Zn-based organic coordination nanoparticles, a preparation method thereof, a photoresist composition and applications thereof

Abstract

This invention provides Zn-based organic coordination nanoparticles, their preparation method, a photoresist composition, and their applications. The general formula of the Zn-based organic coordination nanoparticles is Zn. x (M) y (N) z x, y, z are integers ≥ 1, M is cinnamic acid and its derivatives; 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. The Zn-based organic coordination nanoparticle photoresist provided in this invention can directly obtain exposure patterns through photon self-initiation by cinnamic acid in the photoresist structure without a photoinitiator, thereby improving exposure efficiency.

Description

A Zn-based organic coordination nanoparticle and its preparation method, a photoresist composition and its application Technical Field

[0001] The embodiments of the present invention relate to the field of photoresist technology, and in particular to a Zn-based organic coordination nanoparticle and its preparation method, a photoresist composition and its application. Background Technology

[0002] Photoresist is a key material for fabricating fine patterns in microelectronics. It typically consists of photoinitiators, photoresist resins, solvents, monomers, and other additives. Photoinitiators are compounds that absorb energy of a specific wavelength in the ultraviolet (250–420 nm) or visible (400–800 nm) region, generating free radicals, cations, etc., thereby initiating monomer polymerization or polymer decomposition. Traditional photoresists and the metal-based photoresists that have been extensively studied in recent years have always required a chemical change under the action of a photoinitiator, resulting in a change in solubility.

[0003] However, photons must first be absorbed and decomposed by the photoinitiator, and then the photoinitiator products react with the photoresist resin. To ensure the solubility of the photoinitiator in the solvent, the amount of photoinitiator added is limited, resulting in low exposure efficiency and low photoresist sensitivity, which greatly affects production efficiency. In addition, photoinitiators are chemically unstable and expensive, thus increasing the cost and difficulty of the production process. Summary of the Invention

[0004] Therefore, it is necessary to address the problems of low exposure efficiency and high cost of traditional photoresists by proposing a new Zn-based organic coordination nanoparticle, its preparation method, a photoresist composition containing it, and its applications.

[0005] In one aspect, the present invention provides Zn-based organic coordination nanoparticles, wherein the general formula of the Zn-based organic coordination nanoparticles 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 general formula (I). Among them, R1, R2, R3, R4, and R5 are independently selected from hydrogen, alkyl, alkoxy, alkyl alcohol, haloalkanes, hydroxyl, methoxy, nitro, -F, -Cl, -Br, or -I;

[0007] Optionally, the structural formula of the compound represented by 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 crystal 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, nitrogen-containing organic ligand, and compound M are mixed and stirred in an organic solvent, followed by post-treatment. The molar percentage range of compound M to the zinc-containing compound is 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-processing includes: stirring at 50°C for 6-24 hours, then vacuum evaporating in a rotary evaporator for 1 hour, and then vacuum drying in a vacuum oven at 50°C for 5 hours.

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

[0016] Optionally, the photoresist composition further includes an organic dispersion solvent 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] In another aspect, the present invention provides a photolithography method, which employs the aforementioned photoresist composition, wherein the photoresist composition is dropped onto a substrate, rotated, heated, and then exposed to electron beam, mid-ultraviolet, deep ultraviolet or extreme ultraviolet light, and developed using a developer.

[0018] Optionally, the exposure dose under medium ultraviolet or deep ultraviolet light is 50 mJ / cm. 2 ~500mJ / cm 2 .

[0019] Optionally, 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, tetrahydronaphthalene, decahydronaphthalene, isopropanol, n-butanol, n-hexane, and cyclohexane, and the developing temperature is 20℃~50℃.

[0020] In another aspect, the present invention provides the use of Zn-based organic coordination nanoparticles in the field of photoresists, including electron beam, mid-ultraviolet, deep ultraviolet or extreme ultraviolet photoresists.

[0021] The Zn-based organic coordination nanoparticle photoresist provided in this invention, on the one hand, can directly obtain exposure patterns through photon self-initiation by cinnamic acid in the photoresist structure without a photoinitiator, thereby improving exposure efficiency; on the other hand, the Zn-based organic coordination nanoparticle photoresist provided by this invention does not contain a photoinitiator, reducing production costs. Furthermore, the Zn-based organic coordination nanoparticle photoresist of this invention crystallizes with zinc as the centered crystal, which can improve the storage stability of the photoresist. Attached Figure Description

[0022] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of this application. For those skilled in the art, other drawings can be obtained based on the provided drawings without creative effort.

