UV resist, UV resist patterning methods and applications

Abstract

This invention provides an ultraviolet resist and a patterning method for an ultraviolet resist that can significantly reduce the exposure dose and increase the speed of photoresist by selecting a photosensitizer. [Solution] The ultraviolet resist comprises an organic solvent, a photosensitizer, and zirconium oxide nanoclusters. The general formula for zirconium oxide nanoclusters is Zr x O y (OH) z L m The formula is such that 2≦x≦20, 2≦y≦40, 0≦z≦40, 4≦m≦40, and L is a carboxyl group-containing organic ligand. The photosensitizer has structural formula (1), and in formula (1), R 1 This is shown by equation (2). JPEG2026102744000018.jpg34170 JPEG2026102744000019.jpg17170

Description

Technical Field

[0001] The present invention claims priority based on a Chinese patent application filed with the China National Intellectual Property Administration on June 21, 2022, with an application number of 202210701897.5 and an invention title of "Ultraviolet Resist, Patterning Method and Use of Ultraviolet Resist", and a Chinese patent application filed with the China National Intellectual Property Administration on June 21, 2022, with an application number of 202210701894.1 and an invention title of "Ultraviolet Resist and Patterning Method of Ultraviolet Resist", and incorporates all the contents of the above Chinese patent applications by reference into the present invention. The present invention relates to the technical field of photoresists, and specifically relates to ultraviolet resists, patterning methods and uses of ultraviolet resists.

Background Art

[0002] At present, large-scale integrated circuits in the semiconductor industry are all processed and manufactured by photolithography technology. The integration, yield and cost of integrated circuits are directly determined by the resolution and line width of photolithography processing technology. Photolithography processing technology refers to a micro-nano processing technology that transfers the pattern on a mask to an exposure substrate by changing the solubility of a photoresist under an exposure beam. A photoresist is a mixed material sensitive to light or radiation. Current ultraviolet resists are mainly composed of a film-forming resin, a photosensitizer, a solvent and other additives, and the film-forming resin is the main component of the photoresist.

[0003] Currently commercially available ultraviolet resists are mainly photosensitive materials with a polymer compound as the film-forming resin, and require a large exposure dose during use and have low sensitivity.

Summary of the Invention

Problems to be Solved by the Invention

[0004] Therefore, the present invention provides an ultraviolet resist, a patterning method and a use of the ultraviolet resist, which have a small exposure dose and high sensitivity.

Means for Solving the Problem

[0005] One aspect of the present invention provides an ultraviolet resist, which contains an organic solvent, a photosensitizer, and zirconium oxide nanoclusters. The general formula of the zirconium oxide nanoclusters is Zr x O y (OH) z L m where 2 ≤ x ≤ 20, 2 ≤ y ≤ 40, 0 ≤ z ≤ 40, 4 ≤ m ≤ 40, and L is a carboxyl group-containing organic ligand. The photosensitizer has the structural formula (1), and in formula (1), R 1 is represented by formula (2), and * represents the binding site. <Chemical Formula 1> JPEG2026102744000002.jpg34170<Chemical Formula 2> JPEG2026102744000003.jpg17170

[0006] R 2 and R 3 are each independently selected from -F, -Cl, -Br, or -I each time they appear.

[0007] Optionally, in the above ultraviolet resist, R 2 and R 3 are both -Cl.

[0008] Optionally, in the above ultraviolet resist, the carboxyl group-containing organic ligand contains at least one of an acrylic ligand, a methacrylic ligand, a 1-hydroxy-2-naphthoic acid ligand, and a salicylic acid ligand.

[0009] Optionally, in the above ultraviolet resist, the mass percentage of the zirconium oxide nanoclusters in the organic solvent is 0.5% to 15%, and the mass percentage of the photosensitizer is 0.001% to 1%.

[0010] Selectively, in the above ultraviolet resist, the organic solvent comprises at least one of ethyl lactate, anisole, propylene glycol monomethyl ether acetate, methyl isobutyl ketone, and isopropyl alcohol.

[0011] Another aspect of the present invention further provides a method for patterning an ultraviolet resist, the method comprising the steps of: spin-coating the above-mentioned ultraviolet resist onto a substrate and then drying it to form an ultraviolet resist film; and exposing the ultraviolet resist film to ultraviolet lithography using a mask, then developing it in a developer to form a lithography pattern.

[0012] Selectively, the developer comprises at least one of toluene, xylene, 1,2-diacetoxypropane, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, isopropyl alcohol, isobutyl alcohol, isoamyl alcohol, 4-methyl-2-pentanol, isopropoxyethanol, 1-methoxy-2-propanol, 1-propoxy-2-propanol, 1-butoxy-2-propanol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, propylene glycol ethyl ether, 2-heptanone, and 2-butanone.

[0013] Selectively, in the above UV resist patterning method, the UV lithography exposure light source is either 365 nm UV, 254 nm deep UV, or 13.5 nm extreme UV. Furthermore, the exposure dose is 7 mJcm when the UV lithography exposure light source is 254 nm deep UV. -2 The above is true, and when the light source for ultraviolet lithography exposure is ultraviolet light with a wavelength of 365 nm, the required energy is 300 mJcm². -2 That's all.

[0014] Selectively, the above ultraviolet resists can also be used as electron beam photoresists.

