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

Abstract

The embodiment of the invention provides Zn-based organic coordination nanoparticles, a preparation method thereof, a photoresist composition and application thereof, the Zn-based organic coordination nanoparticles have a general formula of Znx (M) y (N) z, x, y and z are integers greater than or equal to 1, and M is cinnamic acid and derivatives thereof; n is any one or more of organic fatty amines and derivatives thereof, pyridine and derivatives thereof, pyrrole and derivatives thereof, pyrimidine and derivatives thereof, pyridazine and derivatives thereof, piperidine and derivatives thereof, and amide and derivatives thereof. According to the Zn-based organic coordination nanoparticle photoresist provided by the embodiment of the invention, an exposure pattern can be directly obtained through self-initiation of cinnamic acid absorption photons in the photoresist structure in the absence of a photoinitiator, so that the exposure efficiency is improved.

Description

Technical Field

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

[0002] Photoresist is a key material for fine pattern processing in microelectronics technology. It is usually composed of photoinitiators, photoresist resins, solvents, monomers and other additives. Among them, photoinitiators are a class of compounds that can absorb energy of a certain wavelength in the ultraviolet region (250-420nm) or visible light region (400-800nm) to produce free radicals, cations, etc., thereby initiating monomer polymerization or polymer decomposition. Traditional photoresists and metal-based photoresists that have been widely studied in recent years have always needed to undergo chemical changes under the action of photoinitiators, thereby producing changes in solubility.

[0003] However, photons need to be absorbed by the photoinitiator first and then decomposed. Then the photoinitiator product reacts with the photoresist resin. In order to ensure the solubility of the photoinitiator in the solvent, the amount of photoinitiator added is limited, so the exposure efficiency is low and the sensitivity of the photoresist is low, which greatly affects the production efficiency. In addition, the chemical properties of the photoinitiator are unstable and expensive, which increases the cost and difficulty of the production process. Summary of the invention

[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.

[0005] In one aspect, the present invention provides a Zn-based organic coordination nanoparticle, wherein the Zn-based organic coordination nanoparticle has the general formula of 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), 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, wherein 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 with a rotary evaporator for 1 h, and then vacuum drying in a vacuum oven at 50° C. for 5 h.

[0015] Another aspect of the present invention provides a photoresist composition comprising the aforementioned nanoparticles.

[0016] Optionally, the photoresist composition further includes 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, 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, 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.

[0018] Optional exposure dose of 50mJ / cm2 in mid-UV or deep-UV 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, tetralin, decalin, isopropanol, n-butanol, n-hexane and cyclohexane, and the developing temperature is 20°C to 50°C.

[0020] 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.

[0021] The Zn-based organic coordination nanoparticle photoresist provided by the embodiment of the present invention can, on the one hand, directly obtain an exposure pattern by self-initiating by absorbing photons by cinnamic acid in the photoresist structure without 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. 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. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only embodiments of the present application. For ordinary technicians in this field, other drawings can be obtained based on the provided drawings without paying any creative work.

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

[0024] Figure 2 The nuclear magnetic hydrogen spectrum of the Zn-based organic coordination nanoparticles and raw materials of Example 1 of the present invention;

[0025] Figure 3 This is a sample image of the Zn-based organic coordination nanoparticles of Example 1 of the present invention exposed at 254 nm;

[0026] Figure 4 This is a sample image of the Zn-based organic coordination nanoparticles of Example 1 of the present invention exposed at 248 nm;

[0027] Figure 5 This is a sample 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 This is a sample image of the Zn-based organic coordination nanoparticles of Example 2 of the present invention exposed at 254 nm;

[0029] Figure 7 This is a sample image of the Zn-based organic coordination nanoparticles of Example 3 of the present invention exposed at 254 nm;

[0030] Figure 8 This is an exposure sample image of comparative example 1 of the present invention. DETAILED DESCRIPTION

[0031] References to embodiments of the present invention will now be provided in detail, one or more examples of which are described below. Each example is provided as an explanation rather than a limitation of the present invention. In fact, 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 present invention. For example, a feature illustrated or described as part of one embodiment may be used in another embodiment to produce a further embodiment.

[0032] Therefore, it is intended that the present invention covers such modifications and variations that fall 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 of ordinary skill in the art will appreciate that this discussion is only a description of exemplary embodiments and is not intended to limit the broader aspects of the present invention.

[0033] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art of the present invention. The terms used herein in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more related listed items.

