2 of the present invention at 254 nm;

[0028] FIG7 is an exposure sample image of Zn-based organic coordination nanoparticles according to Example 3 of the present invention at 254 nm;

[0029] FIG8 is an exposure sample image of Comparative Example 1 of the present invention;

[0030] FIG9 is a hydrogen NMR spectrum of the Zn-based organic coordination nanoparticles and raw materials of Example 7 of the present invention;

[0031] FIG10 is an infrared spectrum of the Zn-based organic coordination nanoparticle photoresist according to Example 7 of the present invention;

[0032] FIG11 is an exposure sample image of Zn-based organic coordination nanoparticles according to Example 7 of the present invention at 254 nm;

[0033] FIG12 is a sample image of the photoresist of the comparative example of the present invention exposed at 254 nm. Modes for Carrying Out the Invention

[0034] Reference will now be made in detail to embodiments of the present invention, one or more examples of which are described below. Each example is provided to illustrate, not to limit, the present invention. Indeed, it will be apparent to those skilled in the art that various modifications and variations may be made to the present invention without departing from the scope or spirit of the invention. For example, features illustrated or described as part of one embodiment may be used in another embodiment to produce further embodiments.

[0035] Therefore, it is intended that the present invention covers such modifications and variations as come within the scope of the appended claims and their equivalents. Other objects, features, and aspects of the present invention are disclosed in or are obvious from the following detailed description. Those skilled in the art will appreciate that this discussion is merely a description of exemplary embodiments and is not intended to limit the broader aspects of the present invention.

[0036] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this invention pertains. The terms used herein in the specification of the present invention are for the purpose of describing specific embodiments only and are not intended to limit the present invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0037] Except as shown in the operating examples or otherwise indicated, all numbers used in the specification and claims to express the amount of ingredients, physicochemical properties, etc. are understood to be adjusted by the term "about" in all cases. For example, therefore, unless otherwise indicated, the numerical parameters listed in the above specification and the appended claims are approximate values, and those skilled in the art will be able to appropriately change these approximate values ​​using the teachings disclosed herein to seek to obtain the desired properties. The use of numerical ranges expressed as endpoints includes all numbers within the range and any range within the range, for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4 and 5, etc.

[0038] Photoresist "sensitivity" refers to the minimum light energy or minimum charge (for electron beams) incident on a unit area that causes the photoresist to react completely. In the present invention, the unit of ultraviolet photoresist sensitivity is mJcm -2 Indicates (the smaller the value, the higher the photoresist sensitivity); the unit of electron beam photoresist sensitivity is μCcm -2 The smaller the value, the higher the sensitivity of the photoresist. Photoresist sensitivity can also be reflected by the minimum exposure dose, which is exposure dose = light intensity × exposure time.

[0039] The embodiment of the present invention provides a Zn-based organic coordination nanoparticle, the general formula of the Zn-based organic coordination nanoparticle is Zn x (M) y (N) z , x, y, z are integers ≥ 1, M is cinnamic acid and its derivatives, and N is any one or more of organic fatty amines and their derivatives, pyridine and its derivatives, pyrrole and its derivatives, pyrimidine and its derivatives, pyridazine and its derivatives, piperidine and its derivatives, and amides and their derivatives.

[0040] Cinnamic acid derivatives refer to cinnamic acid derivatives in which the hydrogen atoms on the benzene ring are replaced by one or more substituents. The substituents may be selected from, but are not limited to, one or more of halogen, carboxyl, carbonyl, hydroxyl, amino, R, OR, NR2, SR, C(O)R, C(O)OR, C(O)NR2, CN, CF3, NO2, SO2, SOR, and SO3R. R may independently be, but are not limited to, C1-C 10 Alkyl, C2-C 10 Alkenyl, C2-C 10 In some embodiments, R is independently C1-C4 alkyl, C2-C4 alkenyl, or C2-C4 alkynyl, and specifically, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, vinyl, propenyl, or ethynyl.

[0041] The organic fatty amines are selected from any one or more of triisopropylamine, diethylamine, triethylamine, triethanolamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, and diisopropylethylamine; pyridine and its derivatives are selected from any one or more of methylpyridine, vinylpyridine, methylpyridine, perhydropyridine, α-pyridine, etc.; pyrrole and its derivatives are selected from any one or more of tetrahydropyrrole, methylpyrrole, and vinylpyrrole; pyridazine and its derivatives are selected from any one or more of vinylpyridazine and divinylpyridazine; piperidine and its derivatives are selected from any one or more of piperidine, vinylpiperidine, and 3-methylpiperidine; and amides and their derivatives are selected from any one or more of formamide, stearamide, succinamide, oxamide, acrylamide, and nicotinamide.

[0042] The Zn-based organic coordination nanoparticles provided by the present invention utilize the synergistic interaction between zinc atoms, cinnamic acid and its derivatives, and nitrogen-containing organic ligands. The highly reactive -CHCHCOOH group in cinnamic acid directly captures photons, making the photoresist particles inherently photosensitized. This allows them to be used directly as photoresists for pattern fabrication without a photoinitiator. Furthermore, the inclusion of cinnamic acid as a ligand enhances the material's solubility in organic reagents, facilitating storage and application.

[0043] In one embodiment, M is a compound of formula (I), wherein R1, R2, R3, R4, and R5 are independently selected from hydrogen, alkyl, alkoxy, alkyl alcohol, halogenated hydrocarbon, hydroxy, methoxy, nitro, -F, -Cl, -Br, or -I;

[0044] The alkyl group may be a straight-chain alkyl group or a branched alkyl group. For example, the alkyl group may be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl. An alkoxy group refers to a combination of an alkyl group and an oxygen atom, and specifically, it may be an ethylene oxide group or a propylene oxide group. An alkyl alcohol refers to a combination of an alkyl group and a hydroxyl group, and may be a straight-chain alkyl alcohol or a branched alkyl alcohol. Specifically, the alkyl alcohol may be ethanol, propanol, butanol, isobutanol, or amyl alcohol.

[0045] Specifically, the structural formula of the compound of M can be

[0046] N can be diethylamine, tetrahydropyrrole, piperidine, or diisopropylethylamine.