[0015] One aspect of the present invention provides an ultraviolet resist comprising an organic solvent, a photosensitizer, and zirconium oxide nanoclusters. The general formula of the zirconium oxide nanoclusters is Zr x O y (OH) z L m The formula is such that 2≦x≦20, 2≦y≦40, 0≦z≦40, 4≦m≦40, and L is a carboxyl group-containing organic ligand. The photosensitizer has structural formula (1), and in the formula R 1 is one of equations (3), (4), or (5), and * represents the bonding site, R 2 and R 3 Each instance of -F, -Cl, -Br, or -I is independently selected. <C1> JPEG2026102744000004.jpg34170<3> JPEG2026102744000005.jpg17170<4> JPEG2026102744000006.jpg20170<5> JPEG2026102744000007.jpg23170

[0016] Selectively, in the above ultraviolet resist, R 2 and R 3 All of them are -Cl.

[0017] Selectively, in the above ultraviolet resist, the carboxyl group-containing organic ligand includes at least one of the following: an acrylic ligand, a methacrylic ligand, a 1-hydroxy-2-naphthoic acid ligand, and a salicylic acid ligand.

[0018] Selectively, in the above ultraviolet resist, the mass percentage of zirconium oxide nanoclusters in the organic solvent is 0.5% to 15%, and the mass percentage of the photosensitizer in the organic solvent is 0.001% to 1%.

[0019] Selectively, in the above ultraviolet resist, the organic solvent comprises at least one of ethyl lactate, anisole, propylene glycol monomethyl ether acetate, methyl isobutyl ketone, and isopropyl alcohol.

[0020] Another aspect of the present invention further provides a method for patterning an ultraviolet resist, the method comprising the steps of: spin-coating the above-mentioned ultraviolet resist onto a substrate and then drying it to form an ultraviolet resist film; and exposing the ultraviolet resist film to ultraviolet lithography using a mask, then developing it in a developer to form a lithography pattern.

[0021] Selectively, the developer comprises at least one of toluene, xylene, 1,2-diacetoxypropane, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, isopropyl alcohol, isobutyl alcohol, isoamyl alcohol, 4-methyl-2-pentanol, isopropoxyethanol, 1-methoxy-2-propanol, 1-propoxy-2-propanol, 1-butoxy-2-propanol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, propylene glycol ethyl ether, 2-heptanone, and 2-butanone.

[0022] Selectively, in the above UV resist patterning method, the UV lithography exposure light source is UV with a wavelength of 365 nm, deep UV with a wavelength of 254 nm, or extreme UV with a wavelength of 13.5 nm. Furthermore, the exposure dose is 12 mJcm when the UV lithography exposure light source is deep UV with a wavelength of 254 nm. -2 The above is true, and when the light source for ultraviolet lithography exposure is ultraviolet light with a wavelength of 365 nm, the required energy is 200 mJcm². -2 That's all. [Effects of the Invention]

[0023] The UV resist of the present invention uses zirconium oxide nanoclusters as the film-forming resin, resulting in a single scale of only 1 nm to 5 nm, which is far smaller than the size of polymer chains (generally larger than 20 nm). Therefore, compared to conventional polymer resin-type photoresists, the UV resist of the present invention can photoetch patterns with smaller line widths. When the zirconium oxide nanocluster film-forming resin is effectively compatible with the photosensitizer, the sensitivity of the UV resist is greatly improved, the exposure dose is greatly reduced, and the photolithography efficiency is greatly improved. Furthermore, the presence of metal oxides results in excellent mechanical properties and etching resistance of the photoresist, and high pattern fidelity with virtually no deformation or peeling of the exposed pattern during the subsequent development process. [Brief explanation of the drawing]

[0024] [Figure 1A] This is the exposure pattern obtained at an exposure wavelength of 254 nm in Example 1 of the present invention. [Figure 1B] This is the exposure pattern obtained at an exposure wavelength of 254 nm in Example 1 of the present invention. [Figure 2A] This is the exposure pattern obtained at an exposure wavelength of 365 nm in Example 1 of the present invention. [Figure 2B] This is the exposure pattern obtained at an exposure wavelength of 365 nm in Example 1 of the present invention. [Figure 3] This is the exposure pattern obtained by electron beam lithography exposure in Example 2 of the present invention. [Figure 4A] This is the exposure pattern obtained at an exposure wavelength of 254 nm in Comparative Example 1 of the present invention. [Figure 4B] This is the exposure pattern obtained at an exposure wavelength of 254 nm in Comparative Example 1 of the present invention. [Figure 5A] This is the exposure pattern obtained at an exposure wavelength of 365 nm in Comparative Example 1 of the present invention. [Figure 5B] This is the exposure pattern obtained at an exposure wavelength of 365 nm in Comparative Example 1 of the present invention. [Figure 6A]This is the exposure pattern obtained at an exposure wavelength of 254 nm in Example 3 of the present invention. [Figure 6B] This is the exposure pattern obtained at an exposure wavelength of 254 nm in Example 3 of the present invention. [Figure 7A] This is the exposure pattern obtained at an exposure wavelength of 365 nm in Example 3 of the present invention. [Figure 7B] This is the exposure pattern obtained at an exposure wavelength of 365 nm in Example 3 of the present invention. [Figure 8A] This is the exposure pattern obtained at an exposure wavelength of 254 nm in Example 4 of the present invention. [Figure 8B] This is the exposure pattern obtained at an exposure wavelength of 254 nm in Example 4 of the present invention. [Figure 9A] This is the exposure pattern obtained at an exposure wavelength of 365 nm in Example 4 of the present invention. [Figure 9B] This is the exposure pattern obtained at an exposure wavelength of 365 nm in Example 4 of the present invention. [Figure 10A] This is the exposure pattern obtained at an exposure wavelength of 254 nm in Example 5 of the present invention. [Figure 10B] This is the exposure pattern obtained at an exposure wavelength of 254 nm in Example 5 of the present invention. [Figure 11A] This is the exposure pattern obtained at an exposure wavelength of 365 nm in Example 5 of the present invention. [Figure 11B] This is the exposure pattern obtained at an exposure wavelength of 365 nm in Example 5 of the present invention. [Figure 12A] This is the exposure pattern obtained at an exposure wavelength of 254 nm in Comparative Example 2 of the present invention. [Figure 12B] This is the exposure pattern obtained at an exposure wavelength of 254 nm in Comparative Example 2 of the present invention. [Figure 13A] This is the exposure pattern obtained at an exposure wavelength of 365 nm in Comparative Example 2 of the present invention. [Figure 13B] This is the exposure pattern obtained at an exposure wavelength of 365 nm in Comparative Example 2 of the present invention. [Modes for carrying out the invention]