[0034] Except as shown in the operating examples or otherwise indicated, all numbers used in the specification and claims to indicate 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 attached claims are approximate values, and those skilled in the art can use the teachings disclosed herein to seek to obtain the desired properties and appropriately change these approximate values. 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.

[0035] 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 The smaller the value, the higher the sensitivity of the photoresist. The unit of electron beam photoresist sensitivity is μC cm -2 The smaller the value, the higher the sensitivity of the photoresist. The sensitivity of the photoresist can also be reflected by the minimum exposure dose, which is exposure dose = light intensity × exposure time.

[0036] 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.

[0037] Cinnamic acid derivatives refer to cinnamic acid with one or more substituents replacing the hydrogen atoms on the benzene ring. The substituents may be selected from, but not limited to, halogen, carboxyl, carbonyl, hydroxyl, amino, R, OR, NR2, SR, C(O)R, C(O)OR, C(O)NR2, CN, CF3, NO2, SO2, SOR, SO3R. R may be independently, but 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, C2 Specific examples of the C4 alkynyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, ethenyl, propenyl, ethynyl and the like.

[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, 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; 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 the embodiment of the present invention, through the synergistic effect between zinc atoms, cinnamic acid and its derivatives and nitrogen-containing organic ligands, and the -CHCHCOOH in cinnamic acid has high reactivity, directly captures photons, so that the photoresist particles themselves can be photosensitized, and can be directly used as photoresist for pattern manufacturing without photoinitiator. In addition, due to the introduction of cinnamic acid as a ligand, the solubility of the material in the organic reagent is improved, which is convenient for storage and application.

[0040] In a specific 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, hydroxyl, methoxy, nitro, -F, -Cl, -Br, or -I;

[0041] The alkyl group may be a straight chain alkyl group or a branched chain alkyl group, for example, the alkyl group may be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, or a decyl group. The 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. The 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 chain alkyl alcohol, and specifically, the alkyl alcohol may be ethanol, propanol, butanol, isobutanol, amyl alcohol, 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 crystal is 1nm-4nm.

[0048] The Zn-based organic coordination nanoparticle photoresist provided by the embodiment of the present invention can, on the one hand, directly obtain an exposure pattern by self-initiating by absorbing photons by cinnamic acid in the photoresist structure without 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. Furthermore, the Zn-based organic coordination nanoparticle photoresist of the present invention crystallizes out crystals centered on zinc, which can improve the storage stability of the photoresist.

[0049] The method for preparing the above-mentioned Zn-based organic coordination nanoparticles comprises the following steps:

[0050] 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).

[0051] Further, in order to ensure the photolithography effect, 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, the exposure pattern cannot be obtained. Further, in order to ensure that the exposure pattern is obtained under long-term exposure (exposure time is greater than 1s), the molar percentage range of the M compound to the zinc-containing compound can be greater than 6:1, and further, the molar percentage range of the M compound to the zinc-containing compound can be 2:1-5:1.

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

[0055] 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.

[0056] 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.

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

[0058] Furthermore, the photoresist composition also includes 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, propylene glycol ethyl ether acetate, 1-ethoxy-2-propanol, methanol, ethanol, and propanol.

[0059] Too much photoresist may not be dissolved; 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 a range of 1 wt% to 10 wt%.

[0060] 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 electron beam, mid-ultraviolet, deep ultraviolet or extreme ultraviolet, and developing with a developer.

[0061] The exposure condition is 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.

[0062] 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 exposure area, and is not conducive to the formation of the difference in solubility between the exposure area and the non-exposure area, resulting in poor development effect. Compared with bare metal nanoparticles, the polymerization of nanoparticles containing organic ligands is easier to carry out. 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 the exchange reaction of organic ligands, thereby reducing the degree of polymerization in the exposure 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.

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

[0064] 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.

[0065] 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, such as 25°C, 30°C, 40°C, etc.

[0066] The thickness of the pre-film layer cannot be too thick or too thin. If it is too thick, the lines of the lithography machine will collapse easily, and if it is too thin, the lines will be easily 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, 90nm to 100nm.

[0067] 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.

[0068] The following is described in detail with reference to specific embodiments:

[0069] Example 1

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

[0071] The raw materials and photoresist were characterized by nuclear magnetic hydrogen spectrum, and the test results are as follows: Figure 2 As shown. Among them, zinc acetate: 1 H NMR (400 MHz, DMSO-d6) δ1.82 (s, 6H); Diethylamine: 1H NMR (400 MHz, DMSO-d6) δ 2.50 (q, J = 7.1 Hz, 4H), 0.98 (t, J = 7.1 Hz, 6H); Cinnamic acid: 1 H 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 (400MHz, DMSO-d6) δ4.03 (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).

