An organic compound, a photoresist containing the same, and applications thereof

Abstract

The present application provides an organic compound, a photoresist containing the same and applications thereof, the organic compound has a structure as shown in formula I, through the design of molecular structure, it has the function of antioxidant, can effectively improve the etching performance of photoresist in dry etching as a photoetching aid. The photoresist containing the same has excellent etching performance and developing property, especially has excellent etching selectivity, can prevent the appearance of photoresist edge line from excessive etching, the slope is large, the line width is small and other abnormal morphology, can effectively reduce and avoid the problem of etching residue and subsequent stripping difficulty, significantly optimizes the etching morphology, can fully meet the processing demand of high precision, fine pattern / line.

Description

Technical Field

[0001] This invention belongs to the field of photoresist material technology, specifically relating to an organic compound, a photoresist containing the same, and their applications. Background Technology

[0002] Photoresist, also known as photoresist, can create micron- or nanometer-scale images through exposure imaging technology. It is used in the processing of substrates such as semiconductor chips, control circuits for LCD panels, and printed circuit boards. Photoresists are generally divided into positive and negative photoresists. With positive photoresist, the exposed areas are washed away by the developer after exposure, leaving the unexposed areas on the substrate, thus forming a relief pattern identical to that on the photomask. With negative photoresist, the unexposed areas are washed away by the developer, forming a relief pattern that is completely reversed from that on the photomask.

[0003] Traditional g-line, i-line, and full-band ghi-line positive photoresists typically employ a combination of alkali-soluble resin and diazo photosensitive agent. The alkali-soluble resin is soluble under strong alkali conditions. When the resin combines with the photosensitive agent, the alkali-soluble groups of the resin are protected by diazonaphthoquinone, rendering the resin insoluble. In this case, the photosensitive agent acts as a dissolution inhibitor. After exposure, the diazonaphthoquinone groups decompose to produce carboxylic acid, making the resin soluble again. The presence of carboxylic acid significantly increases the solubility of the resin composition in the developer, at which point the photosensitive agent acts as a dissolution enhancer. Utilizing the difference in development speed between exposed and unexposed areas, positive photoresist is coated onto glass or silicon wafers to form a film. Through mask exposure and development, the desired micron or nanometer patterns can be obtained.

[0004] In TFT panel manufacturing and semiconductor processes, positive photoresists are used for patterning semiconductor, metal, and inorganic layers, and as a key material, they determine the yield of the process. With the continuous improvement of circuit precision, the etching performance requirements of photoresists are becoming increasingly stringent, especially in plasma dry etching processes, where photoresists are required to possess excellent etching selectivity, low etching residue, and good etching morphology. However, existing photoresists still have significant shortcomings in etching performance, making it difficult to meet the process requirements of high-precision circuits. Therefore, developing photoresist materials that can improve etching selectivity, reduce etching residue, and improve etching morphology is an urgent problem to be solved in this field. Summary of the Invention

[0005] To address the shortcomings of existing technologies, the present invention aims to provide an organic compound, a photoresist containing the same, and their applications. Through the design of the molecular structure, the organic compound can be used as a photolithography aid to effectively improve the etching performance of the photoresist in dry etching, enabling the photoresist containing the same to have an excellent etching selectivity, reduce etching residue, avoid the problem of subsequent stripping difficulties, and significantly improve the etching morphology.

[0006] To achieve this objective, the present invention adopts the following technical solution:

[0007] In a first aspect, the present invention provides an organic compound having a structure as shown in Formula I:

[0008]

[0009] In Formula I, Y1 and Y2 are each independently selected from any one of the following: single bond, C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, etc.) straight-chain or branched alkylene group, C2-C10 (e.g., C3, C4, C5, C6, C7, C8, C9, etc.) straight-chain or branched alkyne group, C2-C10 (e.g., C3, C4, C5, C6, C7, C8, C9, etc.) straight-chain or branched alkyne group, and C6-C30 (e.g., C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C25, C26, C28, etc.) arylene group.

[0010] In Formula I, R1, R2, and R3 are each independently selected from hydrogen, substituted or unsubstituted tert-butyl, and hydroxyl groups.

[0011] In Formula I, R4, R5, and R6 are each independently selected from any one of the following: hydrogen, substituted or unsubstituted C1-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, etc.) straight-chain or branched alkyl, substituted or unsubstituted C2-C10 (e.g., C3, C4, C5, C6, C7, C8, C9, etc.) alkenyl, substituted or unsubstituted C2-C10 (e.g., C3, C4, C5, C6, C7, C8, C9, etc.) alkynyl, and substituted or unsubstituted C6-C30 (e.g., C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C25, C26, C28, etc.) aryl.