[0023] Figure 1 is a single crystal diagram of the Zn-based organic coordination nanoparticles of Example 1 of the present invention;

[0024] Figure 2 shows the 1H NMR spectra of the Zn-based organic coordination nanoparticles and raw materials in Example 1 of this invention;

[0025] Figure 3 is an image of the Zn-based organic coordination nanoparticles of Example 1 of the present invention exposed at 254 nm.

[0026] Figure 4 is an image of the Zn-based organic coordination nanoparticles of Example 1 of the present invention exposed at 248 nm.

[0027] Figure 5 is an image of the Zn-based organic coordination nanoparticles of Example 1 of the present invention exposed under an electron beam (E-beam).

[0028] Figure 6 is an image of the Zn-based organic coordination nanoparticles of Example 2 of the present invention exposed at 254 nm.

[0029] Figure 7 is an image of the Zn-based organic coordination nanoparticles of Example 3 of the present invention exposed at 254 nm.

[0030] Figure 8 is an exposure sample of Comparative Example 1 of the present invention. Detailed Implementation

[0031] Reference will now be made to detailed embodiments of the present invention, one or more of which are described below. Each example is provided for explanation and not for limitation of the invention. In fact, it will be apparent to those skilled in the art that various modifications and variations can be made to the invention without departing from its scope or spirit. For example, features described or illustrated as part of one embodiment may be used in another embodiment to produce further embodiments.

[0032] Therefore, this invention is intended to cover such modifications and variations falling within the scope of the appended claims and their equivalents. Other objects, features, and aspects of the invention are disclosed in or will be apparent from the following detailed description. It will be understood by those skilled in the art that this discussion is merely a description of exemplary embodiments and is not intended to limit the broader aspects of the invention.

[0033] 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 specification of this invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.

[0034] Unless otherwise shown or indicated in the operational embodiments, all figures used to represent the amounts, physicochemical properties, etc., of ingredients in the specification and claims are to be understood to be adjusted by the term "about" in all cases. For example, therefore, unless stated to the contrary, the numerical parameters listed in the foregoing specification and appended claims are approximations, and those skilled in the art can appropriately modify these approximations to obtain the desired characteristics by utilizing the teachings disclosed herein. The use of numerical ranges indicated by endpoints includes all numbers within that range and any range within that range; for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, etc.

[0035] Photoresist "sensitivity" refers to the minimum light energy or minimum charge (for electron beam photoresist) incident per unit area that causes the photoresist to react completely. In this invention, the unit for ultraviolet photoresist sensitivity is mJ / cm². -2 (The smaller the value, the higher the photoresist sensitivity); the unit for electron beam photoresist sensitivity is μC / cm. -2 This indicates (the smaller the value, the higher the photoresist sensitivity). Photoresist sensitivity can also be reflected by the minimum exposure dose, where exposure dose = light intensity × exposure time.

[0036] This invention provides a Zn-based organic coordination nanoparticle, wherein 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.

[0037] Cinnamic acid derivatives refer to benzene rings of cinnamic acid with one or more substituents replacing hydrogen atoms. The substituents can be selected from, but are not limited to, halogens, carboxyl groups, carbonyl groups, hydroxyl groups, amino groups, R, OR, NR2, SR, C(O)R, C(O)OR, C(O)NR2, CN, CF3, NO2, SO2, SOR, and SO3R. R can be independently, but is not limited to, C1. C 10 Alkyl chain, C2 C 10 Alkenyl, C2 C 10 Alkyne group. In some embodiments, R is independently C1. C4 alkyl chain, C2 C4 alkenyl, C2 C4 chain alkynyl group, specifically, can be, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, vinyl, propenyl, ethynyl, etc.

[0038] 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, methylpyridinane, perhydropyridine, and α-pyridine; 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, oxalamide, acrylamide, and nicotinamide.

[0039] The Zn-based organic coordination nanoparticles provided in this invention utilize the synergistic effect between zinc atoms, cinnamic acid and its derivatives, and nitrogen-containing organic ligands. Furthermore, the -CHCHCOOH group in cinnamic acid exhibits high reactivity, directly capturing photons. This allows the photoresist particles themselves to be photosensitive, enabling them to be used directly as photoresist for pattern fabrication without a photoinitiator. Additionally, the introduction of cinnamic acid as a ligand improves the material's solubility in organic reagents, facilitating storage and application.

