Zn-based organic coordination nanoparticles, photoresist composition, and its manufacturing method and application

Abstract

The present invention relates to Zn-based organic coordination nanoparticles, photoresist compositions, and their preparation and application. The nanoparticles have a metal-organic one-dimensional repeating chain structure, and the general structural formula is [ZnX2(CH3COO) Y ]n, where X is selected from a benzoic acid group or a m-methylbenzoic acid group, Y is selected from organic amine-based ligands, and n is the degree of polymerization, which is greater than or equal to 1. The Zn-based organic coordination nanoparticles can be used to form photoresist compositions and can be applied to mid-ultraviolet, electron beam, and extreme ultraviolet lithography to obtain high-quality exposure patterns, and therefore the Zn-based organic coordination nanoparticles of the present invention have significant application potential and value.

Description

[Technical Field]

[0001] The present invention relates to the technical field of photoresist, and in particular to Zn-based organic coordination nanoparticles, photoresist compositions and their preparation methods and applications. [Background technology]

[0002] Lithography is the technology that transfers the pattern on a reticle onto a substrate using photoresist under the action of a certain amount of energy, and is the core of chip manufacturing. In the manufacturing process of integrated circuits, lithography costs account for one-third or even more of the total cost, and the size and quality of the lithography have a significant impact on the performance of the chip. With the continuous development of lithography technology, the linewidth of the light source is constantly shrinking, and 13.5nm extreme ultraviolet light source exposure technology is gradually becoming the main choice for lithography nodes below 7nm.

[0003] Photoresist is a type of photosensitive material whose main function is to transfer chip design patterns from a reticle onto a substrate. During this process, photoresist undergoes a chemical reaction under the irradiation of light, resulting in a change in dissolution rate. As the exposure wavelength gradually decreases in the lithography process, the accompanying photoresist material also changes accordingly. According to the difference in exposure wavelength, photoresist can be divided into G-line photoresist, I-line photoresist, 248nm photoresist, 193nm photoresist, and 13.5nm extreme ultraviolet (EUV) photoresist.

[0004] Extreme ultraviolet lithography technology has low light source power and low light source conversion efficiency. Therefore, conventional organic polymer photoresists and molecular glass photoresists mainly composed of elements such as C and O have low photon absorption and low sensitivity, making them inapplicable. To improve the photon absorption rate of photoresists, metal elements with relatively large optical absorption cross-sections have been introduced. In recent years, research into metal-organic photoresists has gradually deepened. The zirconium oxide nanoparticle photoresist developed by Ober Laboratory at Cornell University and Brainard Laboratory at the State University of New York has a photon absorption rate of 4.2 mJ / cm. 2 This has achieved extremely high photosensitivity and a linewidth resolution of 26 nm. However, the nanoparticles produced by the gel-sol method have a wider size distribution, which causes differences in dissolution rate during organic development, resulting in line edge roughness of 5.9 nm. In 2009, Inpria Company's patent WO2009 / 120169A also produced a photoresist mixture containing HfO2+ or ZrO2+ metal oxide organic ligands, which, after coating, exposure, development, and other processes, could produce patterns with an LER of 2.25 nm and a maximum of 60 nm. Subsequently, Inpria further developed Sn-based metal oxide organic ligand compositions and organic-inorganic nanoclusters, and demonstrated their feasibility as EUV photoresists (TW1719360B, TW201943724A, TW202110863A, WO2019195522A). However, due to the inherent toxicity of Sn, Sn-based organic ligand photoresist compositions still face safety risks in the manufacturing process, which also restricts their industrial application and widespread use.

[0005] In order to further obtain safer and more reliable metal organic ligand photoresists, Zn element system has become a potential choice, and the present invention aims to develop a novel photoresist of Zn-based organic ligands with less roughness, higher resolution, wider applicability, and safer and healthier. Summary of the Invention [Problem to be solved by the invention]

[0006] Based on the above, it is necessary to provide new Zn-based organic coordination nanoparticles, photoresist compositions, and their preparation methods and applications to address the problems of high edge roughness and lower resolution of features obtained by lithography with conventional photoresists. [Means for solving the problem]

[0007] The present invention first provides Zn-based organic coordination nanoparticles, which have a metal-organic one-dimensional repeating chain structure and a general structural formula of [ZnX2(CH3COO) Y ] n where X is selected from a benzoic acid group or a m-methylbenzoic acid group, Y is selected from organic amine-based ligands, and n is the degree of polymerization, n being greater than or equal to 1. The size of the produced Zn-based organic coordination nanoparticles is 1 nm to 4 nm.

[0008] Furthermore, the organic amine ligand is selected from N-methylpiperidine, N-methylpyrrolidine, hexamethylenediamine, and methylpyrrolidine.

[0009] The present invention further provides a method for preparing Zn-based organic coordination nanoparticles, the method comprising: (1) mixing a zinc metal salt with an organic solvent to obtain a zinc metal salt solution; Step (2) of mixing the zinc metal salt solution with a first organic ligand and a second organic ligand, and heating and stirring to cause a reaction; and (3) removing any solvent remaining in the reaction product.

[0010] Furthermore, the first organic ligand is benzoic acid or m-methylbenzoic acid, and the second organic ligand is selected from N-methylpiperidine, N-methylpyrrolidine, hexamethylenediamine, and methylpyrrolidine.

[0011] The molar ratio of the metal salt of zinc to the first organic ligand and the second organic ligand is (0.2-1):(0.4-1):(0.3-1), and preferably the molar ratio of the metal salt of zinc to the first organic ligand and the second organic ligand is 1:(3-5):(2-5).

[0012] Furthermore, in step (2), the heating and stirring is carried out at a temperature in the range of 50°C to 80°C for a period of 10 hours to 40 hours.

[0013] Furthermore, in step (3), the solvent removal method may be vacuum rotary evaporation, the temperature may be 20°C to 80°C, the pressure of the vacuum rotary evaporation may be 20 mbar to 60 mbar, and the time of the vacuum rotary evaporation may be 30 to 60 minutes.

[0014] The present invention further provides Zn-based organic coordination nanoparticles, which are obtained by the above-mentioned production method.

[0015] The present invention further provides a Zn-based organic coordination nanoparticle photoresist composition, which comprises the above-mentioned Zn-based organic coordination nanoparticles, a photooxidant, and an organic dispersion solvent, wherein the mass percentage of the Zn-based organic coordination nanoparticles is 3% to 20%, and the mass percentage of the photooxidant is 5% to 10%.