[0012] The substituents in R1, R2, R3, R4, R5, and R6 are each independently selected from at least one of halogens, C1-C10 straight-chain or branched alkyl groups, and C6-C30 aryl groups.

[0013] In this invention, the "substituted or unsubstituted" group can replace one substituent or multiple substituents. When there are multiple substituents (at least two), they can be the same or different substituents; the same expression used below has the same meaning. Unless otherwise specified, the selection range of substituents is as shown above and will not be repeated.

[0014] The present invention provides an organic compound having a structure shown in Formula I, which has the function of an antioxidant through the design of its molecular structure. Specifically, in the structure of the organic compound, there is one or two tert-butyl groups at the ortho position of the phenolic hydroxyl group. Such antioxidants capture free radicals to convert peroxy free radicals into hydroperoxides, and the generated phenoxy free radicals contain tert-butyl groups. Due to steric hindrance effects, their reaction activity is low, which can prevent the formation of new oxidation cycles. When the organic compound is applied to a photoresist, it can significantly improve the etching performance of the photoresist in dry etching, especially enhance the etching resistance to oxygen-containing plasma, enabling the photoresist and the etched layer to have excellent etching selectivity, and preventing abnormal morphologies such as excessive slopes and reduced line widths at the edges of the photoresist caused by over-etching. At the same time, the organic compound can prevent the phenomenon that the carbonization deposition caused by excessive oxidation of organic matter during the etching process is difficult to strip and remove. Especially for deep hole etching, it can effectively avoid the problems of etching residues and subsequent stripping difficulties, thereby significantly improving the etching performance and meeting the processing requirements of high-precision and fine patterns / circuits.

[0015] It should be noted that in the present invention, for the convenience of description, the possible functions of each group / feature are described separately, but this does not mean that these groups / features act independently. In fact, the essential reason for obtaining good performance is the optimized combination of the entire molecular structure, which is the result of the synergistic effect between each group, rather than the effect of a single group / feature.

[0016] The following are the preferred technical solutions of the present invention, but they do not limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the objectives and beneficial effects of the present invention can be better achieved.

[0017] In the present invention, for the description of chemical elements, unless otherwise specified, the concept of isotopes with the same chemical properties is included. For example, hydrogen (H) includes 13 H (protium), 2 H (deuterium, D), 3 H (tritium, T), etc.; carbon (C) includes 12 C, 13 C, etc.

[0018] In the present invention, the expression "Ca-Cb" represents that the group has a carbon atom number of a - b; generally, unless otherwise specified, the carbon atom number does not include the carbon atom number of substituents.

[0019] In the present invention, "each independently" means that when its subject has multiple, they can be the same or different from each other.

[0020] In the present invention, "-*" and "*" both represent the connection sites of groups.

[0021] In this invention, the C1-C10 straight-chain or branched alkyl groups can be straight-chain or branched alkyl groups of C1, C2, C3, C4, C5, C6, C7, C8, C9, and C10, and exemplary include but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 2-methylbutyl, n-pentyl, isopentyl, neopentyl, n-hexyl, neohexyl, 2-ethylhexyl, n-octyl, n-heptyl, n-nonyl, n-decyl, etc.

[0022] The C1-C10 straight-chain or branched alkylene groups can be straight-chain or branched alkylene groups of C1, C2, C3, C4, C5, C6, C7, C8, C9, and C10. A specific example is a divalent group formed by losing one hydrogen atom from the aforementioned straight-chain or branched alkyl group.

[0023] In this invention, the C2-C10 alkenyl groups can all be straight-chain or branched alkenyl groups of C2, C3, C4, C5, C6, C7, C8, C9, and C10, containing at least one C=C, and exemplary including but not limited to: vinyl, propenyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, butadienyl, pentadienyl, etc.

[0024] The C2-C10 straight-chain or branched alkenyl groups can be straight-chain or branched alkenyl groups of C2, C3, C4, C5, C6, C7, C8, C9, and C10, containing at least one C=C. A specific example is a divalent group obtained by losing a hydrogen atom from the aforementioned straight-chain or branched alkenyl group.

[0025] In this invention, the C2-C10 alkynyl groups can all be straight-chain or branched alkynyl groups of C2, C3, C4, C5, C6, C7, C8, C9, and C10, containing at least one C≡C, including but not limited to: ethynyl, propynyl, propynyl, butynyl, pentynyl, hexynyl, hepynyl, octyynyl, nonynyl, decynyl, etc.

[0026] The C2-C10 straight-chain or branched alkyne groups can be straight-chain or branched alkyne groups of C2, C3, C4, C5, C6, C7, C8, C9, and C10, containing at least one C≡C. A specific example is a divalent group obtained by losing a hydrogen atom from the aforementioned straight-chain or branched alkyne group.