[0047] The structural formula of the Zn-based organic coordination nanoparticles can be

[0048] Zn(C6H5CHCHCOO)4(C4H 11 N)2H2;

[0049] Zn(CH3C6H5CHCHCOO)4(C4H 11 N)2H2;

[0050] Zn(C6H5CClCHCOO)4(C4H 11 N)2H2.

[0051] The size of the Zn-based organic coordination nanoparticle crystals is 1 nm to 4 nm.

[0052] The Zn-based organic coordination nanoparticle photoresist provided by the embodiments of the present invention, on the one hand, can directly obtain an exposure pattern without a photoinitiator through self-initiation by cinnamic acid in the photoresist structure absorbing photons, thereby improving exposure efficiency. On the other hand, the Zn-based organic coordination nanoparticle photoresist provided by the present invention does not contain a photoinitiator, reducing costs in the production process. Furthermore, the Zn-based organic coordination nanoparticle photoresist of the present invention crystallizes zinc-centered crystals, which can improve the storage stability of the photoresist.

[0053] The method for preparing the above-mentioned Zn-based organic coordination nanoparticles comprises the following steps:

[0054] The zinc-containing compound, the nitrogen-containing organic ligand and the M compound are mixed and stirred in an organic solvent and then post-treated to obtain the compound, wherein the molar ratio of the zinc-containing compound, the nitrogen-containing organic ligand and the M compound is 1:2:(1-6).

[0055] Furthermore, to ensure the photolithographic effect, the molar ratio of the M compound to the zinc-containing compound is in the range of 1:1 to 6:1. If the molar ratio of cinnamic acid and its derivatives to the zinc-containing compound is too large or too small, even if the particles have good film-forming properties, an exposure pattern cannot be obtained. Furthermore, to ensure that an exposure pattern is obtained under long-term exposure (exposure time greater than 1 second), the molar ratio of the M compound to the zinc-containing compound can be greater than 6:1. Furthermore, the molar ratio of the M compound to the zinc-containing compound can be in the range of 2:1-5:1.

[0056] The zinc-containing compound is selected from zinc salts such as zinc acetate, zinc acetate dihydrate, zinc chloride or zinc sulfate.

[0057] The nitrogen-containing organic ligand is selected from organic amines such as diethylamine, tetrahydropyrrole, piperidine or diisopropylethylamine.

[0058] The post-treatment comprises: stirring at 50° C. for 6 h to 24 h, then vacuum evaporating the mixture using a rotary evaporator for 1 h, and then vacuum drying the mixture in a vacuum oven at 50° C. for 5 h.

[0059] The purpose of vacuum rotary evaporation is to remove the organic solvent faster. Of course, in other embodiments, other methods can also be used to remove the organic solvent.

[0060] The temperature of the vacuum rotary evaporation is 20° C. to 80° C. For example, it can be selected from 20° C., 25° C., 30° C., 35° C., 40° C., 45° C., 50° C., 55° C., 60° C., 65° C., 70° C., 75° C., 80° C., etc.

[0061] The present invention also provides a photoresist composition comprising the aforementioned nanoparticles.

[0062] Furthermore, the photoresist composition also includes an organic dispersing solvent, which is selected from any one or more of ethyl acetate, butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol methyl ether, propylene glycol ethyl ether acetate, 1-ethoxy-2-propanol, methanol, ethanol, and propanol.

[0063] Too much photoresist may not dissolve; too little photoresist may not form a film. Therefore, in a specific embodiment, the solid content of Zn-based nanoparticles in the photoresist composition should be controlled within the range of 1 wt% to 10 wt%.

[0064] The present invention also provides a photolithography method, comprising the above-mentioned photoresist composition, dropping the photoresist composition onto a substrate, rotating, heating, then exposing with an electron beam, mid-ultraviolet, deep ultraviolet or extreme ultraviolet, and developing with a developer.

[0065] 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.

[0066] 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, the polymerization of nanoparticles containing organic ligands is easier to proceed. If the exposure dose is too large, the organic ligands may fall off directly from the metal oxide to form fragments, and the photoresist particles can no longer undergo exchange reactions with organic ligands, thereby reducing the degree of polymerization in the exposed area. Therefore, in a specific embodiment, the exposure dose under medium ultraviolet conditions can be 50mJ / cm 2 ~500mJ / cm 2 , specifically, it can be 50mJ / cm 2 , 100mJ / cm 2 , 200mJ / cm 2 , 500mJ / cm 2 wait.

[0067] The substrate is selected from a silicon plate. Other substrates that are insoluble in developer can also be selected according to actual needs.

[0068] 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.

[0069] The developer is selected from a mixture of any one or more of indene, indane, quinoline, 1-methylnaphthalene, toluene, o-xylene, m-xylene, mesitylene, ethyl acetate, butyl acetate, ethanol, n-propanol, tetralin, decalin, isopropanol, n-butanol, n-hexane and cyclohexane, and the developing temperature is 20°C to 50°C, such as 25°C, 30°C, 40°C, etc.

[0070] The thickness of the pre-film layer should not be too thick or too thin. If it is too thick, the lines of the lithography machine will easily collapse, and if it is too thin, the lines will easily be washed away. Therefore, in a specific embodiment, the thickness of the pre-film layer after removing the organic dispersion 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.

[0071] Furthermore, the above-mentioned Zn-based organic coordination nanoparticles are used in the field of photoresists, including electron beam, mid-ultraviolet, deep ultraviolet or extreme ultraviolet photoresists.