[0040] In one specific embodiment, M is a compound of general formula (I). Among them, R1, R2, R3, R4, and R5 are independently selected from hydrogen, alkyl, alkoxy, alkyl alcohol, haloalkanes, hydroxyl, methoxy, nitro, -F, -Cl, -Br, or -I;

[0041] Alkyl groups can be straight-chain or branched. Examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. Alkoxy groups refer to the combination of an alkyl group and an oxygen atom; specifically, they can be ethylene oxide or propylene oxide. Alkyl alcohols refer to the combination of an alkyl group and a hydroxyl group; they can be straight-chain or branched. Specifically, alkyl alcohols can be ethanol, propanol, butanol, isobutanol, pentanol, etc.

[0042] Specifically, the structural formula of the compound of M can be:

[0043] N can be diethylamine, tetrahydropyrrole, piperidine, or diisopropylethylamine.

[0044] The structural formula of the Zn-based organic coordination nanoparticles can be Zn(C6H5CHCHCOO)4(C4H 11 N)2H2;

[0045] Zn(CH3C6H5CHCHCOO)4(C4H 11 N)2H2;

[0046] Zn(C6H5CClCHCOO)4(C4H 11 N)2H2.

[0047] The size of the Zn-based organic coordination nanoparticle crystals is 1 nm-4 nm.

[0048] The Zn-based organic coordination nanoparticle photoresist provided in this invention, on the one hand, can directly obtain exposure patterns through photon self-initiation by cinnamic acid in the photoresist structure without a photoinitiator, thereby improving exposure efficiency. On the other hand, the Zn-based organic coordination nanoparticle photoresist provided by this invention does not contain a photoinitiator, reducing production costs. Furthermore, the Zn-based organic coordination nanoparticle photoresist of this invention crystallizes with zinc as the core, which can improve the storage stability of the photoresist.

[0049] The preparation method of the above-mentioned Zn-based organic coordination nanoparticles includes the following steps:

[0050] The zinc-containing compound, nitrogen-containing organic ligand, and compound M were mixed and stirred in an organic solvent, followed by post-treatment. The molar ratio of the zinc-containing compound, nitrogen-containing organic ligand, and compound M was 1:2:(1-6).

[0051] Furthermore, to ensure effective photolithography, the molar percentage range of the M compound to the zinc-containing compound is 1:1 to 6:1. If the molar percentage range 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 exposure (exposure time greater than 1 second), the molar percentage range of the M compound to the zinc-containing compound can be greater than 6:1; more specifically, the molar percentage range of the M compound to the zinc-containing compound can be 2:1 to 5:1.

[0052] The zinc-containing compound is selected from zinc salts such as zinc acetate, zinc acetate dihydrate, zinc chloride, or zinc sulfate.

[0053] The nitrogen-containing organic ligand is selected from organic amines such as diethylamine, tetrahydropyrrole, piperidine, or diisopropylethylamine.

[0054] The post-processing includes: stirring at 50°C for 6-24 hours, then vacuum evaporating in a rotary evaporator for 1 hour, and then vacuum drying in a vacuum oven at 50°C for 5 hours.

[0055] The purpose of vacuum rotary evaporation is to remove the organic solvent more quickly. Of course, in other embodiments, other methods may be used to remove the organic solvent.

[0056] The temperature for vacuum rotary evaporation is 20℃ to 80℃. For example, it can be selected from 20℃, 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃, etc.

[0057] The present invention also provides a photoresist composition comprising the aforementioned nanoparticles.

[0058] Furthermore, the photoresist composition also includes an organic dispersion solvent 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.

[0059] Too much photoresist may prevent dissolution; too little photoresist may prevent film formation. Therefore, in one 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%.

[0060] The present invention also provides a photolithography method comprising the aforementioned photoresist composition, wherein the photoresist composition is dropped onto a substrate, rotated, heated, and then exposed to electron beam, mid-ultraviolet, deep ultraviolet or extreme ultraviolet light, and developed using a developer.

[0061] The exposure conditions are selected from any one of mid-ultraviolet, deep ultraviolet, electron beam, and extreme ultraviolet. The photoresist composition of the present invention can be used under any exposure condition.