[0027] In this invention, the C6-C30 aryl groups can all be aryl groups of C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, etc., including monocyclic aryl and fused-ring aryl groups, and exemplary including but not limited to: phenyl, biphenyl, terphenyl, tetraphenyl, naphthyl, anthracene, phenanthryl, indene, fluorenyl and its derivatives (9,9-dimethylfluorenyl, 9,9-diethylfluorenyl, 9,9-dipropylfluorenyl, 9,9-dibutylfluorenyl, 9,9-dipentylfluorenyl, 9,9-dihexylfluorenyl, 9,9-diphenylfluorenyl, 9,9-dinaphthylfluorenyl, spirodifluorenyl, benzo[fluorenyl], etc.), fluoranyl, triphenylene, pyrene, perylene, etc. It should be noted that monocyclic aryl and fused-ring aryl groups linked by single bonds also fall under the category of aryl groups, such as phenylnaphthyl, naphthylphenyl, and binaphthyl.

[0028] The C6-C30 arylene groups can all be arylene groups of C6, C9, C10, C12, C14, C16, C18, C20, C22, C24, C26, C28, etc., including monocyclic arylene groups and fused-ring arylene groups. A specific example is a divalent group obtained by losing a hydrogen atom from the aforementioned aryl group.

[0029] In this invention, the halogen can be fluorine, chlorine, bromine, or iodine. The same descriptions used below have the same meaning.

[0030] In Formula I, Y1 and Y2 are each independently selected from any one of the following: single bond, C1-C10 straight-chain or branched alkylene group, C2-C10 straight-chain or branched alkenylene group, C2-C10 straight-chain or branched alkyneylene group, and C6-C30 arylene group; when Y1 is a single bond, it means that the benzene ring containing R6 is directly connected to Y2 through a single bond; when Y2 is a single bond, it means that the quaternary carbon is directly connected to Y1 through a single bond; when both Y1 and Y2 are single bonds, it means that the benzene ring containing R6 is directly connected to the quaternary carbon through a single bond.

[0031] Preferably, Y1 and Y2 are each independently selected from any one of a single bond, a C2-C8 straight-chain or branched alkylene group, a C2-C8 straight-chain or branched alkenyl group, or a C6-C12 arylene group; more preferably, a single bond, a C2-C6 straight-chain or branched alkylene group, a C2-C6 straight-chain or branched alkenyl group, or a phenylene group; further preferably, a single bond or any one of the following groups:

[0032]

[0033] Here, -* represents the linking site of a group.

[0034] More preferably, Y1 and Y2 are each independently selected from single bonds,

[0035] Preferably, R1, R2, and R3 are each independently selected from hydrogen, substituted or unsubstituted tert-butyl, and hydroxyl groups.

[0036] Preferably, the substituents in R1, R2, and R3 are each independently selected from at least one of halogens, C1-C8 straight-chain or branched alkyl groups, and phenyl groups.

[0037] More preferably, R1, R2, and R3 are each independently selected from hydrogen, tert-butyl, or hydroxyl.

[0038] Preferably, R1, R2, and R3 are the same group.

[0039] Preferably, R4, R5, and R6 are each independently selected from any one of hydrogen, substituted or unsubstituted C1-C8 straight-chain or branched alkyl groups, substituted or unsubstituted C2-C8 alkenyl groups, and substituted or unsubstituted C6-C12 aryl groups.

[0040] Preferably, the substituents in R4, R5, and R6 are each independently selected from at least one of halogens, C1-C8 straight-chain or branched alkyl groups, and phenyl groups.

[0041] Preferably, R4, R5, and R6 are each independently selected from hydrogen, C1-C5 straight-chain or branched alkyl groups.

[0042] Preferably, R4, R5, and R6 are the same group.

[0043] Preferably, the organic compound has the structure shown in any one of the following:

[0044]

[0045]

[0046] In a second aspect, the present invention provides a photoresist comprising the organic compound described in the first aspect.

[0047] The photoresist provided by this invention introduces an organic compound with the structure shown in Formula I. As a photolithography aid, it can effectively improve the photoresist's resistance to plasma etching, giving the photoresist excellent etching performance and developability, higher etching selectivity, and preventing abnormal morphology such as excessive slope and small line width caused by excessive etching of the photoresist edges. At the same time, it effectively prevents stripping residue after etching, significantly optimizes the etching morphology, and can fully meet the processing requirements of high-precision and fine-grained patterns / circuits.

[0048] The photoresist of this invention is a positive photoresist.

[0049] Preferably, the photoresist comprises a combination of an alkali-soluble resin, a photosensitizer, a crosslinking agent, and the organic compound.

[0050] Preferably, the alkali-soluble resin includes phenolic resin, and more preferably linear phenolic resin.