[0025] One or more embodiments of the present invention are described below with detailed reference. Each embodiment is provided for illustrative purposes only and is not intended to limit the present invention. In fact, it will be apparent to those skilled in the art that various modifications and changes can be made to the present invention without departing from the scope or spirit of the invention. For example, features described or mentioned as part of one embodiment may be used in another embodiment to bring about further embodiments.

[0026] Accordingly, the present invention is intended to encompass such modifications and changes that fall within the appended claims and their equivalent scope. Other subjects, features, and aspects of the present invention are disclosed in or become apparent from the following detailed description. Those skilled in the art should understand that this discussion is merely an illustrative description of exemplary embodiments and is not intended to limit broader aspects of the present invention.

[0027] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. Terms used herein in the description of the present invention are for the sole purpose of describing specific embodiments and are not intended to limit the invention. The term “and / or” as used herein includes any combination of one or more of the items listed relating herein, and all combinations thereof. Where used herein, the terms “include,” “contain,” “have,” “contain,” or other variations thereof are intended to include non-exclusive inclusion. For example, a composition, step, method, article, or apparatus containing the enumerated elements is not limited to those elements and may include other elements not expressly enumerated or inherent to such composition, step, method, article, or apparatus elements.

[0028] In this specification and in the claims, all numbers used to indicate the quantity of components, physicochemical properties, etc., should be understood to be adjusted in all cases by the term "approximately," unless otherwise indicated in the operational examples or otherwise. Therefore, for example, unless otherwise specified, all numerical parameters listed in the above specification and the appended claims are approximations, and those skilled in the art can appropriately modify these approximations to obtain the desired properties using the teachings disclosed herein. Numerical ranges expressed at endpoints include all numbers within that range, as well as any range within that range, for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, etc.

[0029] The "sensitivity" of a photoresist refers to the minimum energy or minimum charge of light incident on a unit area that causes the entire photoresist to react (in the case of electron beam adhesives). In this invention, the unit of sensitivity of ultraviolet resist is mJcm. -2 It is expressed as (the smaller the number, the higher the sensitivity of the photoresist). The unit of sensitivity for electron beam photoresist is μCcm. -2 This can be expressed as follows (the smaller the value, the higher the sensitivity of the photoresist). The sensitivity of the photoresist may also be reflected by the minimum exposure dose, i.e., exposure dose = light intensity × exposure time.

[0030] One aspect of the present invention provides an ultraviolet resist comprising an organic solvent, a photosensitizer, and zirconium oxide nanoclusters. The general formula for zirconium oxide nanoclusters is Zr x O y (OH) z L m In the formula, 2≦x≦20, 2≦y≦40, 0≦z≦40, 4≦m≦40, and L is a carboxyl group-containing organic ligand. The photosensitizer has a structural formula (1), wherein in formula (1), R 1 This is shown in equation (2), where * represents the bonding site, and R 2 and R 3Each instance of -F, -Cl, -Br, or -I is independently selected. <C1> JPEG2026102744000008.jpg34170<2> JPEG2026102744000009.jpg17170

[0031] The photosensitizer in the aforementioned UV resist has high efficiency in generating photodegradable acid. The acid generated by photodegradation can rapidly trigger a chemical reaction in zirconium oxide nanoclusters, resulting in a highly sensitive UV resist and a reduction in exposure dose.

[0032] The UV resist of the present invention uses zirconium oxide nanoclusters as the film-forming resin, resulting in a single scale of only 1 nm to 5 nm, which is far smaller than the size of polymer chains (generally larger than 20 nm). Therefore, compared to conventional polymer resin-type photoresists, the UV resist of the present invention can photoetch patterns with smaller line widths. When the zirconium oxide nanocluster film-forming resin is effectively compatible with the photosensitizer, the sensitivity of the UV resist is greatly improved, the exposure dose is greatly reduced, and the photolithography efficiency is greatly improved. Furthermore, the presence of metal oxides results in excellent mechanical properties and etching resistance of the photoresist, and high pattern fidelity with virtually no deformation or peeling of the exposed pattern during the subsequent development process.