[0062] The exposure dose should be controlled within a suitable range. Too low an exposure dose results in insufficient energy, which is detrimental to the polymerization of photoresist particles in the exposed area, hindering the formation of a solubility difference between the exposed and unexposed areas, leading to poor development. Compared to bare metal nanoparticles, nanoparticles containing organic ligands polymerize more easily. Excessive exposure dose may cause the organic ligands to detach directly from the metal oxide, forming fragments, preventing the photoresist particles from undergoing organic ligand exchange reactions and reducing the degree of polymerization in the exposed area. Therefore, in one specific embodiment, the exposure dose under mid-ultraviolet conditions can be 50 mJ / cm². 2 ~500mJ / cm 2 Specifically, it could be 50 mJ / cm 2 100mJ / cm 2 200mJ / cm 2 500mJ / cm 2 wait.

[0063] The substrate is selected from silicon substrates. Other substrates that are insoluble in developer can also be selected according to actual needs.

[0064] Regarding masks, deep ultraviolet and longer wavelength light sources are used as transmission masks, while extreme ultraviolet light is used as a reflection mask. The electron beam is exposed according to the pattern set in the software.

[0065] The developer is selected from any one or more of indene, indene, quinoline, 1-methylnaphthalene, toluene, o-xylene, m-xylene, mesitylene, ethyl acetate, butyl acetate, ethanol, n-propanol, tetrahydronaphthalene, decahydronaphthalene, isopropanol, n-butanol, n-hexane, and cyclohexane. The developing temperature is 20℃ to 50℃, such as 25℃, 30℃, 40℃, etc.

[0066] The thickness of the pre-formed film cannot be too thick or too thin. If it is too thick, the lithography lines are prone to collapse; if it is too thin, the lines are easily washed away. Therefore, in one specific embodiment, the thickness of the pre-formed film after removing the organic dispersion solvent can be 10nm to 100nm. Specifically, the thickness of the pre-formed film 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.

[0067] Furthermore, the aforementioned Zn-based organic coordination nanoparticles are used in the field of photoresists, including electron beam, mid-ultraviolet, deep ultraviolet, or extreme ultraviolet photoresists.

[0068] The following detailed explanation is provided with reference to specific embodiments:

[0069] Example 1

[0070] Weigh appropriate amounts of zinc acetate dihydrate, cinnamic acid, and diethylamine, wherein the molar percentages of zinc acetate dihydrate, cinnamic acid, and diethylamine are 2:4:3. Disperse these in a 150 mL round-bottom flask with a certain amount of ethyl acetate and heat at 50 °C for 6-24 h to obtain the reaction product. Cool the reaction product and then remove the solvent ethyl acetate by rotary evaporation at 50 °C for 1 h. Then, vacuum dry at 50 °C for 5 h to obtain Zn-based coordinated nanoparticle photoresist. After standing for a period of time, obvious crystals appear in the product. At this point, the photoresist is a mixture containing crystals. As shown in Figure 1, the crystal structure is analyzed to confirm the true structure and atomic positions of the crystals. The single crystal structure of the photoresist is Zn(C6H5CHCHCOO)4(C4H 11 N)2H2.

[0071] The raw materials used and the obtained photoresist were characterized by 1H NMR spectroscopy, and the test results are shown in Figure 2. Among them, zinc acetate: 1 ¹H NMR (400MHz, DMSO-d6) δ 1.82 (s, 6H); diethylamine: 1 ¹H NMR (400MHz, DMSO-d⁶) δ 2.50 (q, J = 7.1Hz, 4H), 0.98 (t, J = 7.1Hz, 6H); Cinnamic acid: 1¹H NMR (400MHz, DMSO-d6) δ 12.45 (s, 1H), 7.70 (dd, J = 6.7, 2.9Hz, 2H), 7.62 (d, J = 15.9Hz, 1H), 7.43 (dd, J = 4.8, 1.9Hz, 3H), 6.56 (dd, J = 16.0, 1.1Hz, 1H); Ethyl acetate: 1 ¹H NMR (400MHz, DMSO-d⁶) δ 4.03 (q, J = 7.1Hz, 2H), 1.99 (s, 3H), 1.18 (t, J = 7.1Hz, 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).