[0051] Preferably, the weight-average molecular weight of the phenolic resin is 2000-30000, for example, it can be 3000, 4000, 5000, 6000, 8000, 10000, 12000, 15000, 18000, 20000, 22000, 25000 or 28000, as well as specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0052] In this invention, the phenolic resin is polymerized from phenolic compounds and aldehyde compounds.

[0053] Preferably, the phenolic compound includes any one or a combination of at least two of the following: phenol, cresol, xylenol, ethylphenol, propylphenol, butylphenol, tert-butylphenol, di-tert-butylphenol, octylphenol, fluorophenol, chlorophenol, bromophenol, iodophenol, naphthol, anthraquinone, dihydroxybenzene, dihydroxynaphthalene, biphenol, bisphenol, aminophenol, nitrophenol, and phloroglucinol.

[0054] Preferably, the aldehyde compounds include any one or a combination of at least two of formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, hexanal, trichloroacetaldehyde, furfural, glyoxal, allylaldehyde, benzaldehyde, crotonaldehyde, o-tolualdehyde, and salicylaldehyde.

[0055] More preferably, the phenolic resin includes any one or a combination of at least two of the following: linear phenolic resin polymerized from cresol and formaldehyde; linear phenolic resin polymerized from xylenol and formaldehyde; linear phenolic resin polymerized from di-tert-butylphenol and formaldehyde; linear phenolic resin polymerized from dihydroxynaphthalene and formaldehyde; linear phenolic resin polymerized from phloroglucinol and formaldehyde; and linear phenolic resin polymerized from xylenol, formaldehyde, and salicylaldehyde.

[0056] Preferably, the photosensitizer is a compound containing a diazonoquinone group.

[0057] Preferably, the structure of the diazonoquinone group is as follows: -* represents the linking site of a functional group.

[0058] As a preferred embodiment of the present invention, the photosensitizer contains a diazononaphthoquinone group and is a diazononaphthoquinone-type photosensitizer, including but not limited to: any one or a combination of at least two of the following: disubstituted ester compounds of diazononaphthoquinone sulfonyl halides (e.g., diazononaphthoquinone sulfonyl chloride) and trihydroxybenzophenone; and trisubstituted ester compounds of diazononaphthoquinone sulfonyl halides (e.g., diazononaphthoquinone sulfonyl chloride) and tetrahydroxybenzophenone.

[0059] Preferably, the crosslinking agent comprises any one or a combination of at least two of amine crosslinking agents, epoxy crosslinking agents, ether crosslinking agents, and urea crosslinking agents. More preferably, it comprises any one or a combination of at least two of hexamethylenetetramine, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 1,4-butanediol diglycidyl ether, hexamethylenemethyl melamine, hexamethylene melamine, tris(alkoxycarbonylamino)triazine, and 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidineone.

[0060] Preferably, the photoresist further includes a solvent and / or additives.

[0061] Preferably, the solvent is a solvent commonly used in the art, including but not limited to: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol butyl methyl ether, diethylene glycol butyl ethyl ether, diethylene glycol diethyl ether ethyl acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol butyl methyl ether, dipropylene glycol ethylhexyl ether, triethylene glycol dimethyl ether, triethylene glycol tert-butyl ether, chloroform, xylene, ethyl lactate, γ-butyrolactone, N-methylpyrrolidone, benzyl alcohol, dimethyl ether, etc. The following are any one or a combination of at least two of the following: methyl sulfoxide, diethyl carbonate, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, methyl cyclohexyl acetate, n-nonyl acetate, methyl acetoacetate, ethyl acetoacetate, methyl lactate, n-butyl lactate, n-pentyl lactate, diethyl malonate, dimethyl phthalate, diethyl phthalate, 1,3-propanesulfonyl lactone, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-pentane, isopentane, n-hexane, isohexane, and n-heptane.

[0062] Preferably, the additives include any one or a combination of at least two of the following: coupling agents, surfactants, defoamers, photoacid generators, thermal acid generators, and ultraviolet absorbers.

[0063] Preferably, the coupling agent includes a silane coupling agent and / or a titanate coupling agent, which can improve the adhesion between the photoresist cured film and the substrate.

[0064] Preferably, the silane coupling agent is a coupling agent well known to those skilled in the art, and exemplary includes, but is not limited to, any one or a combination of at least two of the following: trimethoxysilylbenzoic acid, vinyltrimethoxysilane, vinyltriacetoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-isocyanate propyltriethoxysilane, γ-glycidylpropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-ureidopropyltriethoxysilane, (3-epoxypropoxypropyl)triethoxysilane, N-(3-(trimethylsilyl)propyl)aniline, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, tridecafluorooctyltrimethoxysilane, and n-octyltrimethoxysilane. Alternatively, different types of silane coupling agents can be mixed to improve the adaptability of the photoresist cured film to different types of substrates and achieve good adhesion strength on different types of substrates.