[0072] The following is elaborated in detail with reference to specific embodiments:

[0073] Example 1

[0074] Appropriate amounts of zinc acetate dihydrate, cinnamic acid, and diethylamine were weighed, with the molar ratio of zinc acetate dihydrate, cinnamic acid, and diethylamine being 2:4:3. These were dispersed in a 150 mL round-bottom flask with a certain amount of ethyl acetate and heated at 50°C with stirring for 6-24 hours to obtain a reaction product. The reaction product was cooled and then rotary evaporated at 50°C for 1 hour to remove the solvent, ethyl acetate. The product was then vacuum dried at 50°C for 5 hours to obtain a Zn-based coordinated nanoparticle photoresist. After standing for a period of time, obvious crystals appeared in the product. At this point, the photoresist is a mixture containing crystals. As shown in Figure 1, the crystal structure was analyzed to confirm the true structure and atomic position of the crystal. Analysis revealed that the single crystal structure formula in the photoresist is Zn(C6H5CHCHCOO)4(C4H 11 N)2H2. The raw materials used and the obtained photoresist were characterized by nuclear magnetic hydrogen spectrum, and the test results are shown in Figure 2. Among them, zinc acetate: 1 H NMR (400 MHz, DMSO-d6) δ 1.82 (s, 6H); diethylamine: 1 H NMR (400 MHz, DMSO-d6) δ 2.50 (q, J = 7.1 Hz, 4H), 0.98 (t, J = 7.1 Hz, 6H); Cinnamic acid: 1H NMR (400 MHz, DMSO-d6) δ 12.45 (s, 1H), 7.70 (dd, J = 6.7, 2.9 Hz, 2H), 7.62 (d, J = 15.9 Hz, 1H), 7.43 (dd, J = 4.8, 1.9 Hz, 3H), 6.56 (dd, J = 16.0, 1.1 Hz, 1H); Ethyl acetate: 1 H NMR (400 MHz, DMSO-d6) δ 4.03 (q, J = 7.1 Hz, 2H), 1.99 (s, 3H), 1.18 (t, J = 7.1 Hz, 3H); Zn-based coordinated nanoparticle photoresist: 1 H NMR (400MHz, DMSO-d6) δ7.62-7.58 (m, 2H), 7.43-7.31 (m, 4H), 6.57 (d, J=15.8Hz, 1H), 2.92 (q, J=7.3Hz, 3H), 1.87 (s, 4H), 1.17 (q, J=7.0Hz, 5H).

[0075] As shown in the NMR spectrum in Figure 2, after the photoresist is synthesized, the monomers undergo coordination, resulting in peak shifts. The peaks associated with the diethylamine structure shift from positions 0.98 and 2.50 to 1.17 and 2.92, respectively; the peak associated with the methyl group in zinc acetate shifts from 1.82 to 1.87; and the peak associated with cinnamic acid shifts from positions 7.62, 7.70, 7.43, and 6.56 to positions 7.60, 7.38, and 6.57. Other peaks in the photoresist NMR are those of the solvent ethyl acetate.

[0076] Example 2

[0077] The difference between Example 2 and Example 1 is that the molar ratio of cinnamic acid and zinc acetate dihydrate is replaced with 1:1, and the remaining operations are the same as Example 1.

[0078] Example 3

[0079] The difference between Example 3 and Example 1 is that the molar ratio of cinnamic acid and zinc acetate dihydrate is replaced with 6:1, and the remaining operations are the same as Example 1.

[0080] Example 4

[0081] The Zn-based organic-coordinated nano-photoresist in Example 1 and an organic solvent (propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, or propylene glycol monoethyl ether) are prepared into a photoresist solution with a solid content of 5wt% in a certain proportion. After dissolving, filter to remove impurities in the prepared photoresist solution. Add 5 drops of photoresist solution to the substrate, set the rotation speed to 2000r / min, and rotate for 1min. Then heat on a hot plate at 80℃ for 1min. Then expose using a medium ultraviolet exposure machine and an electron beam exposure machine respectively. After exposure, take out the substrate and develop with mesitylene for 1-20s. After development, blow dry the substrate (nitrogen) and observe the photolithography imaging results. Wherein, Figure 3 is a medium ultraviolet (254nm) exposure image with a dose of 130J / cm 2 Figure 4 is a deep ultraviolet (248nm) exposure diagram with a dose of 30J / cm 2 Figure 5 is an electron beam exposure diagram with a dose of 500μCcm -2 The photolithographic pattern was obtained by adopting a small dose exposure, indicating that the Zn-based coordinated nano-photoresist prepared in this application has high sensitivity.

[0082] Example 5

[0083] The Zn-based organic-coordinated nanophotoresist in Example 2 and an organic solvent (propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, or propylene glycol monoethyl ether) were mixed in a certain proportion to form a photoresist solution with a solid content of 5 wt%, dissolved, and filtered. Five drops of the photoresist solution were added to the substrate, and the rotation speed was set to 2000 r / min and rotated for 1 minute. The substrate was then heated on a hot plate at 80°C for 1 minute. The substrate was then exposed using a medium-UV exposure machine with a dose of 100 mJ / cm. -2 After exposure, remove the substrate and develop with mesitylene for 1-20 seconds. After development, blow dry the substrate (with nitrogen) and observe the photolithography imaging results, as shown in Figure 6.

[0084] Example 6

[0085] The Zn-based organic-coordinated nano-photoresist in Example 3 and an organic solvent (propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, or propylene glycol monoethyl ether) were mixed in a certain proportion to form a photoresist solution with a solid content of 5wt%, dissolved and filtered. Five drops of photoresist solution were added to the substrate, the rotation speed was set to 2000r / min, and the rotation was performed for 1min. Then, the substrate was heated at 80℃ for 1min on a hot plate. Then, the substrate was exposed using a medium-ultraviolet exposure machine and an electron beam exposure machine respectively. After exposure, the substrate was taken out and the substrate was heated at 100mJcm -2 After exposure to mid-UVC, the substrate was developed in mesitylene for 1 second. After development, the substrate was blown dry (with nitrogen) and the photolithographic image was observed. The results showed that the material had acceptable film-forming properties, and the exposed pattern could be obtained after 1 second of development, as shown in Figure 7.

[0086] Comparative Example 1

[0087] The cinnamic acid in Example 1 was replaced with benzoic acid, and 10% of photoinitiator was added during the preparation of the photoresist solution. The photoresist solution was exposed using a deep ultraviolet (248 nm) exposure machine with an exposure dose of 150 mJ cm -2 , the exposure diagram is shown in Figure 8.

[0088] Comparative Example 2

[0089] The difference between Comparative Example 2 and Example 1 is that the molar ratio of cinnamic acid and zinc acetate dihydrate is replaced with 1:8, diethylamine is added during the synthesis process, and a clear solution is obtained. The material still has good film-forming properties. However, at 100mJcm -2 After exposure to mid-UV, it cannot be developed in mesitylene.