[0033] In some embodiments, R 2 and R 3 All of them are -Cl.

[0034] In some embodiments, the carboxyl group-containing organic ligand includes, but is not limited to, acrylic ligands, methacrylic ligands, 1-hydroxy-2-naphthoic acid ligands, salicylic acid ligands, and the like.

[0035] In some embodiments, the mass percentage of zirconium oxide nanoclusters in the organic solvent may be 0.5% to 15%, or it may be 1%, 1.5%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 14.5%, etc.

[0036] In some embodiments, the mass percentage of the photosensitizer in the organic solvent may be 0.001% to 1%, or it may be 0.002%, 0.003%, 0.005%, 0.006%, 0.008%, 0.01%, 0.02%, 0.05%, 0.08%, 0.1%, 0.12%, 0.15%, 0.3%, 0.5%, 0.8%, etc.

[0037] In some embodiments, by selecting an organic solvent that has good solubility for the photosensitizer and zirconium oxide nanoclusters, the photosensitizer and zirconium oxide nanoclusters are better dissolved and uniformly dispersed in the organic solvent. After spin-coating the UV resist onto a substrate and drying to form a UV resist film, it is possible to ensure that the photosensitizer and zirconium oxide nanoclusters are uniformly dispersed in the UV resist film. After lithography exposure, the exposed areas of the UV resist become difficult to dissolve in the developer, but the unexposed areas of the UV resist can be accurately and rapidly dissolved in the developer. Preferably, the organic solvent may be any one of those commonly used in the art, and includes, but is not limited to, ethyl lactate, anisole, propylene glycol monomethyl ether acetate, methyl isobutyl ketone, and isopropyl alcohol.

[0038] Another aspect of the present invention further provides a method for patterning an ultraviolet resist, the method comprising the steps of: spin-coating the above-mentioned ultraviolet resist onto a substrate and then drying it to form an ultraviolet resist film; and exposing the ultraviolet resist film to ultraviolet lithography using a mask, then developing it in a developer to form a lithography pattern.

[0039] In some embodiments, the developer includes, but is not limited to, toluene, xylene, 1,2-diacetoxypropane, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, isopropyl alcohol, isobutyl alcohol, isoamyl alcohol, 4-methyl-2-pentanol, isopropoxyethanol, 1-methoxy-2-propanol, 1-propoxy-2-propanol, 1-butoxy-2-propanol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, propylene glycol ethyl ether, 2-heptanone, and 2-butanone.

[0040] In some embodiments, the light source for ultraviolet lithography exposure is deep ultraviolet light with a wavelength of 254 nm or ultraviolet light with a wavelength of 365 nm. The exposure dose is 7 mJcm² when the light source for ultraviolet lithography exposure is deep ultraviolet light with a wavelength of 254 nm. -2 The above is true, and when the light source for ultraviolet lithography exposure is ultraviolet light with a wavelength of 365 nm, the required energy is 300 mJcm². -2 That's all.

[0041] In some embodiments, the above ultraviolet resist can also be used as an electron beam photoresist, and when lithography exposure is performed using an electron beam as the light source, the amount of exposure agent is low, 120 μCcm -2 The following is also acceptable.

[0042] In some embodiments, the substrate may be one of the substrate materials commonly used in this field, such as a silicon wafer, a quartz wafer, or a glass wafer.

[0043] In some embodiments, when forming a lithography pattern, it is necessary to block light with a mask in order to form an ultraviolet lithography pattern having a predetermined shape.

[0044] Another aspect of the present invention further provides an ultraviolet resist comprising an organic solvent, a photosensitizer, and zirconium oxide nanoclusters. The general formula for zirconium oxide nanoclusters is Zr x O y (OH) z L m The formula is such that 2≦x≦20, 2≦y≦40, 0≦z≦40, 4≦m≦40, and L is a carboxyl group-containing organic ligand. The photosensitizer has structural formula (1), and in formula (1), R 1 R is an alkyl-substituted or unsubstituted furyl vinyl or benzodioxolane, 2 and R 3 Each instance of -F, -Cl, -Br, or -I is independently selected. <C1> JPEG2026102744000010.jpg34170

[0045] The UV resist of the present invention uses zirconium oxide nanoclusters as the film-forming resin, resulting in a single scale of only 1 nm to 5 nm, which is far smaller than the size of polymer chains (generally larger than 20 nm). Therefore, compared to conventional polymer resin-type photoresists, the UV resist of the present invention can photoetch patterns with smaller line widths. When the zirconium oxide nanocluster film-forming resin is effectively compatible with the photosensitizer, the sensitivity of the UV resist is greatly improved, the exposure dose is greatly reduced, and the photolithography efficiency is greatly improved. Furthermore, the presence of metal oxides results in excellent mechanical properties and etching resistance of the photoresist, and high pattern fidelity with virtually no deformation or peeling of the exposed pattern during the subsequent development process.

[0046] In some embodiments, R 1 is one of the bases selected from the following equations (3), (4), and (5). In the equations, * represents a binding site. <3> JPEG2026102744000011.jpg17170<4> JPEG2026102744000012.jpg20170<5> JPEG2026102744000013.jpg23170

[0047] In some embodiments, R 2 and R 3 All of them are -Cl.