[0065] Preferably, the surfactant includes any one or a combination of at least two of polyethylene glycol surfactants, fluorinated surfactants, and polyether-modified siloxane surfactants.

[0066] For example, the surfactant includes any one or a combination of at least two of polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oil ether, F55, and F559.

[0067] Preferably, the defoamer includes any one or a combination of at least two of the following: silicone defoamer, polyether defoamer, and polyether-modified polysiloxane defoamer.

[0068] Preferably, the photoacid-generating agent includes any one or a combination of at least two of thionium salts, iodonium salts, and diazonium salts.

[0069] For example, the photoacid-generating agent includes any one or a combination of at least two of the following: diazonium sulfate, diazonium hydrochloride, diazonium sulfonate, diazonium fluoroborate, diazonium fluorophosphate, diazonium fluoroantimonate, diazonium perchlorate, triphenylthionium hexafluoroantimonate, triphenylthionium trifluoromethanesulfonic acid, bis(p-toluenesulfonyl)diazomethane, di(cycloethylsulfonyl)diazomethane, and xylyliodonium trifluoromethanesulfonic acid.

[0070] Preferably, the thermal acid-producing agent is a compound that produces a strong acid, such as p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, etc., and particularly preferably an acid-producing agent whose thermal decomposition temperature is between 90-250°C. It can be used in the form of a salt (such as an ammonium salt or a thioonium salt) or in the form of an imide sulfonate ester or other chemical bond.

[0071] Preferably, the ultraviolet absorber is well known to those skilled in the art, and includes, but is not limited to, any one or a combination of at least two of the following: 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, phenyl phthalate, 2,4-dihydroxybenzophenone, and 4-benzoyloxy-2,2,6,6-tetramethylpiperidine.

[0072] As a preferred embodiment of the present invention, the photoresist comprises the following components by weight percentage:

[0073]

[0074] Preferably, the mass percentage of alkali-soluble resin in the photoresist is 8-15%, for example, it can be 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5% or 14%, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0075] Preferably, the photosensitive agent in the photoresist has a mass percentage content of 1-5%, for example, it can be 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0076] Preferably, the mass percentage of the crosslinking agent in the photoresist is 0.1-2%, for example, it can be 0.2%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0077] Preferably, the mass percentage of the organic compound in the photoresist is 0.2-3%, for example, it can be 0.4%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.2%, 2.5%, 2.8%, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range, but 0.3-3% is further preferred.

[0078] Preferably, the mass percentage of the additive in the photoresist is 0.1-2%, for example, it can be 0.2%, 0.5%, 0.8%, 1%, 1.2%, 1.5%, 1.8%, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range, and 0.25-2% is further preferred.

[0079] Preferably, the solvent content in the photoresist is 80-90% by mass, for example, it can be 81%, 82%, 83%, 84%, 85%, 86%, 87%, 88% or 89%, and specific values ​​between the above values. Due to space limitations and for the sake of brevity, the present invention will not exhaustively list the specific values ​​included in the range.

[0080] Preferably, the mass percentage of each of the coupling agent, surfactant, defoamer, photoacid generator, thermal acid generator, and ultraviolet absorber in the photoresist is independently 0.0005-1%, for example, 0.0008%, 0.001%, 0.003%, 0.005%, 0.008%, 0.01%, 0.02%, 0.05%, 0.08%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, or 0.9%, and specific values ​​between the above values ​​are not exhaustively listed here for space limitations and for the sake of brevity.

[0081] Thirdly, the present invention provides the application of the organic compound as described in the first aspect and the photoresist as described in the second aspect in a display panel or semiconductor chip.

[0082] Preferably, the photoresist can be coated, pre-baked, exposed, developed, and post-baked to form a cured film that remains in the display panel or semiconductor chip.

[0083] Compared with the prior art, the present invention has the following beneficial effects:

[0084] The organic compound provided by this invention has the structure shown in Formula I. Through molecular structure design, it possesses antioxidant properties and can be used as a photolithography additive to effectively improve the etching performance of photoresist in dry etching. Photoresist containing this compound exhibits excellent etching performance and developability, especially excellent etching selectivity. It can prevent morphological abnormalities such as excessive slope and insufficient linewidth caused by over-etching of photoresist edges, effectively reduce and avoid etching residue and subsequent stripping difficulties, significantly optimize the etching morphology, and fully meet the processing requirements of high-precision, fine-grained patterns / circuits. Attached Figure Description

[0085] Figure 1 This is a pattern morphology diagram of the photoresist provided in Example 1 before etching;

[0086] Figure 2 The image shows the morphological features of the photoresist provided in Example 1 after etching. Detailed Implementation

[0087] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0088] The organic compounds represented by Formula I of this invention can be synthesized using organic synthesis methods known in the art. Exemplary synthetic routes are given below, but those skilled in the art can also obtain them using other known methods.