[0072] As shown in Figure 2, the NMR spectra revealed that after the photoresist was synthesized, each monomer underwent coordination, resulting in peak shifts. The peaks in the diethylamine structure shifted from 0.98 and 2.50 to 1.17 and 2.92, respectively; the methyl peak in zinc acetate shifted from 1.82 to 1.87; and the peaks in cinnamic acid shifted from 7.62, 7.70, 7.43, and 6.56 to 7.60, 7.38, and 6.57. The other peaks in the photoresist NMR were those of the solvent ethyl acetate.

[0073] Example 2

[0074] 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, while the rest of the operation is the same as in Example 1.

[0075] Example 3

[0076] 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, while the rest of the operation is the same as in Example 1.

[0077] Example 4

[0078] The Zn-based coordinating nanophotoresist from Example 1 was mixed with an organic solvent (propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, or propylene glycol monoethyl ether) in a certain proportion to prepare a photoresist solution with a solid content of 5 wt%. After dissolution, the solution was filtered to remove impurities from the prepared photolithography solution. Five drops of the photoresist solution were added to the substrate, and the rotation speed was set to 2000 r / min for 1 min. Then, the substrate was heated at 80°C on a hot plate for 1 min. Exposure was then performed using a mid-ultraviolet (UV) exposure machine and an electron beam exposure machine, respectively. After exposure, the substrate was removed and developed with trimethylbenzene for 1-20 s. After development, the substrate was dried (with nitrogen) and the photolithography imaging results were observed. Figure 3 shows the mid-ultraviolet (254 nm) exposure image with a dose of 130 J / cm². 2 Figure 4 is a deep ultraviolet (248nm) exposure image with a dose of 30J / cm². 2 Figure 5 is an electron beam exposure image with a dose of 500 μC cm⁻¹. -2 The use of low-dose exposure to obtain photolithographic patterns demonstrates that the Zn-based coordinated nanophotoresist prepared in this application has high sensitivity.

[0079] Example 5

[0080] The Zn-based cohesive nanophotoresist from Example 2 was mixed with an organic solvent (propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, or propylene glycol monoethyl ether) in a certain proportion to prepare a photoresist solution with a solid content of 5 wt%. After dissolution, the solution was filtered. Five drops of the photoresist solution were added to the substrate, and the rotation speed was set to 2000 r / min for 1 min. Then, the substrate was heated to 80°C on a hot plate for 1 min. Finally, the substrate was exposed using a medium ultraviolet irradiation machine with a dose of 100 mJ / cm². -2 After exposure, remove the substrate and develop it with trimethylbenzene for 1-20 seconds. After development, dry the substrate with nitrogen and observe the photolithography imaging results, as shown in Figure 6.

[0081] Example 6

[0082] The Zn-based coordinating nanophotoresist from Example 3 was mixed with an organic solvent (propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, or propylene glycol monoethyl ether) in a certain proportion to prepare a photoresist solution with a solid content of 5 wt%. After dissolution, the solution was filtered. Five drops of the photoresist solution were added to the substrate, and the rotation speed was set to 2000 r / min for 1 min. Then, the substrate was heated to 80°C on a hot plate for 1 min. Exposure was then performed using a mid-ultraviolet lithography machine and an electron beam lithography machine, respectively. After exposure, the substrate was removed and subjected to 100 mJ / cm² exposure. -2 After exposure to medium ultraviolet light, the substrate was developed in trimethylbenzene for 1 second, and then dried with nitrogen gas. The photolithographic image was then observed. The results showed that the film-forming properties of the material were acceptable, and the exposed pattern could be obtained after 1 second of development, as shown in Figure 7.

[0083] Comparative Example 1

[0084] In Example 1, cinnamic acid was replaced with benzoic acid, and 10% photoinitiator was added during the preparation of the photoresist solution. Exposure was performed using a deep ultraviolet (248nm) exposure machine at an exposure dose of 150 mJ / cm². -2 The exposure image is shown in Figure 8.

[0085] Comparative Example 2

[0086] The difference between Comparative Example 2 and Example 1 is that the molar ratio of cinnamic acid and zinc acetate dihydrate was replaced with 1:8, and diethylamine was added during the synthesis process to obtain a clear solution. The material still exhibited good film-forming properties. However, at 100 mJ / cm²... -2 After exposure to medium ultraviolet light, it cannot be developed in trimethylbenzene.

[0087] Comparative Example 3

[0088] The difference between Comparative Example 3 and Example 1 is that the molar ratio of cinnamic acid and zinc acetate dihydrate was replaced with 0:1, diethylamine was added during the synthesis process, a clear solution was obtained, the material could not form a film, and no exposure pattern was found after exposure.