[0016] The photooxidant may be one or more selected from N-hydroxynaphthalimide triflate, 1,4-aminonaphthalenesulfonic acid, 2-amino-5,7-naphthalenedisulfonic acid, tert-butylphenyl iodonium salt perfluorooctanesulfonic acid, triphenylsulfonium perfluorobutanesulfonic acid, triphenylsulfonium perfluorobutyl, and triphenylsulfonium trifluorosulfonic acid, and the organic dispersion solvent may be one or more selected from ethyl acetate, butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl acetate, 1-ethoxy-2 propanol, methanol, ethanol, and propanol.

[0017] Furthermore, the method for preparing the Zn-based organic coordination nanoparticle photoresist composition specifically includes dissolving the obtained nanoparticle composition in an organic dispersion solvent, adding a photo-oxidant until the nanoparticle composition is completely dissolved, and stirring for 5 minutes to obtain a photoresist mixed solution.

[0018] The present invention further provides a method for patterning a photoresist, the method comprising: (1) applying the photoresist composition to a surface of a substrate and removing the organic dispersion solvent to form a pre-deposition layer on the surface of the substrate; (2) performing an exposure operation in which a light source is irradiated through a mask onto the pre-coated layer of the substrate to form photoresist particle aggregates in the exposed areas of the pre-coated layer; and (3) applying a developer to the exposed pre-coat layer so that the unexposed areas of the pre-coat layer blocked by the mask are dissolved in the developer, while the exposed areas of the pre-coat layer remain on the substrate because they have formed photoresist particle aggregates.

[0019] Specifically, the exposure conditions may be selected from any one of intermediate ultraviolet light, electron beam, and extreme ultraviolet light, and the exposure dose of ultraviolet light is 50 mJ / cm 2 2 ~500mJ / cm 2 and the electron beam exposure dose is 50 μC / cm 2 ~500μC / cm 2 The thickness of the pre-deposition layer after removing the organic dispersion solvent may be 10 nm to 100 nm.

[0020] The Zn-based organic coordination nanoparticles and their photoresist compositions according to the present invention can be used to form printed circuit boards, and the specific method is as follows: Step (1) of manufacturing a pre-patterned plate having a patterned photoresist layer on a silicon plate substrate according to the above-mentioned photoresist patterning method; (2) etching the pre-patterned plate using a dry or wet method. [Effects of the Invention]

[0021] The Zn-based organic coordination nanoparticles designed and manufactured by the present invention have a metal-organic one-dimensional repeating chain structure. Under light irradiation conditions, the Zn-based organic coordination nanoparticles interact with a photo-oxidizing agent, causing the polarity of the material to change and aggregate, resulting in a change in the solubility of the Zn-based organic coordination nanoparticles before and after light irradiation. Due to these properties, by using the coordination polymer nanoparticles as a photoresist component, it is possible to create a difference in the solubility of the exposed and shaded parts of the photoresist in the developer, so that the exposed parts aggregate in the developer and reduce their solubility, while the shaded parts aggregate in the developer and do not dissolve, allowing the unexposed areas to be removed after development to obtain a pattern of the desired shape.

[0022] In particular, due to the special structure of the Zn-based organic coordination nanoparticles, compared with conventional polymer photoresists and molecular glass photoresists, the use of the Zn-based organic coordination nanoparticles of the present invention as a photoresist component can achieve better lithography performance, such as higher resolution, higher sensitivity, and lower line roughness. Currently, the integrated circuits that use domestically produced photoresists in China are often manufactured at 350 nm or above, but the ArF photoresists used at 193 nm are still in the early stages, and high-end ArF photoresists are basically imported. Therefore, when the Zn-based organic coordination nanoparticles of the present invention are used as a photoresist material for lithography, they can achieve better pattern resolution than conventional technologies, which is a major breakthrough in the domestic production of photoresists.

[0023] In addition, the coordination polymer nanoparticles according to the present invention can be used as a photoresist component to produce patterns under various exposure conditions, such as mid-ultraviolet, electron beam, and extreme ultraviolet, while also achieving extremely high photosensitivity and resolution. Furthermore, the presence of metal elements allows the photoresist according to the present invention to have superior etching resistance compared to polymer photoresists and molecular glass photoresists. [Brief explanation of the drawings]

[0024] [Figure 1] FIG. 1 is a product particle size distribution curve measured by dynamic light scattering particle size measurement (DLS) of the product produced in Example 1. [Figure 2] FIG. 2 shows the basic structural unit of the product produced in Example 1. [Figure 3] FIG. 3 shows the linear repeating chain structure of the product produced in Example 1. [Figure 4] FIG. 4 is an exposure pattern of the photoresist prepared in Example 1 after exposure to mid-ultraviolet light. [Figure 5] FIG. 5 is an exposure pattern obtained after the photoresist prepared in Example 1 is exposed to an electron beam. [Figure 6] FIG. 6 is a product particle size distribution curve measured by dynamic light scattering particle size measurement (DLS) of the product produced in Example 2. [Figure 7] FIG. 7 shows the nuclear magnetic hydrogen spectra of the product produced in Example 2 and the product and the raw materials charged. [Figure 8] FIG. 8 shows the basic structural unit of the product produced in Example 2. [Figure 9] FIG. 9 shows the linear repeating chain structure of the product produced in Example 2. [Figure 10] FIG. 10 is an exposure pattern of the photoresist prepared in Example 2 after exposure to mid-ultraviolet light. [Figure 11] FIG. 11 is an exposure pattern obtained after the photoresist prepared in Example 2 is exposed to an electron beam. [Figure 12] FIG. 12 is a product particle size distribution curve measured by dynamic light scattering particle size measurement (DLS) of the product produced in Example 3. [Figure 13] FIG. 13 shows the nuclear magnetic hydrogen spectra of the product produced in Example 3 and the product and the raw materials charged. [Figure 14]FIG. 14 shows the basic structural unit of the product produced in Example 3. [Figure 15] FIG. 15 shows the linear repeating chain structure of the product produced in Example 3. [Figure 16] FIG. 16 is an exposure pattern of the photoresist prepared in Example 3 after exposure to mid-ultraviolet light. [Figure 17] FIG. 17 is an exposure pattern obtained after the photoresist prepared in Example 3 is exposed to an electron beam. [Figure 18] FIG. 18 is a product particle size distribution curve measured by dynamic light scattering particle size measurement (DLS) of the product produced in Example 4. [Figure 19] FIG. 19 shows the nuclear magnetic hydrogen spectra of the product produced in Example 4 and the product and the raw materials charged. [Figure 20] FIG. 20 is an exposure pattern of the photoresist prepared in Example 4 after exposure to mid-ultraviolet light. [Figure 21] FIG. 21 is an exposure pattern obtained after the photoresist prepared in Example 4 was exposed to an electron beam. [Figure 22] FIG. 22 is a product particle size distribution curve measured by dynamic light scattering particle size measurement (DLS) of the product produced in Example 5. [Figure 23] FIG. 23 shows the nuclear magnetic hydrogen spectra of the product produced in Example 5 and the product and the raw materials charged. [Figure 24] FIG. 24 shows the basic structural unit of the product produced in Example 5. [Figure 25] FIG. 25 shows the linear repeating chain structure of the product produced in Example 5. [Figure 26] FIG. 26 is an exposure pattern of the photoresist prepared in Example 5 after exposure to mid-ultraviolet light. [Figure 27] FIG. 27 is an exposure pattern obtained after the photoresist prepared in Example 5 was exposed to an electron beam. DETAILED DESCRIPTION OF THE INVENTION