[0048] In some embodiments, the photosensitizer is one or more of 2-(1,3-benzodioxolan-5-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, and 2-[2-(5-methylfuran-2-yl)vinyl)-4,6-bis(trichloromethyl)-1,3,5-triazine.

[0049] In some embodiments, the carboxyl group-containing organic ligands include, but are not limited to, acrylic ligands, methacrylic ligands, 1-hydroxy-2-naphthoic acid ligands, and salicylic acid ligands.

[0050] In some embodiments, the mass percentage of zirconium oxide nanoclusters in the organic solvent may be 0.5% to 15%, or it may be 1%, 1.5%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 14.5%, etc.

[0051] In some embodiments, the mass percentage of the photosensitizer in the organic solvent may be 0.001% to 1%, or it may be 0.002%, 0.003%, 0.005%, 0.006%, 0.008%, 0.01%, 0.02%, 0.05%, 0.08%, 0.1%, 0.12%, 0.15%, 0.3%, 0.5%, 0.8%, etc.

[0052] In some embodiments, by selecting an organic solvent that has good solubility for the photosensitizer and zirconium oxide nanoclusters, the photosensitizer and zirconium oxide nanoclusters are better dissolved and uniformly dispersed in the organic solvent. After spin-coating the UV resist onto a substrate and drying to form a UV resist film, it is possible to ensure that the photosensitizer and zirconium oxide nanoclusters are uniformly dispersed in the UV resist film. After lithography exposure, the exposed areas of the UV resist become difficult to dissolve in the developer, but the unexposed areas of the UV resist can be accurately and rapidly dissolved in the developer. Preferably, the organic solvent may be one or more of those commonly used in the art, and includes, but is not limited to, ethyl lactate, anisole, propylene glycol monomethyl ether acetate, methyl isobutyl ketone, and isopropyl alcohol.

[0053] Another aspect of the present invention further provides a method for patterning an ultraviolet resist, the method comprising the steps of: spin-coating the above-mentioned ultraviolet resist onto a substrate and then drying it to form an ultraviolet resist film; and exposing the ultraviolet resist film to ultraviolet lithography using a mask, then developing it in a developer to form a lithography pattern.

[0054] In some embodiments, the developer includes, but is not limited to, toluene, xylene, 1,2-diacetoxypropane, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, isopropyl alcohol, isobutyl alcohol, isoamyl alcohol, 4-methyl-2-pentanol, isopropoxyethanol, 1-methoxy-2-propanol, 1-propoxy-2-propanol, 1-butoxy-2-propanol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, propylene glycol ethyl ether, 2-heptanone, and 2-butanone.

[0055] In some embodiments, the light source for ultraviolet lithography exposure is deep ultraviolet light with a wavelength of 254 nm or ultraviolet light with a wavelength of 365 nm. The exposure dose is 12 mJcm² when the light source for ultraviolet lithography exposure is deep ultraviolet light with a wavelength of 254 nm. -2 The above is true, and when the light source for ultraviolet lithography exposure is ultraviolet light with a wavelength of 365 nm, the required energy is 200 mJcm². -2 That's fine too.

[0056] In some embodiments, the substrate may be one of the substrate materials commonly used in this field, such as a silicon wafer, a quartz wafer, or a glass wafer.

[0057] In some embodiments, when forming a lithography pattern, it is necessary to block light with a mask in order to form an ultraviolet lithography pattern having a predetermined shape.

[0058] The ultraviolet resist, the patterning method for ultraviolet resist, and the applications of the present invention will be described in more detail below, in accordance with specific examples. (Example 1)

[0059] 0.03 g of 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-S-triazine and 0.75 g of zirconium oxide nanoclusters (Zr6O4(OH)4(CH2=CCH3COO) 12 The UV resist solution was dissolved in 14.25 g of propylene glycol monomethyl ether acetate solvent and stirred until completely dissolved. The UV resist solution was then filtered twice through a filter film with a pore size of 0.22 μm. The filtered UV resist solution was placed in a brown glass bottle and stored in a dark place at room temperature.

[0060] A suitable amount of the prepared UV resist solution is dropped onto the surface of a clean silicon wafer, and the wafer is rotated at 2000 rpm and accelerated at 500 rpms. -1The substrate material was placed in a spin coater and spin-coated for 1 minute. Then, the substrate material was removed and dried in an adhesive dryer at 90°C for 1 minute. Furthermore, the substrate material was placed in an ultraviolet contact lithography apparatus, a mask was positioned, and lithographic exposure was performed using ultraviolet light at wavelengths of 254 nm and 365 nm as light sources. When performing lithographic exposure using ultraviolet light at wavelengths of 254 nm and 365 nm as light sources, the exposure dose was 7 mJcm². -2 and 300 mJcm -2 The development time was 15 seconds in all cases. After UV exposure, the substrate material was removed and developed in 1,2-diacetoxypropane. After development, the developer remaining on the surface of the substrate material was dried with a nitrogen gas gun. Patterns obtained by lithography exposure with light sources at wavelengths of 254 nm and 365 nm were observed with a metallurgical microscope. The results are shown in Figures 1A, 1B, 2A, and 2B. (Example 2)

[0061] 0.01 g of 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-S-triazine and 0.5 g of zirconium oxide nanocluster (Zr6O4(OH)4(CH2=CCH3COO) 12 The electron beam photoresist solution was dissolved in 9.5 g of propylene glycol monomethyl ether acetate solvent and stirred until completely dissolved. The electron beam photoresist solution was then filtered twice through a filter film with a pore size of 0.22 μm. After filtration, the electron beam photoresist solution was placed in a brown glass bottle and stored in a dark place at room temperature.