[0090] Comparative Example 3

[0091] Comparative Example 3 differs from Example 1 in that the molar ratio of cinnamic acid to zinc acetate dihydrate is replaced with 0:1, diethylamine is added during the synthesis process, a clear solution is obtained, the material cannot form a film, and no exposure pattern is formed after exposure.

[0092] It can be concluded from Examples 1-3 that the Zn-based nanoparticle photoresists prepared in the embodiments of the present invention can form photolithographic images without the need for a photoinitiator.

[0093] Combining Example 1 and Comparative Example 1, it can be seen that Example 1 obtains an exposure pattern with a line width of 500nm without adding a photoinitiator, and the dosage is only 1 / 3 of that of the comparative example. This shows that the Zn-based nanoparticle photoresist prepared in the embodiment of the present invention can directly obtain an exposure pattern without a photoinitiator through the self-initiation of photons absorbed by cinnamic acid in the photoresist structure, thereby improving the exposure efficiency. Comparative Examples 2 and 3 show that the proportion of cinnamic acid has a significant impact on the performance of the synthesized Zn-based nanoparticle photoresist. When the proportion range of Zn-based nanoparticle photoresist is not appropriate, no exposure pattern can be obtained.

[0094] In summary, the nanoparticles prepared in the embodiments of the present invention and the corresponding compositions demonstrate excellent lithographic performance under both mid-UV and electron beam conditions. They can directly produce exposed patterns without a photoinitiator through self-initiation by cinnamic acid in the photoresist structure, thereby improving exposure efficiency. Furthermore, the Zn-based organic coordination nanoparticle photoresist provided by the present invention does not contain a photoinitiator, reducing production costs. Furthermore, the Zn-based organic coordination nanoparticle photoresist of the present invention produces zinc-centered crystals, which can improve the storage stability of the photoresist.

[0095] Photoresist is a key material for fine patterning in microelectronics. It typically consists of a photoinitiator, photoresist resin, solvent, monomer, and other additives. Photoinitiators are compounds that absorb energy of a certain wavelength in the ultraviolet (250-420 nm) or visible (400-800 nm) region, generating free radicals, cations, and other substances, thereby initiating monomer polymerization or polymer decomposition. Traditional photoresists, and the metal-based photoresists that have been extensively studied in recent years, have historically required the chemical changes caused by photoinitiators to produce changes in solubility.

[0096] However, photons must first be absorbed and decomposed by the photoinitiator, and then the photoinitiator products must react with the photoresist resin. To ensure its solubility in the solvent, the amount of photoinitiator added is limited, resulting in low exposure efficiency and low photoresist sensitivity, significantly affecting production efficiency. Furthermore, photoinitiators are chemically unstable and expensive, adding cost and difficulty to the production process.

[0097] Based on this, it is necessary to propose a new Zn-based organic coordination nanoparticle and a preparation method thereof, a photoresist composition containing the same and its application to address the problems of low exposure efficiency and high cost of traditional photoresists.

[0098] In one aspect, the present invention provides a Zn-based organic coordination nanoparticle, which is obtained by the following preparation method:

[0099] The zinc-containing compound, the nitrogen-containing organic ligand and the compound A are mixed and stirred in an organic solvent and then post-treated to obtain the compound A, wherein the compound A is benzoylformic acid and its derivatives.

[0100] Optionally, the molar percentage range of the compound A relative to the zinc-containing compound is ≥2:1.

[0101] Optionally, the compound A is a compound represented by general formula (II), Wherein, R1, R2, R3, R4, and R5 are independently selected from hydrogen, alkyl, alkoxy, alkyl alcohol, halogenated hydrocarbon, hydroxyl, methoxy, nitro, -F, -Cl, -Br, or -I.

[0102] Optionally, the structural formula of the compound represented by the general formula (II) is

[0103] Optionally, the nitrogen-containing organic ligand is selected from diethylamine, tetrahydropyrrole, piperidine or diisopropylethylamine, and the zinc-containing compound is selected from zinc acetate, zinc acetate dihydrate, zinc chloride or zinc sulfate.

[0104] In another aspect, the present invention provides a method for preparing Zn-based organic coordination nanoparticles, comprising the following steps:

[0105] Mixing a zinc-containing compound, a nitrogen-containing organic ligand, and a compound A in an organic solvent and stirring to obtain a clear solution, wherein the compound A is benzoylformic acid and its derivatives;

[0106] The clarified solution is post-treated, and the post-treatment includes: stirring at 50° C. for 6 h to 24 h, then vacuum evaporating for 1 h using a rotary evaporator, and then vacuum drying in a vacuum oven at 50° C. for 5 h.

[0107] Optionally, the molar percentage range of the compound A relative to the zinc-containing compound is ≥2:1.

[0108] Optionally, the nitrogen-containing organic ligand is selected from organic amines such as diethylamine, tetrahydropyrrole, piperidine or diisopropylethylamine; and the zinc-containing compound is selected from zinc acetate, zinc acetate dihydrate, zinc chloride or zinc sulfate.

[0109] In another aspect, the present invention provides a photoresist composition comprising the aforementioned nanoparticles.

[0110] Optionally, the photoresist composition further comprises an organic dispersing solvent, and 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.

[0111] Optionally, the solid content of the Zn-based organic coordination nanoparticles is in the range of 1 wt% to 10 wt%.

[0112] On the other hand, the present invention provides a photolithography method, which uses the above-mentioned photoresist composition, drops the photoresist composition onto a substrate, rotates, heats, and then exposes it with an electron beam, mid-ultraviolet, deep ultraviolet or extreme ultraviolet, and develops it with a developer.

[0113] Optional, exposure dose under mid-UV is 5mJ / cm 2 ~500mJ / cm 2 .

[0114] Optionally, the developer is selected from a mixture of any one or more of indene, indane, quinoline, 1-methylnaphthalene, toluene, o-xylene, m-xylene, ethyl acetate, butyl acetate, isopropanol, ethanol, n-propanol, tetralin, decalin, n-butanol, n-hexane and cyclohexane, and the developing temperature is 20°C to 50°C.

[0115] Another aspect of the present invention provides a use of Zn-based organic coordination nanoparticles for use in the field of photoresists, including electron beam, mid-ultraviolet, deep ultraviolet or extreme ultraviolet photoresists.