[0025] To facilitate an understanding of the present invention, the present invention will now be described more fully with reference to the accompanying drawings, in which preferred embodiments of the present invention are shown. However, the present invention may be embodied in many different forms and is not limited to the embodiments set forth herein. Rather, the purpose of providing these embodiments is to provide a more thorough and complete understanding of the present disclosure.

[0026] 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 the present invention pertains. In this specification, the terms used in the specification of the present invention are only for describing specific examples and are not intended to limit the present invention.

[0027] The following are specific examples, which are intended to explain the present invention in more detail and help the skilled person and researchers in this field to further understand the present invention, and the relevant technical conditions etc. are not intended to limit the present invention in any way. Any modifications made within the scope of the claims of the present invention are within the scope of protection of the claims of the present invention.

[0028] Examples of the present invention provide Zn-based organic coordination nanoparticles, having the general chemical formula [ZnX2(CH3COO)Y] n where X is a benzoic acid ligand or a m-methylbenzoic acid ligand, Y is a ligand selected from N-methylpiperidine, N-methylpyrrolidine, hexamethylenediamine, and methylpyrrolidine, and n is the degree of polymerization, n is 1 or greater, and as the n value increases, the nanoparticles form a metal-organic one-dimensional repeating chain structure. Furthermore, the size of the nanoparticles is 1 nm to 4 nm.

[0029] The present invention also provides a method for preparing Zn-based organic coordination nanoparticles, the method comprising: (1) mixing a zinc metal salt with an organic solvent to obtain a zinc metal salt solution; Step (2) of mixing the zinc metal salt solution with the first organic ligand and the second organic ligand, and heating and stirring to cause a reaction; and (3) removing any solvent remaining in the reaction product, Here, the first organic ligand is benzoic acid or m-methylbenzoic acid, and the second organic ligand is selected from N-methylpiperidine, N-methylpyrrolidine, hexamethylenediamine, and methylpyrrolidine.

[0030] Furthermore, the molar ratio of the metal salt of zinc to the first organic ligand and the second organic ligand is (0.2 to 1):(0.4 to 1):(0.3 to 1), Furthermore, in a preferred embodiment, as long as the molar ratio of the zinc metal salt, the first organic ligand, and the second organic ligand is within the range of 1:(3-5):(2-5), Zn-based organic coordination nanoparticles can be obtained.

[0031] Furthermore, in step (2), the heating and stirring is carried out at a temperature range of 50°C to 80°C for a time period of 10 hours to 40 hours. If the temperature is too low, the reaction rate will be too slow, and if the temperature is too high, the reaction will be unstable and Zn-based organic coordination nanoparticles will not be obtained.

[0032] Furthermore, in step (3), the solvent removal method can be any conventional method in the art, such as vacuum rotary evaporation. Specifically, when using vacuum rotary evaporation, the temperature can be 20°C to 80°C, and can be, for example, selected from 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, 55°C, 60°C, 65°C, 70°C, and 75°C. During the vacuum rotary evaporation process, if the temperature is too low, the reaction rate will be too slow, and if the temperature is too high, the properties of the coordination polymer nanoparticles in vacuum will be unstable and the atomic groups will be easily destroyed. The pressure of the vacuum rotary evaporation can be any value between 20mbar and 60mbar. For example, the pressure may be 25 mbar, 30 mbar, 35 mbar, 40 mbar, 45 mbar, 50 mbar, or 55 mbar, and the time for the vacuum rotary evaporation may be any value between 30 minutes and 60 minutes, for example, 35 minutes, 40 minutes, 45 minutes, 50 minutes, or 55 minutes.

[0033] The present invention further provides a Zn-based organic coordination nanoparticle photoresist composition, which comprises the Zn-based organic coordination nanoparticles prepared above, a photooxidant, and an organic dispersion solvent, wherein the weight percentage of the Zn-based organic coordination nanoparticles may be 3% to 20%, and the weight percentage of the photooxidant may be 5% to 10%.

[0034] The photooxidant may be one or more selected from N-hydroxynaphthalimide triflate, 1,4-aminonaphthalenesulfonic acid, 2-amino-5,7-naphthalenedisulfonic acid, tert-butylphenyliodonium salt perfluorooctanesulfonic acid, triphenylsulfonium perfluorobutanesulfonic acid, triphenylsulfonium perfluorobutyl, and triphenylsulfonium trifluorosulfonic acid. The organic dispersion solvent may be one or more selected from ethyl acetate, butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl acetate, 1-ethoxy-2-propanol, methanol, ethanol, and propanol.

[0035] Furthermore, the preparation process of the Zn-based organic coordination nanoparticle photoresist composition is as follows: dissolve the obtained nanoparticle composition in an organic dispersion solvent, then add a photo-oxidant until it is completely dissolved, and stir for 5 minutes to obtain a photoresist mixed solution.

[0036] An embodiment of the present invention further provides a method for patterning a photoresist, the method comprising: (1) applying the photoresist composition to a surface of a substrate and removing the organic dispersion solvent to form a pre-deposition layer on the surface of the substrate; (2) performing an exposure operation in which a light source is irradiated through a mask onto the pre-coated layer of the substrate to form photoresist particle aggregates in the exposed areas of the pre-coated layer; and (3) applying a developer to the exposed pre-coat layer so that the unexposed areas of the pre-coat layer blocked by the mask are dissolved in the developer, while the exposed areas of the pre-coat layer remain on the substrate because they have formed photoresist particle aggregates.