[0062] An appropriate amount of the prepared electron beam photoresist solution is dropped onto the surface of a clean silicon wafer, and the device is subjected to a rotation speed of 2000 rpm and an acceleration of 500 rpms. -1 The substrate material was placed in a spin coater and spin-coated for 1 minute. Afterward, the substrate material was removed and dried in an adhesive dryer at 90°C for 1 minute. Furthermore, the substrate material was placed in an electron beam lithography apparatus and lithographic exposure was performed using an electron beam as the light source. When performing lithographic exposure using an electron beam as the light source, the exposure dose was 120 μC / cm². -2The development time was 25 seconds. After electron beam exposure, the substrate material was removed and developed in 1,2-diacetoxypropane. After development, the developer remaining on the surface of the substrate material was dried with a nitrogen gas gun. The pattern obtained by electron beam lithography exposure was observed with a high-resolution scanning electron microscope. The results are shown in Figure 3. The resolution of the pattern obtained by this electron beam lithography exposure was 60 nm.

[0063] Thus, the ultraviolet resist according to Example 2 was used in electron beam lithography to obtain a clear exposure pattern. When lithography exposure was performed using an electron beam as the light source, the exposure dose was low, 120 μCcm². -2 The following is also acceptable. (Example 3)

[0064] 0.03g of 2-(1,3-benzodioxolan-5-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine and 0.75g of zirconium oxide nanocluster (Zr6O4(OH)4(CH2=CCH3COO) 12 The UV resist solution was dissolved in 14.25 g of propylene glycol monomethyl ether acetate solvent and stirred until completely dissolved. The UV resist solution was then filtered twice through a 0.22 μm pore size filter film. After filtration, the UV resist solution was placed in a brown glass bottle and stored in a dark place at room temperature.

[0065] A suitable amount of the prepared UV resist solution is dropped onto the surface of a clean silicon wafer, and the wafer is rotated at 2000 rpm and accelerated at 500 rpms. -1 The substrate material was placed in a spin coater and spin-coated for 1 minute. Then, the substrate material was removed and dried in an adhesive dryer at 90°C for 1 minute. Furthermore, the substrate material was placed in an ultraviolet contact lithography apparatus, a mask was positioned, and lithographic exposure was performed using ultraviolet light at wavelengths of 254 nm and 365 nm as light sources. When performing lithographic exposure using ultraviolet light at wavelengths of 254 nm and 365 nm as light sources, the exposure dose was 12 mJcm² each. -2 and 200 mJcm -2The development time was 15 seconds in all cases. After UV exposure, the substrate material was removed and developed in 1,2-diacetoxypropane. After development, the developer remaining on the surface of the substrate material was dried with a nitrogen gas gun. Patterns obtained by lithography exposure with light sources at wavelengths of 254 nm and 365 nm were observed with a metallurgical microscope. The results are shown in Figures 6A, 6B, 7A, and 7B. (Example 4)

[0066] 0.03 g of 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine and 0.75 g of zirconium oxide nanocluster (Zr6O4(OH)4(CH2=CCH3COO) 12 The UV resist solution was dissolved in 14.25 g of propylene glycol monomethyl ether acetate solvent and stirred until completely dissolved. The UV resist solution was then filtered twice through a 0.22 μm pore size filter film. After filtration, the UV resist solution was placed in a brown glass bottle and stored in a dark place at room temperature.

[0067] A suitable amount of the prepared UV resist solution is dropped onto the surface of a clean silicon wafer, and the wafer is rotated at 2000 rpm and accelerated at 500 rpms. -1 The substrate material was placed in a spin coater and spin-coated for 1 minute. Then, the substrate material was removed and dried in an adhesive dryer at 90°C for 1 minute. Furthermore, the substrate material was placed in an ultraviolet contact lithography apparatus, a mask was positioned, and lithographic exposure was performed using ultraviolet light at wavelengths of 254 nm and 365 nm as light sources. When performing lithographic exposure using ultraviolet light at wavelengths of 254 nm and 365 nm as light sources, the exposure dose was 54 mJcm², respectively. -2 and 800 mJcm -2 The development time was 15 seconds in all cases. After UV exposure, the substrate material was removed and developed in 1,2-diacetoxypropane. After development, the developer remaining on the surface of the substrate material was dried with a nitrogen gas gun. The patterns obtained by lithography exposure with light sources at wavelengths of 254 nm and 365 nm were observed with a metallurgical microscope. The results are shown in Figures 8A, 8B, 9A, and 9B. (Example 5)

[0068] 0.03g of 2-[2-(5-methylfuran-2-yl)vinyl)-4,6-bis(trichloromethyl)-1,3,5-triazine and 0.75g of zirconium oxide nanocluster (Zr6O4(OH)4(CH2=CCH3COO) 12 The UV resist solution was dissolved in 14.25 g of propylene glycol monomethyl ether acetate solvent and stirred until completely dissolved. The UV resist solution was then filtered twice through a 0.22 μm pore size filter film. After filtration, the UV resist solution was placed in a brown glass bottle and stored in a dark place at room temperature.