[0089] Based on Examples 1-3, it can be concluded that the Zn-based nanoparticle photoresists prepared in the embodiments of the present invention can form photolithographic images without the need for photoinitiators.

[0090] As can be seen from Example 1 and Comparative Example 1, Example 1 obtained an exposure pattern with a linewidth of 500 nm without adding a photoinitiator, and the dosage was only 1 / 3 of that in the comparative example. This indicates that the Zn-based nanoparticle photoresist prepared in this embodiment of the invention can directly obtain an exposure pattern through photon self-initiation by cinnamic acid in the photoresist structure without a photoinitiator, thereby improving the exposure efficiency.

[0091] 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 of Zn-based nanoparticle photoresist is not appropriate, exposure patterns cannot be obtained.

[0092] In summary, the nanoparticles and corresponding compositions prepared in the embodiments of this invention have demonstrated excellent photolithography performance under medium ultraviolet and electron beam conditions. They can directly obtain exposure patterns without a photoinitiator by self-initiating through photon absorption by cinnamic acid in the photoresist structure, thereby improving exposure efficiency. Furthermore, the Zn-based organic coordination nanoparticle photoresist provided by this invention does not contain a photoinitiator, reducing production costs. Moreover, the Zn-based organic coordination nanoparticle photoresist of this invention crystallizes with zinc as the central crystal, which improves the storage stability of the photoresist.

[0093] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above 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.

[0094] The embodiments described above are merely illustrative of several implementations of this application, 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 those skilled in the art can make various modifications and improvements without departing from the concept of this application, and these all fall within the protection scope of this application. Therefore, the protection scope of this patent application should 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 The structural formula of the compound M is an integer where x, y, and z are all ≥ 1. 、 、 or N is diethylamine, tetrahydropyrrole, piperidine, or diisopropylethylamine.

2. The Zn-based organic coordination nanoparticles as described in claim 1, characterized in that, The structural formula of the compound represented by general formula (Ⅰ) is: 。 3. The Zn-based organic coordination nanoparticles as described in 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.

4. The Zn-based organic coordination nanoparticles as described in claim 1, characterized in that, The size of the Zn-based organic coordination nanoparticle crystals is 1 nm-4 nm.

5. The method for preparing Zn-based organic coordination nanoparticles according to any one of claims 1-4, characterized in that, The process includes the following steps: mixing and stirring a zinc-containing compound, a nitrogen-containing organic ligand, and a compound M in an organic solvent, followed by post-treatment, wherein the molar percentage of the compound M to the zinc-containing compound ranges from 1:1 to 6:

1.

6. The method for preparing Zn-based organic coordination nanoparticles as described in claim 5, characterized in that, The zinc-containing compound is selected from zinc acetate, zinc acetate dihydrate, zinc chloride, or zinc sulfate.

7. The method for preparing Zn-based organic coordination nanoparticles as described in claim 5, characterized in that, The post-processing includes: stirring at 50°C for 6-24 hours, then vacuum evaporating in a rotary evaporator for 1 hour, and then vacuum drying in a vacuum oven at 50°C for 5 hours.

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

9. The photoresist composition according to claim 8, characterized in that, It also includes an organic dispersion 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.

10. A photolithography method, characterized in that, Using the photoresist composition of claim 8 or 9, the photoresist composition is dropped onto a substrate, rotated, heated, and then exposed with an electron beam, mid-ultraviolet, deep ultraviolet, or extreme ultraviolet light, and developed with a developer.

11. The photolithography method according to claim 10, characterized in that, Exposure dose under medium or deep ultraviolet light is 50 mJ / cm 2 ~500 mJ / cm 2 .

12. The photolithography method according to claim 10, characterized in that, The developer is selected from any one or more of indene, indene, quinoline, 1-methylnaphthalene, toluene, o-xylene, m-xylene, mesitylene, ethyl acetate, butyl acetate, ethanol, n-propanol, tetrahydronaphthalene, decahydronaphthalene, isopropanol, n-butanol, n-hexane, and cyclohexane, and the developing temperature is 20℃~50℃.

13. The use of the Zn-based organic coordination nanoparticles according to any one of claims 1-4, characterized in that, Electron beam, mid-ultraviolet, deep ultraviolet, or extreme ultraviolet photoresists are used in the field of photoresist.

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