[0037] In step (2), the exposure conditions can be selected from any one of mid-ultraviolet light, electron beam, and extreme ultraviolet light. Furthermore, for the mask, the deep ultraviolet and longer wavelength light sources are transmissive masks, and the extreme ultraviolet light is a reflective mask, and the electron beam is exposed according to a pattern set in software. The substrate is selected from a silicon plate, and other substrates that are insoluble in the developer can also be selected according to actual needs.

[0038] Furthermore, the exposure dose of the exposure operation is 50 mJ / cm 2 ~500mJ / cm 2The exposure dose should be controlled within an appropriate range; if the exposure dose is too low, the energy will be too low, which is unfavorable for the polymerization of photoresist particles in the exposed areas, and will result in the formation of a solubility difference between the exposed and unexposed areas, resulting in poor development. Compared with bare metal nanoparticles, the polymerization of nanoparticles containing organic ligands is easier; if the exposure dose is too high, the organic ligands may directly detach from the metal oxide to form fragments, preventing the photoresist particles from undergoing an organic ligand exchange reaction, which will reduce the degree of polymerization in the exposed areas.

[0039] In step (3), the developer is selected from the group consisting of decahydronaphthalene, tetralin, indene, indane, quinoline, 1-methylnaphthalene, methylbenzene, ortho-xylene, meta-xylene, para-xylene, ethyl acetate, butyl acetate, ethanol, normal propyl alcohol, isopropyl alcohol, n-butyl alcohol, normal hexane, and cyclohexane. In some embodiments, the development temperature may be room temperature, for example, 20°C to 50°C.

[0040] The developer is primarily used to dissolve unagglomerated coordination polymer nanoparticles. The organic ligands in the coordination polymer nanoparticles in the exposed regions and the ligands generated in the photooxidizer interact with each other, changing polarity and causing aggregation to occur. The aggregates in the exposed regions may not dissolve in the developer, or may have low solubility in the developer and partially dissolve, but the exposed regions may still be covered with aggregates. The developer and the organic dispersing solvent in the photoresist composition may be the same or different. Preferably, the solubility of the coordination polymer in the developer is lower than its solubility in the organic dispersing solvent, thereby preventing the coordination polymer from dissolving in the developer due to its low degree of polymerization after exposure, dissolving or partially dissolving the exposed regions, and resulting in an inaccurate exposure pattern.

[0041] In step (3), the thickness of the pre-deposition layer after removing the organic dispersion solvent may be 10 nm to 100 nm. Specifically, the thickness of the pre-deposition layer may be 10 nm to 20 nm, 20 nm to 30 nm, 30 nm to 40 nm, 40 nm to 50 nm, 50 nm to 60 nm, 60 nm to 70 nm, 70 nm to 80 nm, 80 nm to 90 nm, or 90 nm to 100 nm.

[0042] The present invention further provides a method for forming a printed circuit board, which includes the steps of: (1) preparing a pre-patterned board having a patterned photoresist layer on a silicon substrate according to the photoresist patterning method; and (2) etching the pre-patterned board using a dry or wet method.

[0043] Hereinafter, a detailed description will be given with reference to specific examples. Example 1 (1) Preparation of Zn-based organic coordination nanoparticles Add 4.396 g (36 mmol) of benzoic acid and 2.678 g (27 mmol) of N-methylpiperidine to a flask and mix. Add 15 mL of ethyl acetate and mix for 5 minutes. The resulting solution is designated as A. Add 3.951 g (18 mmol) of zinc acetate dihydrate to a flask and add 30 mL of ethyl acetate. The resulting solution is designated as B. Add solution A dropwise to solution B in the flask and stir at 65 °C for 16 hours. After the reaction is complete, evaporate the mixture at 50 °C for 40 minutes using a rotary evaporator, controlling the pressure at 40 mbar to obtain the synthesized product. An appropriate amount of the product was analyzed by dynamic light scattering (DLS) to obtain the product particle size distribution curve (shown in Figure 1). As can be seen from Figure 1, the average particle size of the suspended particles in the synthesized product was 1.5 nm, and the particle size distribution interval was narrower, which indicates the higher particle size consistency of the nanoparticles. Furthermore, the structure and composition of the synthesized product were measured. Figure 2 shows the basic structural unit of the synthesized product. The structural formula of this basic structural unit is Zn(C6H5COO)2(CH3COO)(CH3C5H 10FIG. 3 shows a one-dimensional repeating chain structure formed by polymerization based on the basic structural unit, and the structure is [Zn(C6H5COO)2(CH3COO)(CH3C5H 10 N)H] n is.

[0044] (2) Preparation of Zn-based organic coordination nanoparticle photoresist composition 0.5 g of the Zn-based organic coordination nanoparticles prepared above was taken, and 0.05 g of N-hydroxynaphthalimide triflate was selected. The Zn-based organic coordination nanoparticles and N-hydroxynaphthalimide triflate were dissolved in 9.45 g of propylene glycol monomethyl ether acetate to prepare a Zn-based organic coordination nanoparticle photoresist composition.

[0045] (3) Preparation of Zn-based organic coordination nanoparticle photoresist coating The Zn-based organic coordination nanoparticle photoresist solution prepared in step (2) was applied to a 2-inch silicon wafer at a rotation speed of 2000 rpm for 1 minute, and then baked at 80°C for 1 minute to obtain a Zn-based organic coordination nanoparticle photoresist pre-coating layer with a thickness of 30 nm.

[0046] (4) Exposure of Zn-based organic coordination nanoparticle photoresist coating The exposure operation is performed by exposing to 254 nm mid-ultraviolet light, and the light source is transmitted through a mask to irradiate the pre-coating layer of the substrate, so that photoresist particle aggregates are formed in the exposed areas of the pre-coating layer, the substrate is selected from a silicon plate, and the exposure dose of the exposure operation is 150 mJ / cm 2 or exposed to an electron beam, the exposure dose of the exposure operation being 190 μC / cm 2 is.

[0047] (5) Development Decahydronaphthalene was selected as the developer and applied to the exposed pre-coated layer. The unexposed areas of the pre-coated layer, which were blocked by the mask, were dissolved in the developer. However, the exposed areas of the pre-coated layer remained on the substrate because they had formed photoresist particle aggregates. The development temperature was room temperature, 26°C.