[0116] The Zn-based organic coordination nanoparticle photoresist provided in an embodiment of the present invention, on the one hand, can directly obtain an exposure pattern by self-initiating by benzoylformic acid in the photoresist structure absorbing photons in the absence of a photoinitiator, thereby improving the exposure efficiency; on the other hand, the Zn-based organic coordination nanoparticle photoresist provided by the present invention does not contain a photoinitiator, thereby reducing the cost in the production process.

[0117] Reference will now be made in detail to embodiments of the invention, one or more examples of which are described below.

[0118] Each example is provided by way of explanation and not limitation of the present invention. Indeed, it will be apparent to those skilled in the art that various modifications and variations may be made to the present invention without departing from the scope or spirit of the invention. For example, features illustrated or described as part of one embodiment may be used in another embodiment to produce a still further embodiment.

[0119] Therefore, it is intended that the present invention covers such modifications and variations as come within the scope of the appended claims and their equivalents. Other objects, features, and aspects of the present invention are disclosed in or are obvious from the following detailed description. Those skilled in the art will appreciate that this discussion is merely a description of exemplary embodiments and is not intended to limit the broader aspects of the present invention.

[0120] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which this invention pertains. The terms used herein in the specification of the present invention are for the purpose of describing specific embodiments only and are not intended to limit the present invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0121] Except as shown in the operating examples or otherwise indicated, all numbers used in the specification and claims to express the amount of ingredients, physicochemical properties, etc. are understood to be adjusted by the term "about" in all cases. For example, therefore, unless otherwise indicated, the numerical parameters listed in the above specification and the appended claims are approximate values, and those skilled in the art will be able to appropriately change these approximate values ​​using the teachings disclosed herein to seek to obtain the desired properties. The use of numerical ranges expressed as endpoints includes all numbers within the range and any range within the range, for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4 and 5, etc.

[0122] Photoresist "sensitivity" refers to the minimum light energy or minimum charge (for electron beams) incident on a unit area that causes the photoresist to react completely. In the present invention, the unit of ultraviolet photoresist sensitivity is mJcm -2Indicates (the smaller the value, the higher the photoresist sensitivity); the unit of electron beam photoresist sensitivity is μCcm -2 The smaller the value, the higher the sensitivity of the photoresist. Photoresist sensitivity can also be reflected by the minimum exposure dose, which is exposure dose = light intensity × exposure time.

[0123] The present invention provides a Zn-based organic coordination nanoparticle, which is prepared by the following method:

[0124] The zinc-containing compound, the nitrogen-containing organic ligand and the compound A are mixed and stirred in an organic solvent and then post-treated to obtain the compound A, wherein the compound A is benzoylformic acid and its derivatives.

[0125] Benzoylformic acid derivatives refer to benzoylformic acid derivatives in which the hydrogen atoms on the benzene ring are replaced by one or more substituents. The substituents may be selected from, but are not limited to, one or more of halogen, carboxyl, carbonyl, hydroxyl, amino, R, OR, NR2, SR, C(O)R, C(O)OR, C(O)NR2, CN, CF3, NO2, SO2, SOR, and SO3R. R may independently be, but are not limited to, C1-C 10 Alkyl, C2-C 10 Alkenyl, C2-C 10 In some embodiments, R is independently C1-C4 alkyl, C2-C4 alkenyl, or C2-C4 alkynyl, and specifically, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, vinyl, propenyl, or ethynyl.

[0126] In a specific embodiment, compound A is a compound of formula (II), Wherein, R1, R2, R3, R4, and R5 are independently selected from hydrogen, alkyl, alkoxy, alkyl alcohol, halogenated hydrocarbon, hydroxyl, methoxy, nitro, -F, -Cl, -Br, or -I; the alkyl group may be a linear alkyl group or a branched alkyl group, for example, the alkyl group may be methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, or decyl. Alkoxy refers to a combination of an alkyl group and an oxygen atom, specifically, an ethylene oxide group or a propylene oxide group. Alkyl alcohol refers to a combination of an alkyl group and a hydroxyl group, and may be a linear alkyl alcohol or a branched alkyl alcohol, specifically, an alkyl alcohol may be ethanol, propanol, butanol, isobutanol, or pentanol.

[0127] Specifically, the structural formula of compound A can be

[0128] The nitrogen-containing organic ligand is any one or more of organic fatty amines and their derivatives, pyridine and its derivatives, pyrrole and its derivatives, pyrimidine and its derivatives, pyridazine and its derivatives, piperidine and its derivatives, and amides and their derivatives. The organic fatty amines are selected from any one or more of triisopropylamine, triethanolamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, and diisopropylethylamine; pyridine and its derivatives are selected from any one or more of methylpyridine, vinylpyridine, methylpyridine alkane, perhydropyridine, α-pyridine, etc.; pyrrole and its derivatives are selected from any one or more of tetrahydropyrrole, methylpyrrole, and vinylpyrrole; pyridazine and its derivatives are selected from any one or more of vinylpyridazine and divinylpyridazine; piperidine and its derivatives are selected from any one or more of piperidine, vinylpiperidine, and 3-methylpiperidine; amides and their derivatives are selected from any one or more of formamide, stearamide, succinamide, oxamide, acrylamide, and nicotinamide. In a specific embodiment, the nitrogen-containing organic ligand is selected from organic amines such as diethylamine, tetrahydropyrrole, piperidine, or diisopropylethylamine;

[0129] The zinc-containing compound is selected from zinc salts such as zinc acetate, zinc acetate dihydrate, zinc chloride or zinc sulfate.

[0130] The molar ratio of the zinc-containing compound: benzoylformic acid and the nitrogen-containing organic ligand is in the range of 1: (1-6): (2-8).

[0131] As the amount of compound A increases, the number of -COCOOH groups increases, and the efficiency of photoresist nanoparticles in capturing photons increases. In a specific embodiment, the molar percentage range of the compound A relative to the zinc-containing compound is ≥2:1.

[0132] The post-treatment comprises: stirring at 50° C. for 6 h to 24 h, then vacuum evaporating the mixture using a rotary evaporator for 1 h, and then vacuum drying the mixture in a vacuum oven at 50° C. for 5 h.