[0069] A suitable amount of the prepared UV resist solution is dropped onto the surface of a clean silicon wafer, and the wafer is rotated at 2000 rpm and accelerated at 500 rpms. -1 The substrate material was placed in a spin coater and spin-coated for 1 minute. Then, the substrate material was removed and dried in an adhesive dryer at 90°C for 1 minute. Furthermore, the substrate material was placed in an ultraviolet contact lithography apparatus, a mask was positioned, and lithographic exposure was performed using ultraviolet light at wavelengths of 254 nm and 365 nm as light sources. When performing lithographic exposure using ultraviolet light at wavelengths of 254 nm and 365 nm as light sources, the exposure dose was 72 mJcm², respectively. -2 and 3600 mJcm -2 The development time was 15 seconds in all cases. After UV exposure, the substrate material was removed and developed in 1,2-diacetoxypropane. After development, the developer remaining on the surface of the substrate material was dried with a nitrogen gas gun. The patterns obtained by lithography exposure with light sources at wavelengths of 254 nm and 365 nm were observed with a metallurgical microscope. The results are shown in Figures 10A, 10B, 11A, and 11B. (Comparative Example 1)

[0070] Comparative Example 1 is almost the same as the preparation method of Example 1, but differs in that the photosensitizer is 2-(4-methoxystyrene)-4,6-bis(trichloromethyl)-1,3,5-triazine and in the exposure dose. The specific steps are as follows: 0.03 g of 2-(4-methoxystyrene)-4,6-bis(trichloromethyl)-1,3,5-triazine and 0.75 g of zirconium oxide nanocluster (Zr6O4(OH)4(CH2=CCH3COO) 12 The UV resist solution was dissolved in 14.25 g of propylene glycol monomethyl ether acetate solvent and stirred until completely dissolved. The UV resist solution was then filtered twice through a 0.22 μm pore size filter film. After filtration, the UV resist solution was placed in a brown glass bottle and stored in a dark place at room temperature.

[0071] A suitable amount of the prepared UV resist solution is dropped onto the surface of a clean silicon wafer, and the wafer is rotated at 2000 rpm and accelerated at 500 rpms. -1 The substrate material was placed in a spin coater and spin-coated for 1 minute. Then, the substrate material was removed and dried in an adhesive dryer at 90°C for 1 minute. Furthermore, the substrate material was placed in an ultraviolet contact lithography apparatus, a mask was positioned, and lithographic exposure was performed using ultraviolet light at wavelengths of 254 nm and 365 nm as light sources. When performing lithographic exposure using ultraviolet light at wavelengths of 254 nm and 365 nm as light sources, the exposure dose was 18 mJcm², respectively. -2 and 400 mJcm -2 The development time was 15 seconds in all cases. After UV exposure, the substrate material was removed and developed in 1,2-diacetoxypropane. After development, the developer remaining on the surface of the substrate material was dried with a nitrogen gas gun. The patterns obtained by lithography exposure with light sources at wavelengths of 254 nm and 365 nm were observed with a metallurgical microscope. The results are shown in Figures 4A, 4B, 5A, and 5B.

[0072] The following was confirmed from Example 1 and Comparative Example 1 described above. Under conditions where the exposure light source was ultraviolet light with wavelengths of 254 nm and 365 nm, in Example 1, when 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-S-triazine was selected as the photosensitizer and reacted with zirconium oxide nanoclusters, the exposure dose was 7 mJ cm in each case. -2 and 300 mJcm -2 In contrast, in the comparative example, when 2-(4-methoxystyrene)-4,6-bis(trichloromethyl)-1,3,5-triazine was selected as the photosensitizer and reacted with zirconium oxide nanoclusters, the exposure dose was 18 mJcm² in each case. -2 and 400 mJcm -2 As a result, compared to Comparative Example 1, the photosensitizing effect when 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-S-triazine of Example 1 was reacted with zirconium oxide nanoclusters as a photosensitizer was superior, and the exposure dose was reduced by 61% and 25%, respectively. Example 1 can increase the lithography speed by significantly reducing the amount of UV exposure of the photoresist. (Comparative Example 2)

[0073] 0.03 g of N-hydroxynaphthalimide triflate and 0.75 g of zirconium oxide nanocluster (Zr6O4(OH)4(CH2=CCH3COO) 12 The UV resist solution was dissolved in 14.25 g of propylene glycol monomethyl ether acetate solvent and stirred until completely dissolved. The UV resist solution was then filtered twice through a 0.22 μm pore size filter film. After filtration, the UV resist solution was placed in a brown glass bottle and stored in a dark place at room temperature.

[0074] A suitable amount of the prepared UV resist solution is dropped onto the surface of a clean silicon wafer, and the wafer is rotated at 2000 rpm and accelerated at 500 rpms. -1The substrate material was placed in a spin coater and spin-coated for 1 minute. Then, the substrate material was removed and dried in an adhesive dryer at 90°C for 1 minute. Furthermore, the substrate material was placed in an ultraviolet contact lithography apparatus, a mask was positioned, and lithographic exposure was performed using ultraviolet light at wavelengths of 254 nm and 365 nm as light sources. When performing lithographic exposure using ultraviolet light at wavelengths of 254 nm and 365 nm as light sources, the exposure dose was 144 mJcm², respectively. -2 and 6000 mJcm -2 The development time was 15 seconds in all cases. After UV exposure, the substrate material was removed and developed in 1,2-diacetoxypropane. After development, the developer remaining on the surface of the substrate material was dried with a nitrogen gas gun. Patterns obtained by lithography exposure with light sources at wavelengths of 254 nm and 365 nm were observed with a metallurgical microscope. The results are shown in Figures 12A, 12B, 13A, and 13B.