[0048] Figure 4 shows the exposure pattern of the photoresist prepared in this example after exposure to mid-ultraviolet light. As can be seen from Figure 4, the exposure line width is 10 μm, the lines of the exposure pattern are clear, and the edge roughness is low, which fully meets the requirements for mid-ultraviolet lithography and is higher than the exposure quality of conventional CAR systems. Figure 5 shows the exposure line width of 50 nm obtained after the photoresist prepared with Zn-based organic coordination nanoparticles is exposed to electron beam. As can be seen from Figure 5, all the lines of the lithography pattern are clear, which can meet the requirements for 50 nm exposure pattern and can be used as electron beam photoresist.

[0049] Example 2 (1) Preparation of Zn-based organic coordination nanoparticles Add 4.396 g (36 mmol) of benzoic acid and 2.299 g (27 mmol) of N-methylpyrrolidine to a flask and mix. Add 15 mL of ethyl acetate and mix for 5 minutes. The resulting solution is designated as A. Add 3.951 g (18 mmol) of zinc acetate dihydrate to a flask and add 30 mL of ethyl acetate. The resulting solution is designated as B. Add solution A to solution B in the flask and stir at 65 °C for 16 hours. After the reaction is complete, evaporate the mixture at 50 °C for 40 minutes using a rotary evaporator and control the pressure to 40 mbar to obtain the synthesized product. An appropriate amount of the product was analyzed by dynamic light scattering (DLS) to obtain the product particle size distribution curve (shown in Figure 6). As can be seen from Figure 6, the average particle size of the suspended particles in the synthesized product was 1.9 nm, and the particle size distribution interval was narrower, indicating better nanoparticle size consistency. The manufactured nanoparticles were subjected to nuclear magnetic resonance measurement, and the nuclear magnetic hydrogen spectrum data (see Figure 7) 1HNMR (400MHz, DMSO-d6) δ 7.97-7.89 (m), 7.51-7.35 (m), 2.68 (d, J = 6.9Hz), 2.41 (s), 1.86 (s), 1.59 (p, J = 5.7Hz), 1.45-1.36 (m). The peaks for the N-methylpiperidine structure shifted from 1.34, 1.47, 2.10, and 2.22 to 1.40, 1.59, 2.41, and 2.68, respectively, and the peaks for the methyl groups in zinc acetate shifted from 1.82 to 1. The peaks of the benzoic acid benzene ring shifted from 7.51, 7.63, and 7.95 to 7.39, 7.47, and 7.93, respectively. This indicates that each monomer is coordinated in the nanoparticles. Calculations indicate that the basic structural unit of the nanoparticles is Zn(C6H5COO)2(CH3COO)(CH3C4H8N) (shown in Figure 8), and the one-dimensional repeating chain nano-organic structure formed is [Zn(C6H5COO)2(CH3COO)(CH3C4H8N)]. n and is shown in FIG.

[0050] (2) Preparation of Zn-based organic coordination nanoparticle photoresist composition 0.5 g of the Zn-based organic coordination nanoparticles prepared above was taken, and 0.05 g of N-hydroxynaphthalimide triflate was selected. The Zn-based organic coordination nanoparticles and N-hydroxynaphthalimide triflate were dissolved in 9.45 g of propylene glycol monomethyl ether acetate to prepare a Zn-based organic coordination nanoparticle photoresist composition.

[0051] (3) Preparation of Zn-based organic coordination nanoparticle photoresist coating The Zn-based organic coordination nanoparticle photoresist solution prepared in step (2) was applied to a 2-inch silicon wafer at a rotation speed of 2000 rpm for 1 minute, and then baked at 80°C for 1 minute to obtain a Zn-based organic coordination nanoparticle photoresist pre-coating layer with a thickness of 30 nm.

[0052] (4) Exposure of Zn-based organic coordination nanoparticle photoresist coating The exposure operation is performed by exposing to 254 nm mid-ultraviolet light, and the light source is transmitted through a mask to irradiate the pre-coating layer of the substrate, so that photoresist particle aggregates are formed in the exposed areas of the pre-coating layer, the substrate is selected from a silicon plate, and the exposure dose of the exposure operation is 150 mJ / cm 2 or exposed to an electron beam, the exposure dose of the exposure operation being 190 μC / cm 2 is.

[0053] (5) Development Decahydronaphthalene was selected as the developer and applied to the exposed pre-coated layer. The unexposed areas of the pre-coated layer, which were blocked by the mask, were dissolved in the developer. However, the exposed areas of the pre-coated layer remained on the substrate because they had formed photoresist particle aggregates. The development temperature was room temperature, 26°C.

[0054] Figure 10 shows the exposure pattern of the photoresist prepared in this example after exposure to mid-ultraviolet light. As can be seen from Figure 10, the exposure line width is 10 μm, the lines of the exposure pattern are clear, and the edge roughness is low, which fully meets the requirements for mid-ultraviolet lithography and is higher than the exposure quality of conventional CAR systems. Figure 11 shows the exposure line width of 50 nm obtained after the photoresist prepared with Zn-based organic coordination nanoparticles is exposed to electron beam. As can be seen from Figure 11, all the lines of the lithography pattern are clear, which can meet the requirements for 50 nm exposure pattern and can be used as electron beam photoresist.

[0055] Example 3 (1) Preparation of Zn-based organic coordination nanoparticles 4.936 g (36 mmol) of m-methylbenzoic acid and 2.678 g (27 mmol) of N-methylpiperidine were added to a flask and mixed. 15 mL of ethyl acetate was added and mixed for 5 minutes. The resulting solution was designated as A. 3.951 g (18 mmol) of zinc acetate dihydrate was added to a flask and 30 mL of ethyl acetate was added. The resulting solution was designated as B. Solution A was added dropwise to solution B in the flask and stirred at 65 ° C for 16 hours. After the reaction was completed, the mixture was rotary evaporated at 50 ° C for 40 minutes using a rotary evaporator, and the pressure was controlled at 40 mbar to obtain the synthesized product. An appropriate amount of the product was analyzed by dynamic light scattering (DLS) to obtain the product particle size distribution curve (shown in Figure 12). As can be seen from Figure 12, the average particle size of the suspended particles in the synthesized product was 1.7 nm, and the particle size distribution interval was narrower, indicating higher nanoparticle size consistency. The manufactured nanoparticles were subjected to nuclear magnetic resonance measurement, and the nuclear magnetic hydrogen spectrum data (see Figure 13) 1 HNMR (400MHz, DMSO-d6) δ 7.96-7.89 (m), 7.52-7.43 (m), 7.40 (ddt, J = 8.3, 6.7, 1.4 Hz), 2.68 (d, J = 6.9 Hz), 2.41 (s), 1.86 (s), 1.59 (p, J = 5.7 Hz), 1.46-1.33 (m), and the peaks for the N-methylpiperidine structure are 1. The peaks of the methyl group in zinc acetate shifted from 1.82 to 1.86, the peak of the methyl group in m-methylbenzoic acid shifted from 2.37 to 2.33, and the peaks of the benzene ring shifted from 7.39, 7.44, and 7.76 to 7.40, 7.46, and 7.93. Each monomer coordinated in the nanoparticles, and calculations showed that the basic structural unit of the nanoparticles was Zn(CH3C6H5COO)2(CH3COO)(CH3C5H 10 N) (shown in FIG. 14), and the formed one-dimensional repeating chain nano-organic structure [Zn(CH3C6H5COO)2(CH3COO)(CH3C5H 10 N)] n is shown in Figure 15.