[0072] from Figure 2 It can be seen from the NMR spectrum that after the photoresist is synthesized, each monomer is coordinated and peak shifts occur. The peaks in the diethylamine structure shift from 0.98 and 2.50 to 1.17 and 2.92 respectively; the peak of the methyl group in zinc acetate shifts from 1.82 to 1.87; the peak in cinnamic acid shifts from 7.62, 7.70, 7.43, 6.56 to 7.60, 7.38, 6.57. The other peaks in the photoresist NMR are the peaks 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, and the remaining operations are the same as 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, and the remaining operations are the same as Example 1.

[0077] Example 4

[0078] 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 in a certain proportion into a photoresist solution with a solid content of 5wt%, and filtered after dissolution to remove impurities in the prepared photolithography 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°C for 1min. Then expose with 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 (nitrogen), blow dry the substrate and observe the photolithography imaging results. Among them, Figure 3 This is a mid-UV (254nm) exposure image with a dose of 130J / cm 2 ; Figure 4 This is a deep ultraviolet (248nm) exposure image with a dose of 30J / cm 2 ; Figure 5 This is an electron beam exposure image with a dose of 500uC cm -2 The photolithographic pattern was obtained by using a small dose of exposure, indicating that the Zn-based coordinated nano-photoresist prepared in the present application has high sensitivity.

[0079] Example 5

[0080] The Zn-based organic-coordinated nano-photoresist in Example 2 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, and filtered after dissolving. Five drops of the photoresist solution are added to the substrate, the rotation speed is set to 2000r / min, and rotated for 1min. Then, it is heated on a hot plate at 80°C for 1min. Then, it is exposed with a medium ultraviolet exposure machine, and the dose is 100mJ cm -2 After exposure, remove the substrate and develop it with mesitylene for 1-20 seconds. After development, blow dry the substrate (with nitrogen) and observe the photolithography imaging results. Figure 6 shown.

[0081] Example 6

[0082] 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) are prepared into a photoresist solution with a solid content of 5wt% in a certain proportion, and filtered after dissolving. Five drops of the photoresist solution are added to the substrate, the rotation speed is set to 2000r / min, and rotated for 1min. Then heat on a hot plate at 80℃ for 1min. Then expose with a medium ultraviolet exposure machine and an electron beam exposure machine respectively. After exposure, take out the substrate and irradiate at 100mJ cm -2 After exposure under medium ultraviolet, the substrate was developed in mesitylene for 1 second. After development, the substrate was blown dry (with nitrogen) and the photolithography imaging was observed. The results showed that the film-forming property of the material was acceptable and the exposure pattern could be obtained after developing for 1 second, such as Figure 7 shown.

[0083] Comparative Example 1

[0084] 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 picture is as follows Figure 8 shown.

[0085] Comparative Example 2

[0086] The difference between Comparative Example 2 and Example 1 is that the molar ratio of cinnamic acid to 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. -2 After exposure to mid-UV, it cannot be developed in mesitylene.

[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 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.

[0089] 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 photoinitiators.

[0090] Combining Example 1 with Comparative Example 1, it can be seen that Example 1 obtains an exposure pattern with a line width of 500 nm without adding a photoinitiator, and the dosage is only 1 / 3 of that of the comparative example. This indicates 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 cinnamic acid in the photoresist structure absorbing photons, thereby improving the exposure efficiency.

[0091] Comparative Examples 2 and 3 show that the proportion of cinnamic acid has a great influence on the performance of the synthesized Zn-based nanoparticle photoresist. When the proportion range of the Zn-based nanoparticle photoresist is not appropriate, the exposure pattern cannot be obtained.

[0092] In summary, the nanoparticles prepared in the embodiments of the present invention and the corresponding compositions have verified that the structure has good lithography performance under medium ultraviolet and electron beam conditions. In the absence of a photoinitiator, the cinnamic acid in the photoresist structure absorbs photons and self-initiates to directly obtain an exposure pattern, 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. 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.

[0093] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described 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 above-mentioned embodiments only express several embodiments of the present application, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the patent application. It should be pointed out that, for a person of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present application, and these all belong to the protection scope of the present application. Therefore, the protection scope of the patent application shall be subject to the attached 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.

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