[0089] In one specific embodiment, Y1 and Y2 are single bonds, and the organic compound is prepared via the following representative synthetic route:

[0090]

[0091] In this formula, R1, R2, R3, R4, R5, and R6 have the same definitions as in Formula I; Hal1, Hal2, and Hal3 are each independently selected from halogens, such as any one of F, I, Br, or Cl, preferably Br or Cl. Reaction I is carried out in the presence of tert-butyllithium and dimethyl carbonate. Reaction II is carried out in the presence of HBF4 and organolithium (e.g., methyllithium). Reaction III is carried out in the presence of BBr3.

[0092] It should be noted that obtaining the organic compounds is not limited to the synthetic methods and raw materials used in this invention. Those skilled in the art can also select other methods or routes to obtain the organic compounds proposed in this invention. Compounds synthesized using methods not mentioned in this invention are all raw material products obtained through commercial means, or prepared in-house using these raw material products according to known methods.

[0093] The specific preparation methods of the organic compounds described in this invention will be detailed below using several synthetic examples, but the preparation methods of this invention are not limited to these synthetic examples.

[0094] In the following synthesis examples of this invention, the mass spectrometry data (m / z) of the intermediate and the target product were obtained using an Agilent Qtof G6530 mass spectrometer.

[0095] Synthesis Example 1: Synthesis of Organic Compound A

[0096]

[0097] (1) Synthesis of intermediate 2

[0098] Under nitrogen protection, monomer 1 (2.43 g, 0.01 mol, CAS: 14804-34-3) was dissolved in 100 mL of anhydrous tetrahydrofuran (THF) and cooled to -78 °C. A tert-butyllithium solution (1.7 M, 12 mL, 0.02 mol) was added dropwise to the solution using a syringe, and stirring was continued for 80 min. A dimethyl carbonate solution (0.3 mL, 3.33 mmol dissolved in 10 mL of THF) was added to the solution using a syringe, and the mixture was allowed to return to room temperature naturally and stirred for 40 h. The reaction mixture was quenched by adding 10 mL of water, extracted with ethyl acetate, and purified by column chromatography to obtain 1.52 g of product. Mass spectrometry results: m / z value (M+Na): 541.34.

[0099] (2) Synthesis of intermediate 3

[0100] Under nitrogen protection, intermediate 2 (1.04 g, 2 mmol) was dissolved in 30 mL of acetic anhydride. While stirring, 6 mL of 49% HBF4 solution was added dropwise to the solution using a syringe. Stirring continued for 15 min, followed by high-vacuum drying for 3 h to obtain the crude product. The crude product was dissolved in 40 mL of anhydrous tetrahydrofuran and cooled to -78 °C. A 13 mL solution of methyl lithium (1.4 M, 18.4 mmol) was added dropwise to the solution using a syringe. The mixture was allowed to return to room temperature naturally and stirred for 20 h. The reaction solution was quenched with water, extracted with ethyl acetate, and purified by column chromatography to obtain 0.48 g of the product. Mass spectrometry results: m / z value (M+Na): 539.35.

[0101] (3) Synthesis of organic compound A:

[0102] Under nitrogen protection, intermediate 3 (258 mg, 0.5 mmol) was dissolved in 20 mL of dichloromethane and cooled to -78 °C. BBr3 (0.7 mL, 7.5 mmol) was added dropwise to the solution using a syringe, and the mixture was allowed to return to room temperature naturally and stirred for 20 h. The reaction solution was quenched with a saturated ammonium chloride solution at ice-cold temperature. Extraction with ethyl acetate and purification by column chromatography yielded 167 mg of organic compound A. Mass spectrometry results: m / z value (M+H): 475.31.

[0103] Synthesis Example 2: Synthesis of Organic Compound B

[0104]

[0105]

[0106] The synthesis method was the same as in Synthesis Example 1, except that monomer 1 was replaced with monomer 4 (CAS: 1516-96-7). All other raw materials, steps, and process parameters were the same as in Synthesis Example 1, yielding the target compound B. Mass spectrometry results: m / z value (M+H): 643.51.