[0056] (2) Preparation of Zn-based organic coordination nanoparticle photoresist composition 0.5 g of the Zn-based organic coordination nanoparticles prepared above was taken, and 0.05 g of N-hydroxynaphthalimide triflate was selected. The Zn-based organic coordination nanoparticles and N-hydroxynaphthalimide triflate were dissolved in 9.45 g of propylene glycol monomethyl ether acetate to prepare a Zn-based organic coordination nanoparticle photoresist composition.

[0057] (3) Preparation of Zn-based organic coordination nanoparticle photoresist coating The Zn-based organic coordination nanoparticle photoresist solution prepared in step (2) was applied to a 2-inch silicon wafer at a rotation speed of 2000 rpm for 1 minute, and then baked at 80°C for 1 minute to obtain a Zn-based organic coordination nanoparticle photoresist pre-coating layer with a thickness of 30 nm.

[0058] (4) Exposure of Zn-based organic coordination nanoparticle photoresist coating The exposure operation is performed by exposing to 254 nm mid-ultraviolet light, and the light source is transmitted through a mask to irradiate the pre-coating layer of the substrate, so that photoresist particle aggregates are formed in the exposed areas of the pre-coating layer, the substrate is selected from a silicon plate, and the exposure dose of the exposure operation is 150 mJ / cm 2 or exposed to an electron beam, the exposure dose of the exposure operation being 150 μC / cm 2 is.

[0059] (5) Development Decahydronaphthalene was selected as the developer and applied to the exposed pre-coated layer. The unexposed areas of the pre-coated layer, which were blocked by the mask, were dissolved in the developer. However, the exposed areas of the pre-coated layer remained on the substrate because they had formed photoresist particle aggregates. The development temperature was room temperature, 26°C.

[0060] Figure 16 shows the exposure pattern of the photoresist prepared in this example after exposure to mid-ultraviolet light. As can be seen from Figure 16, the exposure line width is 10 μm, the lines of the exposure pattern are clear, and the edge roughness is low, which fully meets the requirements for mid-ultraviolet light lithography and is higher than the exposure quality of conventional CAR systems. Figure 17 shows the exposure line width of 50 nm obtained after the photoresist prepared with Zn-based organic coordination nanoparticles is exposed to electron beam. As can be seen from Figure 17, all the lines of the lithography pattern are clear, which can meet the requirements for 50 nm exposure pattern and can be used as electron beam photoresist.

[0061] Example 4 (1) Preparation of Zn-based organic coordination nanoparticles Add 4.936 g (36 mmol) of m-methylbenzoic acid and 2.705 g (27 mmol) of hexamethylenediamine to a flask and mix. Add 15 mL of ethyl acetate and dissolve for 5 minutes. The resulting solution is designated as A. Add 3.951 g (18 mmol) of zinc acetate dihydrate to a flask and add 30 mL of ethyl acetate. The resulting solution is designated as B. Add solution A to solution B in the flask and stir at 65 ° C for 16 hours. After the reaction is complete, evaporate the mixture at 50 ° C for 40 minutes using a rotary evaporator and control the pressure at 40 mbar to obtain the synthesized product. An appropriate amount of the product was analyzed by dynamic light scattering (DLS) to obtain the product particle size distribution curve (shown in Figure 18). As can be seen from Figure 18, the average particle size of the suspended particles in the synthesized product was 2.4 nm, and the particle size distribution interval was narrower, indicating better nanoparticle size consistency. The manufactured nanoparticles were subjected to nuclear magnetic resonance measurement, and the nuclear magnetic hydrogen spectrum data (see Figure 19) 1HNMR (400MHz, DMSO-d6) δ 7.75 (d, J = 1.9Hz), 7.71 (tt, J = 4.4, 3.4Hz), 7.30-7.20 (m), 3.07-3.00 (m), 2.33 (s), 1.84 (s), 1.75-1.64 (m), 1.62-1.51 (m). As can be seen from the nuclear magnetic graph, after the nanoparticles were synthesized, each monomer coordinated, causing a peak shift. The peaks of the hexamethylenediamine structure shifted from 1.52 and 2.68 to 1.56, 1.70, and 3.03, respectively; the peak of the methyl group in zinc acetate shifted from 1.82 to 1.84; the peak of the methyl group in m-methylbenzoic acid shifted from 2.37 to 2.33; and the peaks of the benzene ring shifted from 7.39, 7.44, and 7.76 to 7.25, 7.75, and 7.71. Each monomer coordinated in the produced nanoparticles, and calculations showed that the basic structural unit of the produced Zn-based organic coordination nanoparticles was Zn(CH3C6H5COO)2(CH3COO)(CH6H 14 N).

[0062] (2) Preparation of Zn-based organic coordination nanoparticle photoresist composition 0.5 g of the Zn-based organic coordination nanoparticles prepared above was taken, and 0.05 g of N-hydroxynaphthalimide triflate was selected. The Zn-based organic coordination nanoparticles and N-hydroxynaphthalimide triflate were dissolved in 9.45 g of propylene glycol monomethyl ether acetate to prepare a Zn-based organic coordination nanoparticle photoresist composition.

[0063] (3) Preparation of Zn-based organic coordination nanoparticle photoresist coating The Zn-based organic coordination nanoparticle photoresist solution prepared in step (2) was applied to a 2-inch silicon wafer at a rotation speed of 2000 rpm for 1 minute, and then baked at 80°C for 1 minute to obtain a Zn-based organic coordination nanoparticle photoresist pre-coating layer with a thickness of 30 nm.