[0133] The Zn-based organic coordination nanoparticles provided in the embodiments of the present invention, through the synergistic effect between zinc atoms, benzoylformic acid and nitrogen-containing organic ligands, and the -COCOOH in benzoylformic acid has high reactivity, directly captures photons, so that the photoresist particles themselves can be photosensitized, and thus can be directly used as photoresist for pattern manufacturing without photoinitiator conditions.

[0134] The Zn-based organic coordination nanoparticle photoresist provided by the present invention can, on the one hand, directly produce an exposure pattern without a photoinitiator by self-initiating photons absorbed by benzoylformic acid in the photoresist structure, thereby improving exposure efficiency. Furthermore, the Zn-based organic coordination nanoparticle photoresist provided by the present invention does not contain a photoinitiator, reducing production costs.

[0135] The method for preparing the above-mentioned Zn-based organic coordination nanoparticles comprises the following steps:

[0136] Step S1, mixing and stirring a zinc-containing compound, a nitrogen-containing organic ligand, and a compound A in an organic solvent to obtain a clear solution, wherein the compound A is benzoylformic acid and its derivatives;

[0137] The molar ratio of the zinc-containing compound: benzoylformic acid and the nitrogen-containing organic ligand is 1: (1-6): (2-8).

[0138] In one embodiment, the molar ratio of the zinc-containing compound, the nitrogen-containing organic ligand, and the compound A is 2:3:4.

[0139] Furthermore, to ensure photolithographic effects, the molar ratio of compound A to the zinc-containing compound is greater than or equal to 1:1. If the molar ratio of benzoylformic acid and its derivatives to the zinc-containing compound is too small, exposure sensitivity will be greatly reduced or even unable to obtain an exposure pattern.

[0140] The zinc-containing compound is selected from zinc acetate, zinc acetate dihydrate, zinc chloride or zinc sulfate.

[0141] The nitrogen-containing organic ligand is selected from diethylamine, tetrahydropyrrole, piperidine or diisopropylethylamine.

[0142] Step S2, post-treating the clarified solution, wherein the post-treating comprises: stirring at 50° C. for 6 h to 24 h, then vacuum evaporating the solution using a rotary evaporator for 1 h, and then vacuum drying the solution in a vacuum oven at 50° C. for 5 h.

[0143] The purpose of vacuum rotary evaporation is to quickly remove the organic solvent, making it difficult for the nuclei of the zinc-based metal organic nanoparticles to grow, thereby forming single crystals, that is, zinc-based metal organic nanoparticles in a monodisperse state. Of course, in other embodiments, other methods can also be used to remove the organic solvent.

[0144] The temperature of the vacuum rotary evaporation is 20° C. to 80° C. For example, it can be selected from 20° C., 25° C., 30° C., 35° C., 40° C., 45° C., 50° C., 55° C., 60° C., 65° C., 70° C., 75° C., 80° C., etc.

[0145] The present invention also provides a photoresist composition comprising the aforementioned nanoparticles.

[0146] Furthermore, the photoresist composition also includes an organic dispersing solvent, which 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.

[0147] Too much photoresist may not dissolve; too little photoresist may not form a film. Therefore, in a specific embodiment, the solid content of Zn-based nanoparticles in the photoresist composition should be controlled within the range of 1 wt% to 10 wt%.

[0148] The present invention also provides a photolithography method, comprising the above-mentioned photoresist composition, dropping the photoresist composition onto a substrate, rotating, heating, then exposing with an electron beam, mid-ultraviolet, deep ultraviolet or extreme ultraviolet, and developing with a developer.

[0149] 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.

[0150] 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 the difference in solubility 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, it may cause line adhesion and it is impossible to obtain an independent exposure pattern. Therefore, in a specific embodiment, the exposure dose under medium ultraviolet conditions can be 5mJ / cm 2 ~500mJ / cm 2 , specifically, it can be 5mJ / cm 2 , 15mJ / cm 2 , 100mJ / cm 2 , 200mJ / cm 2 The substrate is selected from a silicon plate. Other substrates that are insoluble in the developer can also be selected according to actual needs.

[0151] 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.

[0152] The developer is selected from a mixture of any one or more of indene, indane, quinoline, 1-methylnaphthalene, toluene, o-xylene, m-xylene, ethyl acetate, butyl acetate, ethanol, isopropanol, n-propanol, tetralin, decalin, n-butanol, n-hexane and cyclohexane, and the developing temperature is 20°C to 50°C, such as 25°C, 30°C, 40°C, etc.

[0153] The thickness of the pre-film layer should be neither too thick nor too thin. If it is too thick, the lines of the lithography machine will easily collapse, while if it is too thin, the lines will easily be washed away. Therefore, in a specific embodiment, the thickness of the pre-film layer after removing the organic dispersion 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.

[0154] Furthermore, the above-mentioned Zn-based organic coordination nanoparticles are used in the field of photoresists, including electron beam, mid-ultraviolet, deep ultraviolet or extreme ultraviolet photoresists.

[0155] The following is elaborated in detail with reference to specific embodiments:

[0156] Example 7

[0157] Appropriate amounts of zinc acetate dihydrate, benzoylformic acid, and diethylamine (where the molar ratio is 2:4:3) are weighed and dispersed with ethyl acetate in a 150 mL round-bottom flask. The mixture is heated with stirring at 50°C for 6-24 hours to obtain a reaction product. The reaction product is cooled and then rotary evaporated at 50°C for 1 hour to remove the ethyl acetate solvent. The product is then dried under vacuum at 50°C for 5 hours to obtain a Zn-based coordinated nanoparticle photoresist.