[0107] Synthesis Example 3: Synthesis of Organic Compound C

[0108]

[0109] Monomer 7 (2.06 g, 0.01 mol, CAS: 128-39-2) and monomer 8 (1.78 g, 0.01 mol, CAS: 545-49-72-3) were dissolved in 100 mL of 1,4-dioxane, and dodecyl mercaptan (2.02 g, 0.01 mol) was added. The mixture was stirred at 90 °C for 4 h. After cooling to room temperature, monomer 7 (4.12 g, 0.02 mol) and 37% hydrochloric acid solution (10 mL) were added, and the mixture was stirred at 90 °C for 20 h. After extraction with dichloromethane, washing with water, and purification by column chromatography, 2.7 g of organic compound C was obtained. Mass spectrometry results: m / z value (MH): 759.58.

[0110] The specific components and preparation method of the photoresist of the present invention will be described in detail below using several embodiments as examples, but the photoresist is not limited to these embodiments.

[0111] Example 1

[0112] A photoresist, comprising the following components in parts by weight:

[0113]

[0114] The phenolic resin is a linear phenolic resin (Shengquan Company's 8850), the photosensitizer is a diazonoquinone photosensitizer (Toyo 4NT-350), the crosslinking agent is an amine crosslinking agent (Sanwa MW390), the additives are 0.35 parts of coupling agent (Shin-Etsu KF50) and 0.25 parts of surfactant (DIC F-554), and the solvent is propylene glycol monomethyl ether acetate (PMA).

[0115] The photoresist is prepared as follows: all components are mixed and fully dissolved and dispersed according to the formula to obtain the photoresist.

[0116] Examples 2-6

[0117] A photoresist differs from Example 1 only in the types and / or amounts of its components, as shown in Table 1. The units of amount in Table 1 are "parts by mass". Items not shown in Table 1 are the same as in Example 1.

[0118] Table 1

[0119]

[0120]

[0121] Comparative Example 1

[0122] A photoresist, differing from Example 1 only in that organic compound A is replaced with an equal mass of THPE. The other components and dosages are the same as in Example 1.

[0123] Comparative Example 2

[0124] A photoresist, differing from Example 1 only in that organic compound A is replaced by an equal mass of K5 (structure: Other components and dosages are the same as in Example 1.

[0125] Comparative Example 3

[0126] A photoresist differs from Example 1 only in that organic compound A is replaced with an equal mass of antioxidant BHT (2,6-di-tert-butyl-p-cresol), while the other components and amounts are the same as in Example 1.

[0127] Comparative Example 4

[0128] A photoresist differs from Example 1 only in that organic compound A is replaced with an equal mass of antioxidant 1076 ((β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid octadecyl alcohol), while the other components and amounts are the same as in Example 1.

[0129] The performance of the aforementioned photoresist was tested, and the specific details are as follows:

[0130] First, a glass substrate was prepared, and a 200nm molybdenum layer was magnetron sputtered onto it. The substrate was then irradiated with UV light for 1 minute and cleaned with deionized water. Next, the photoresist to be tested was uniformly coated onto the substrate surface using a spin-coating method. After pre-baking at 110℃ for 140s, a 1.5μm thick film was obtained. Exposure was performed using 365nm UV light, with the mask and coating distance 0μm. A 2.38% TMAH (tetramethylammonium hydroxide) developer was used, and development was carried out at 23℃ for 40s, followed by rinsing with water and drying. After development, the substrate was baked at 130℃ for 120s, and then etched using SF6, Cl2, and O2 plasmas. The residual film rate, etching reduction rate, and etching linewidth variation were measured and calculated, and the data are shown in Table 2.

[0131] Among them, the residual film rate is the ratio of the film thickness after development to the film thickness before development. The calculation formula is: Residual film rate (%) = (FT after development / FT before development) × 100%, where FT refers to the film thickness, which is measured by an ellipsometry. The higher the residual film rate, the better the resistance to development. The etching film reduction rate (%) = (1 - film thickness after etching / film thickness before etching) × 100%. The film thickness before and after etching is obtained by scanning electron microscopy (SEM). The etching film reduction rate is an indicator of etching resistance. The smaller the value, the better the etching resistance. The etching linewidth change value = linewidth before etching - linewidth after etching. The linewidth is obtained by SEM testing. The smaller the etching linewidth change value, the better the etching resistance.

[0132] The morphology of the photoresist before and after etching was tested using a scanning electron microscope (SEM, Hitachi SU8000). The pattern morphology of the photoresist before etching provided in Example 1 is shown below. Figure 1 As shown, the substrate is a 200nm molybdenum metal thin film; the morphology of the etched pattern is as follows. Figure 2 As shown in the figure, there is no residue in the etched area, the etched morphology is good, the slope angle is between 60-80°, the etched CD changes little, and it shows excellent etching performance.