[0064] (4) Exposure of Zn-based organic coordination nanoparticle photoresist coating The exposure operation is performed by exposing to 254 nm mid-ultraviolet light, and the light source is transmitted through a mask to irradiate the pre-coating layer of the substrate, so that photoresist particle aggregates are formed in the exposed areas of the pre-coating layer, the substrate is selected from a silicon plate, and the exposure dose of the exposure operation is 150 mJ / cm 2 or exposed to an electron beam, the exposure dose of the exposure operation being 200 μC / cm 2 is.

[0065] (5) Development Decahydronaphthalene was selected as the developer and applied to the exposed pre-coated layer. The unexposed areas of the pre-coated layer, which were blocked by the mask, were dissolved in the developer. However, the exposed areas of the pre-coated layer remained on the substrate because they had formed photoresist particle aggregates. The development temperature was room temperature, 26°C.

[0066] Figure 20 shows the exposure pattern of the photoresist prepared in this example after exposure to mid-ultraviolet light. As can be seen from Figure 20, the exposure line width is 10 μm, the lines of the exposure pattern are clear, and the edge roughness is low, which fully meets the requirements for mid-ultraviolet lithography and is higher than the exposure quality of conventional CAR systems. Figure 21 shows the exposure line width of 50 nm obtained after the photoresist prepared with Zn-based organic coordination nanoparticles is exposed to electron beam. As can be seen from Figure 21, all the lines of the lithography pattern are clear, which can meet the requirements for 50 nm exposure pattern and can be used as electron beam photoresist.

[0067] Example 5 (1) Preparation of Zn-based organic coordination nanoparticles 4.936 g (36 mmol) of m-methylbenzoic acid and 2.299 g (27 mmol) of N-methylpyrrolidine were added to a flask and mixed. 15 mL of ethyl acetate was added and mixed for 5 minutes. The resulting solution was designated as A. 3.951 g (18 mmol) of zinc acetate dihydrate was added to the flask and 30 mL of ethyl acetate was added. The resulting solution was designated as B. Solution A was added dropwise to solution B in the flask and stirred at 65 ° C for 16 hours. After the reaction was completed, the mixture was rotary evaporated at 50 ° C for 40 minutes using a rotary evaporator, and the pressure was controlled at 40 mbar to obtain the synthesized product. An appropriate amount of the product was analyzed by dynamic light scattering (DLS) to obtain the product particle size distribution curve (shown in Figure 22). As can be seen from Figure 22, the average particle size of the suspended particles in the synthesized product was 2.0 nm, and the particle size distribution interval was narrower, indicating higher nanoparticle size consistency. The manufactured nanoparticles were subjected to nuclear magnetic resonance measurement, and the nuclear magnetic hydrogen spectrum data (see Figure 23) 1 HNMR (400MHz, DMSO-d6) δ 7.75 (s), 7.72 (t, J = 4.7Hz), 7.29 (d, J = 4.7Hz), 2.77 (d, J = 6.5Hz), 2.50-2.42 (m), 2.34 (s), 1.86 (s), 1.84-1.75 (m). As can be seen from the nuclear magnetic graph, after the nanoparticles were synthesized, each monomer coordinated, causing a peak shift and resulting in methyl The peaks for the pyrrolidine structure shifted from 1.67, 2.22, and 2.34 to 1.80, 2.46, and 2.77, respectively; the peak for the methyl group in zinc acetate shifted from 1.82 to 1.86; the peak for the methyl group in m-methylbenzoic acid shifted from 2.35 to 2.34; and the peaks for the benzene ring shifted from 7.39, 7.44, and 7.76 to 7.29, 7.72, and 7.75. Each monomer coordinated in the nanoparticles, and calculations showed that the basic structural unit of the nanoparticles was Zn(CHCHCOO)(CHCOO)(CHCHN)H (see Figure 24). The resulting one-dimensional repeating chain nanoorganic structure is shown in Figure 25.

[0068] (2) Preparation of Zn-based organic coordination nanoparticle photoresist composition 0.5 g of the Zn-based organic coordination nanoparticles prepared above was taken, and 0.05 g of N-hydroxynaphthalimide triflate was selected. The Zn-based organic coordination nanoparticles and N-hydroxynaphthalimide triflate were dissolved in 9.45 g of propylene glycol monomethyl ether acetate to prepare a Zn-based organic coordination nanoparticle photoresist composition.

[0069] (3) Preparation of Zn-based organic coordination nanoparticle photoresist coating The Zn-based organic coordination nanoparticle photoresist solution prepared in step (2) was applied to a 2-inch silicon wafer at a rotation speed of 2000 rpm for 1 minute, and then baked at 80°C for 1 minute to obtain a Zn-based organic coordination nanoparticle photoresist pre-coating layer with a thickness of 30 nm.

[0070] (4) Exposure of Zn-based organic coordination nanoparticle photoresist coating The exposure operation is performed by exposing to 254 nm mid-ultraviolet light, and the light source is transmitted through a mask to irradiate the pre-coating layer of the substrate, so that photoresist particle aggregates are formed in the exposed areas of the pre-coating layer, the substrate is selected from a silicon plate, and the exposure dose of the exposure operation is 150 mJ / cm 2 or exposed to an electron beam, the exposure dose of the exposure operation being 270 μC / cm 2 is.

[0071] (5) Development Decahydronaphthalene was selected as the developer and applied to the exposed pre-coated layer. The unexposed areas of the pre-coated layer, which were blocked by the mask, were dissolved in the developer. However, the exposed areas of the pre-coated layer remained on the substrate because they had formed photoresist particle aggregates. The development temperature was room temperature, 26°C.

[0072] Figure 26 shows the exposure pattern of the photoresist prepared in this example after exposure to mid-ultraviolet light. As can be seen from Figure 26, the exposure line width is 10 μm, the lines of the exposure pattern are clear, and the edge roughness is low, which fully meets the requirements for mid-ultraviolet light lithography and is higher than the exposure quality of conventional CAR systems. Figure 27 shows the exposure line width of 50 nm obtained after the photoresist prepared with Zn-based organic coordination nanoparticles is exposed to electron beam. As can be seen from Figure 27, all the lines of the lithography pattern are clear, which can meet the requirements for 50 nm exposure pattern and can be used as electron beam photoresist.