[0158] The raw materials used and the obtained photoresist were characterized by nuclear magnetic hydrogen spectrum, and the test results are shown in Figure 9. Among them, zinc acetate: 1 H NMR (400 MHz, DMSO-d6) δ 1.82 (s, 6H) diethylamine: 1 H NMR (400 MHz, DMSO-d6) δ 2.50 (q, J = 7.1 Hz, 4H), 0.98 (t, J = 7.1 Hz, 6H) Benzoylformic acid: 1 H NMR (400 MHz, DMSO-d6) δ 7.99-7.92 (m, 2H), 7.83-7.74 (m, 1H), 7.68-7.57 (m, 2H) ethyl acetate: 1 H NMR (400 MHz, DMSO-d6) δ 4.03 (q, J = 7.1 Hz, 2H), 1.99 (s, 3H), 1.18 (t, J = 7.1 Hz, 3H). Photoresist: 1H NMR (400MHz, DMSO-d6) δ7.97-7.87 (m, 2H), 7.67-7.58 (m, 1H), 7.55-7.44 (m, 2H), 2.89 (q, J=7.3Hz, 3H), 1.83 (s, 3H), 1.14 (t, J=7.3Hz, 5H).

[0159] The NMR spectra show that after the photoresist is synthesized, the monomers undergo coordination, resulting in peak shifts. The peaks associated with the diethylamine structure shift from positions 0.98 and 2.50 to 1.14 and 2.89, respectively; the peak associated with the methyl group in zinc acetate shifts from 1.82 to 1.83; and the peak associated with benzoylformic acid shifts from 7.96, 7.78, and 7.63 to 7.92, 7.61, and 7.50. Other peaks in the photoresist NMR are attributed to the solvent ethyl acetate.

[0160] The photoresist of Example 7 was characterized by infrared spectroscopy, as shown in Figure 10. As shown in Figure 10, 1737 cm -1 is the carbonyl peak of benzoylformic acid, 1595 cm -1 、1445cm -1 The peak is the vibration peak of the benzene ring skeleton.

[0161] Example 8

[0162] Weigh an appropriate amount of the photoresist of Example 7 and an organic solvent (propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether or propylene glycol monoethyl ether) and prepare a photoresist solution of a certain concentration (solution solid content 5wt%) in a certain proportion. After dissolving, filter to remove impurities in the prepared photoresist solution. Add 5 drops of photoresist solution to the substrate, set the rotation speed to 2000r / min, and rotate for 1min. Then heat on a hot plate at 80℃ for 1min. Then expose using a medium ultraviolet exposure machine and an electron beam exposure machine respectively. After exposure, take out the substrate and develop it with mesitylene for 1-10s. After development, blow dry the substrate (nitrogen) and observe the photolithography imaging results. Among them, Figure 11 is a medium ultraviolet (254nm) exposure image with a dose of 120mJ / cm 2 ; The photolithographic pattern was obtained by adopting small-dose exposure, indicating that the Zn-based coordinated nano-photoresist prepared in this application has high sensitivity.

[0163] Comparative Example 4

[0164] The benzoylformic acid in Example 7 was replaced with benzoic acid. Appropriate amounts of zinc acetate dihydrate, benzoic acid, and diethylamine were weighed and dispersed in a 150 mL round-bottom flask with a certain amount of ethyl acetate. The mixture was stirred and heated at 65° C. for 6-24 hours to obtain a reaction product. The reaction product was cooled and then rotary evaporated at 65° C. for 1 hour to remove the solvent ethyl acetate. The reaction product was then vacuum dried at 65° C. for 5 hours. 10% of a photoinitiator was added during the preparation of the photoresist solution. The solution was exposed using a mid-UV (254 nm) exposure machine at an exposure dose of 150 mJ / cm. -2 , the exposure diagram is shown in Figure 12.

[0165] Combining Examples 7 and 8, it can be concluded that the Zn-based nanoparticle photoresists prepared in the present invention can form photolithographic patterns without the need for a photoinitiator. Furthermore, the photolithographic patterns obtained by using a small dose of exposure demonstrate the high sensitivity of the Zn-based nanoparticle photoresists prepared in this application.

[0166] Combining Example 7 with Comparative Example 4, it can be seen that the photoresist in Comparative Example 4, which added an initiator, can only produce an exposure pattern under 254nm ultraviolet exposure, while the photoresist of the present invention can be directly exposed without adding a photoinitiator. This indicates that the Zn-based nanoparticle photoresist prepared in the present invention can directly produce an exposure pattern without a photoinitiator through self-initiation by benzoylformic acid in the photoresist structure, thereby improving exposure efficiency.

[0167] In summary, the nanoparticles prepared in the embodiments of the present invention and the corresponding compositions have been verified to have good photolithographic performance under mid-ultraviolet and electron beam conditions. In the absence of a photoinitiator, the exposure pattern can be directly obtained by self-initiation through the absorption of photons by benzoylformic acid in the photoresist structure, thereby improving the exposure efficiency. On the other hand, the Zn-based organic coordination nanoparticle photoresist provided by the present invention does not contain a photoinitiator, which reduces the cost in the production process.

[0168] The technical features of the above-mentioned embodiments can be combined arbitrarily. In order to make the description concise, not all possible combinations of the technical features in the above-mentioned embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0169] The above-described embodiments merely represent several embodiments of the present invention, and while their descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the patent application. It should be noted that a person skilled in the art would be able to make various modifications and improvements without departing from the spirit of the present application, and these modifications and improvements fall within the scope of protection of the present application. Therefore, the scope of protection of the present patent application shall be determined by the appended claims.

Claims

1. A Zn-based organic coordination nanoparticle, characterized in that: The general formula of the Zn-based organic coordination nanoparticles is Zn x (M) y (N) z , x, y, z are all integers ≥ 1, the M compound is cinnamic acid and its derivatives, and N is any one or more of organic fatty amines and their derivatives, pyridine and its derivatives, pyrrole and its derivatives, pyrimidine and its derivatives, pyridazine and its derivatives, piperidine and its derivatives, and amides and their derivatives.

2. The Zn-based organic coordination nanoparticles according to claim 1, characterized in that: M is a compound of general formula (I), Wherein, R1, R2, R3, R4, and R5 are independently selected from hydrogen, alkyl, alkoxy, alkyl alcohol, halogenated hydrocarbon, hydroxyl, methoxy, nitro, -F, -Cl, -Br or -I.

3. The Zn-based organic coordination nanoparticles according to claim 2, characterized in that: The structural formula of the compound represented by the general formula (I) is 4. The Zn-based organic coordination nanoparticles according to claim 1, characterized in that: The N compound is diethylamine, and the structural formula of the Zn-based organic coordination nanoparticles is Zn(C6H5CHCHCOO)4(C4H 11 N)2H2.