[0075] The following was confirmed by Examples 3 to 5 and Comparative Example 2 described above. Under conditions where the exposure light source was ultraviolet light with wavelengths of 254 nm and 365 nm, in Examples 3 to 5, when 2-(1,3-benzodioxolan-5-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, and 2-[2-(5-methylfuran-2-yl)vinyl)-4,6-bis(trichloromethyl)-1,3,5-triazine were selected as photosensitizers and reacted with zirconium oxide nanoclusters, the exposure dose was 12 mJ cm for each example. -2 and 200 mJcm -2 , 54 mJcm -2 and 800 mJcm -2 72 mJcm -2 and 3600 mJcm -2 In contrast, in Comparative Example 2, when a photosensitizer other than those limited in the present invention was selected and reacted with zirconium oxide nanoclusters, the exposure dose was 144 mJcm² in each case. -2 and 6000 mJcm -2As a result, the ultraviolet resist according to the embodiment of the present invention can react with zirconium oxide nanoclusters and a limited photosensitizer during exposure, significantly reducing the amount of ultraviolet exposure dose to the photoresist and increasing the lithography speed.

[0076] Each of the technical features of the above embodiments can be combined in any way, and for the sake of brevity, not all possible combinations of the technical features of the above embodiments are described. However, as long as these combinations of technical features do not result in inconsistencies, they should be considered to fall within the scope described herein.

[0077] The above examples illustrate only a few embodiments of the present invention, and while the description is more specific and detailed, this should not be understood as limiting the scope of the claims. Those skilled in the art should note that some modifications and improvements can be made without departing from the concept of the present invention, and these will fall within the scope of protection of the present invention. Therefore, the scope of protection of the patent for the present invention should be determined by the appended claims.

Claims

1. An ultraviolet resist, comprising an organic solvent, a photosensitizer, and zirconium oxide nanoclusters, The general formula for the zirconium oxide nanocluster is Zr ｘ O ｙ (OH) ｚ L ｍ In the formula, 2 ≤ x ≤ 20, 2 ≤ y ≤ 40, 0 ≤ z ≤ 40, 4 ≤ m ≤ 40, and L is a carboxyl group-containing organic ligand. The photosensitizer has a structural formula (1), wherein R １ is one of equations (3), (4), or (5), and * represents the bonding site, R ２ and R ３ A UV resist characterized in that each instance is independently selected from -F, -Cl, -Br, or -I. <Chemical Formula 1> <Chemical Formula 3> <Chemical Formula 4> <Chemical Formula 5>

2. The aforementioned R ２ and R ３ are both —Cl, and the ultraviolet resist according to claim 1, characterized in that

3. The ultraviolet resist according to claim 1, wherein the carboxyl group-containing organic ligand contains at least one of an acrylic ligand, a methacrylic ligand, a 1-hydroxy-2-naphthoic acid ligand, and a salicylic acid ligand.

4. The ultraviolet resist according to claim 1, wherein the mass percentage of the photosensitizer in the organic solvent is 0.001% to 1%.

5. The ultraviolet resist according to claim 1, wherein the mass percentage of the zirconium oxide nanoclusters in the organic solvent is 0.5% to 15%.

6. The ultraviolet resist according to claim 1, wherein the organic solvent contains at least one of ethyl lactate, anisole, propylene glycol monomethyl ether acetate, methyl isobutyl ketone, and isopropyl alcohol.

7. A method for patterning an ultraviolet resist, comprising the steps of spin-coating the ultraviolet resist according to any one of claims 1 to 6 on a substrate and then drying to form an ultraviolet resist film, and exposing the ultraviolet resist film to ultraviolet lithography through a mask and then developing it in a developer to form a lithography pattern.

8. The method for patterning an ultraviolet resist according to claim 7, wherein the developer contains at least one of toluene, xylene, 1,2-diacetoxypropane, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, isopropyl alcohol, isobutyl alcohol, isoamyl alcohol, 4-methyl-2-pentanol, isopropoxyethanol, 1-methoxy-2-propanol, 1-propoxy-2-propanol, 1-butoxy-2-propanol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol butyl ether, propylene glycol ethyl ether, 2-heptanone, and 2-butanone.

9. The method for patterning an ultraviolet resist according to claim 7, characterized in that the light source for the ultraviolet lithography exposure is ultraviolet light with a wavelength of 365 nm, deep ultraviolet light with a wavelength of 254 nm, or extreme ultraviolet light with a wavelength of 13.5 nm.

10. The exposure dose is 12 mJcm² when the light source for UV lithography exposure is deep ultraviolet light with a wavelength of 254 nm. －２ The above is true, and when the light source for ultraviolet lithography exposure is ultraviolet light with a wavelength of 365 nm, the required energy is 200 mJcm². －２ The method for patterning ultraviolet resist according to claim 7, characterized in that it is as described above.

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