[0073] JPEG2025525925000002.jpg95170

[0074] JPEG2025525925000003.jpg115170

[0075] At present, the integrated circuits using photoresists produced by enterprises engaged in the research, development and industrialization of semiconductor photoresists in China are mostly manufactured using processes above 350nm, but the ArF photoresists used at 193nm are still in the early stages, and high-end ArF photoresists are basically imported. Therefore, when the Zn-based organic coordination nanoparticles of the present invention are used as photoresist materials for lithography, they can achieve better pattern resolution than conventional technologies, which is a major breakthrough in the domestic production of photoresists.

[0076] Furthermore, the presence of metal elements allows the photoresist of the present invention to have superior etching resistance compared to polymer photoresists and molecular glass photoresists.

[0077] The technical features of the embodiments described above may be combined in any manner, and for the sake of brevity, not all possible combinations of the technical features of the embodiments described above are described, but combinations of these technical features should be considered to be within the scope described in this specification unless they are inconsistent. The above-described examples merely illustrate some embodiments of the present invention, and although the descriptions are more specific and detailed, they should not be understood as limiting the patent scope of the invention. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, all of which fall within the scope of protection of the present invention. Therefore, the patent scope of the present invention should be governed by the appended claims.

Claims

1. Zn-based organic coordination nanoparticles, The nanoparticles have a metal-organic one-dimensional repeating chain structure and have the general structural formula [ZnX ２ (CH ３ COO)Y] ｎ wherein X is selected from a benzoic acid group or a m-methylbenzoic acid group, Y is selected from an organic amine-based ligand, the size of the nanoparticles is 1 nm to 4 nm, n is a degree of polymerization and is 1 or more, and the organic amine-based ligand is selected from N-methylpiperidine, N-methylpyrrolidine, hexamethylenediamine, or methylpyrrolidine.

2. A method for producing Zn-based organic coordination nanoparticles, comprising: Step (1) of mixing a zinc metal salt with an organic solvent to obtain a zinc metal salt solution; (2) mixing the zinc metal salt solution with a first organic ligand and a second organic ligand, and heating and stirring to cause a reaction; and (3) removing the solvent remaining in the reaction product.

3. 3. The method for producing Zn-based organically coordinated nanoparticles according to claim 2, wherein the first organic ligand is benzoic acid or m-methylbenzoic acid, and the second organic ligand is selected from N-methylpiperidine, N-methylpyrrolidine, hexamethylenediamine, and methylpyrrolidine.

4. The method for producing Zn-based organically coordinated nanoparticles according to claim 2, characterized in that the molar ratio of the zinc metal salt, the first organic ligand, and the second organic ligand is (0.2 to 1):(0.4 to 1):(0.3 to 1).

5. The method for producing Zn-based organically coordinated nanoparticles according to claim 2, characterized in that the molar ratio of the zinc metal salt, the first organic ligand, and the second organic ligand is 1:(3-5):(2-5).

6. The method for producing Zn-based organically coordinated nanoparticles according to claim 2, characterized in that in step (2), the heating and stirring is carried out at a temperature range of 50°C to 80°C for a time period of 10 hours to 40 hours.

7. 3. The method for preparing Zn-based organically coordinated nanoparticles according to claim 2, wherein in step (3), the solvent is removed by vacuum rotary evaporation, the temperature is 20°C to 80°C, the pressure of the vacuum rotary evaporation is 20mbar to 60mbar, and the time of the vacuum rotary evaporation is 30min to 60min.

8. Zn-based organic coordination nanoparticles, The Zn-based organic coordination nanoparticles are obtained by the method for producing Zn-based organic coordination nanoparticles according to any one of claims 2 to 7.

9. 1. A Zn-based organic coordinated nanoparticle photoresist composition, comprising: A Zn-based organic coordination nanoparticle photoresist composition comprising the Zn-based organic coordination nanoparticles of claim 1 or 8, a photooxidant, and an organic dispersion solvent, wherein the mass percentage of the Zn-based organic coordination nanoparticles is 3% to 20%, and the mass percentage of the photooxidant is 5% to 10%.

10. 10. The photoresist composition of claim 9, wherein the photooxidant is selected from the group consisting of N-hydroxynaphthalimide triflate, 1,4-aminonaphthalenesulfonic acid, 2-amino-5,7-naphthalenedisulfonic acid, tert-butylphenyliodonium salt perfluorooctanesulfonic acid, triphenylsulfonium perfluorobutanesulfonic acid, triphenylsulfonium perfluorobutyl, and triphenylsulfonium trifluorosulfonic acid; and the organic dispersion solvent is selected from the group consisting of ethyl acetate, butyl acetate, propylene glycol monoethyl ether acetate, propylene glycol monomethyl acetate, 1-ethoxy-2-propanol, methanol, ethanol, and propanol.

11. A method for preparing a Zn-based organic coordination nanoparticle photoresist composition, comprising: A method for producing a Zn-group organically coordinated nanoparticle photoresist composition, comprising dissolving the nanoparticles according to claim 1 or 8 in an organic dispersion solvent, adding a photo-oxidizing agent until the nanoparticles are completely dissolved, and stirring for 5 minutes to obtain a photoresist composition.

12. 1. A method for patterning a photoresist, comprising: Step (1): applying the photoresist composition according to claim 9 or 10 to a surface of a substrate, and removing the organic dispersion solvent to form a pre-deposition layer on the surface of the substrate; (2) performing an exposure operation in which a light source is irradiated through a mask onto the pre-coated layer of the substrate, thereby forming photoresist particle aggregates in the exposed areas of the pre-coated layer; and (3) applying a developer to the exposed pre-deposited layer so that the unexposed areas of the pre-deposited layer blocked by the mask are dissolved in the developer, while the exposed areas of the pre-deposited layer remain on the substrate because they have formed photoresist particle agglomerates.

13. The exposure conditions were selected from one of intermediate ultraviolet light, electron beam, and extreme ultraviolet light, and the exposure dose of ultraviolet light was 50 mJ / cm ２ ~500 mJ / cm ２ and the exposure dose of the electron beam is 50 μC / cm ２ ~500μC / cm ２ and the thickness of the pre-deposition layer after removing the organic dispersion solvent is 10 nm to 100 nm.

14. 1. A method of forming a printed circuit board, comprising:

14. A method for patterning a photoresist according to claim 12 or 13, comprising the steps of: (1) manufacturing a pre-patterned plate having a patterned photoresist layer on a silicon plate substrate; (2) etching the pre-patterned board using a dry or wet process.

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