5. The Zn-based organic coordination nanoparticles according to claim 1, characterized in that: The size of the Zn-based organic coordination nanoparticle crystal is 1nm-4nm.

6. The method for preparing Zn-based organic coordination nanoparticles according to any one of claims 1 to 5, characterized in that: The steps include: The zinc-containing compound, the nitrogen-containing organic ligand and the M compound are mixed and stirred in an organic solvent and then post-treated to obtain the compound, wherein the molar percentage of the M compound to the zinc-containing compound is in the range of 1:1 to 6:

1.

7. The method for preparing Zn-based organic coordination nanoparticles according to claim 6, characterized in that: The zinc-containing compound is selected from zinc salts such as zinc acetate, zinc acetate dihydrate, zinc chloride or zinc sulfate.

8. The method for preparing Zn-based organic coordination nanoparticles according to claim 6, characterized in that: The nitrogen-containing organic ligand is selected from organic amines such as diethylamine, tetrahydropyrrole, piperidine, and diisopropylethylamine.

9. The method for preparing Zn-based organic coordination nanoparticles according to claim 6, characterized in that: The post-treatment comprises: stirring at 50° C. for 6 h to 24 h, then vacuum evaporating the mixture using a rotary evaporator for 1 h, and then vacuum drying the mixture in a vacuum oven at 50° C. for 5 h.

10. A photoresist composition, characterized in that: The invention comprises the Zn-based organic coordination nanoparticles as described in any one of claims 1 to 5.

11. The photoresist composition according to claim 10, characterized in that It also includes an organic dispersing solvent, which is selected from any one or more of ethyl acetate, butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol methyl ether, propylene glycol ethyl ether, 1-ethoxy-2-propanol, methanol, ethanol, and propanol.

12. A photolithography method, characterized in that: The photoresist composition according to claim 10 or 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: Exposure dose under mid-UV or deep UV is 50mJ / cm 2 ~500mJ / cm 2 .

14. The photolithography method according to claim 12, characterized in that: The developer is selected from any one or more mixtures of indene, indane, quinoline, 1-methylnaphthalene, toluene, o-xylene, m-xylene, mesitylene, ethyl acetate, butyl acetate, ethanol, n-propanol, tetralin, decalin, isopropanol, n-butanol, n-hexane and cyclohexane, and the developing temperature is 20°C to 50°C.

15. The use of Zn-based organic coordination nanoparticles according to any one of claims 1 to 5, characterized in that: Used in the field of photoresists, including electron beam, mid-UV, deep UV or extreme UV photoresists.

16. A Zn-based organic coordination nanoparticle, characterized in that: The following preparation method is used to obtain: The zinc-containing compound, the nitrogen-containing organic ligand and the A compound are mixed and stirred in an organic solvent and then post-treated to obtain the compound, wherein the A compound is benzoylformic acid and its derivatives.

17. The Zn-based organic coordination nanoparticles according to claim 16, characterized in that: The molar percentage range of the compound A relative to the zinc-containing compound is ≥2:

1.

18. The Zn-based organic coordination nanoparticles according to claim 17, characterized in that: The compound A is a compound represented by the general formula (II), Wherein, R1, R2, R3, R4, and R5 are independently selected from hydrogen, alkyl, alkoxy, alkyl alcohol, halogenated hydrocarbon, hydroxyl, methoxy, nitro, -F, -Cl, -Br or -I.

19. The Zn-based organic coordination nanoparticles according to claim 18, characterized in that: The structural formula of the compound represented by the general formula (II) is 20. The Zn-based organic coordination nanoparticles according to any one of claims 16 to 19, characterized in that: The nitrogen-containing organic ligand is selected from diethylamine, tetrahydropyrrole, piperidine or diisopropylethylamine, and the zinc-containing compound is selected from zinc acetate, zinc acetate dihydrate, zinc chloride or zinc sulfate.

21. A method for preparing Zn-based organic coordination nanoparticles, characterized in that: The steps include: The zinc-containing compound, the nitrogen-containing organic ligand and the compound A are mixed and stirred in an organic solvent to obtain a clear solution, wherein the compound A is benzoylformic acid and its derivatives; The clear solution is post-treated, and the post-treatment includes: stirring at 50° C. for 6 h to 24 h, then vacuum evaporating for 1 h using a rotary evaporator, and then vacuum drying in a vacuum oven at 50° C. for 5 h.

22. The method for preparing Zn-based organic coordination nanoparticles according to claim 21, characterized in that: The molar percentage range of the compound A relative to the zinc-containing compound is ≥2:

1.

23. The method for preparing Zn-based organic coordination nanoparticles according to claim 21, characterized in that: The nitrogen-containing organic ligand is selected from diethylamine, tetrahydropyrrole, piperidine or diisopropylethylamine; the zinc-containing compound is selected from zinc acetate, zinc acetate dihydrate, zinc chloride or zinc sulfate.

24. A photoresist composition, characterized in that The invention comprises the Zn-based organic coordination nanoparticles as described in any one of claims 16 to 20.

25. The photoresist composition according to claim 24, characterized in that It also includes an organic dispersing solvent, which 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.

26. The photoresist composition according to claim 25, characterized in that The solid content of the Zn-based organic-coordinated nanoparticles is in the range of 1 wt % to 10 wt %.

27. A photolithography method, characterized in that: The photoresist composition according to any one of claims 24 to 26 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.

28. The photolithography method according to claim 27, characterized in that: The exposure dose under medium UV is 5mJ / cm 2 ~500mJ / cm 2 .

29. The photolithography method according to claim 28, characterized in that: The developer is selected from any one or more mixtures of indene, indane, quinoline, 1-methylnaphthalene, toluene, o-xylene, m-xylene, ethyl acetate, butyl acetate, ethanol, n-propanol, isopropanol, tetralin, decalin, n-butanol, n-hexane and cyclohexane, and the developing temperature is 20°C to 50°C.

30. The use of Zn-based organic coordination nanoparticles according to any one of claims 16 to 20, characterized in that: Used in the field of photoresists, including electron beam, mid-UV, deep UV or extreme UV photoresists.

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