[0133] Table 2

[0134]

[0135]

[0136] As shown in Table 2 and SEM images, Examples 1-6 of the present invention exhibit superior performance in terms of developability and etching compared to Comparative Examples 1-4. Among them, Examples 1-6 have a residual film rate of ≥92.3%, an etching film reduction rate of ≤20.5%, an etching linewidth variation of ≤0.37μm, good etching morphology, and a slope angle between 60-80°.

[0137] In summary, the organic compound with a specific structure provided by this invention, as a photolithography additive, can effectively improve the developability and etch resistance of the photoresist containing it, increase the etch selectivity, reduce etch residue, optimize the etch morphology, and fully meet the processing requirements of high precision and fine pattern / circuit.

[0138] The applicant declares that this invention illustrates the organic compound, the photoresist containing it, and their applications through the above embodiments. However, this invention is not limited to the above process steps, meaning that this invention does not necessarily rely on the above process steps to be implemented. Those skilled in the art should understand that any improvements to this invention, equivalent substitutions of the raw materials used in this invention, additions of auxiliary components, and selection of specific methods all fall within the protection and disclosure scope of this invention.

Claims

1. An organic compound, characterized in that, The organic compound has the structure shown in Formula I: Among them, Y1 and Y2 are each independently selected from any one of single bond, C1-C10 straight-chain or branched alkylene group, C2-C10 straight-chain or branched alkenyl group, C2-C10 straight-chain or branched alkyne group, and C6-C30 arylene group; R1, R2, and R3 are each independently selected from hydrogen, substituted or unsubstituted tert-butyl, and hydroxyl groups; R4, R5, and R6 are each independently selected from any one of hydrogen, substituted or unsubstituted C1-C10 straight-chain or branched alkyl groups, substituted or unsubstituted C2-C10 alkenyl groups, substituted or unsubstituted C2-C10 alkynyl groups, and substituted or unsubstituted C6-C30 aryl groups. The substituents in R1, R2, R3, R4, R5, and R6 are each independently selected from at least one of halogens, C1-C10 straight-chain or branched alkyl groups, and C6-C30 aryl groups.

2. The organic compound according to claim 1, characterized in that, Y1 and Y2 are each independently selected from any one of single bonds, C2-C8 straight-chain or branched alkylene groups, C2-C8 straight-chain or branched alkenyl groups, and C6-C12 arylene groups, preferably single bonds or any one of the following groups: in, The linking site of the representative group.

3. The organic compound according to claim 1, characterized in that, R1, R2, and R3 are each independently selected from hydrogen, substituted or unsubstituted tert-butyl, and hydroxyl; the substituents in R1, R2, and R3 are each independently selected from at least one of halogen, C1-C8 straight-chain or branched alkyl, and phenyl. Preferably, R4, R5, and R6 are each independently selected from hydrogen, substituted or unsubstituted C1-C8 straight-chain or branched alkyl groups, substituted or unsubstituted C2-C8 alkenyl groups, and substituted or unsubstituted C6-C12 aryl groups; the substituents in R4, R5, and R6 are each independently selected from at least one of halogens, C1-C8 straight-chain or branched alkyl groups, and phenyl groups. Preferably, R4, R5, and R6 are each independently selected from hydrogen, C1-C5 straight-chain or branched alkyl groups.

4. The organic compound according to claim 1, characterized in that, The organic compound has a structure shown in any of the following:

5. A photoresist, characterized in that, The photoresist comprises an organic compound as described in any one of claims 1-4.

6. The photoresist according to claim 5, characterized in that, The photoresist comprises a combination of an alkali-soluble resin, a photosensitizer, a crosslinking agent, and the organic compound.

7. The photoresist according to claim 6, characterized in that, The alkali-soluble resin includes phenolic resin, preferably linear phenolic resin; Preferably, the weight-average molecular weight of the phenolic resin is 2000-30000.

8. The photoresist according to claim 6, characterized in that, The photosensitizer is a compound containing a diazonoquinone group; Preferably, the crosslinking agent comprises any one or a combination of at least two of amine crosslinking agents, epoxy crosslinking agents, ether crosslinking agents, and urea crosslinking agents. More preferably, it comprises any one or a combination of at least two of hexamethylenetetramine, 3-(2,3-epoxypropoxy)propyltrimethoxysilane, 1,4-butanediol diglycidyl ether, hexamethylenemethyl melamine, hexamethylene melamine, tris(alkoxycarbonylamino)triazine, and 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolidineone.

9. The photoresist according to claim 6, characterized in that, The photoresist also includes solvents and / or additives; Preferably, the additives include any one or a combination of at least two of the following: coupling agents, surfactants, defoamers, photoacid generators, thermal acid generators, and ultraviolet absorbers.

10. The photoresist according to any one of claims 5-9, characterized in that, The photoresist comprises the following components by weight percentage:

11. The use of an organic compound as described in any one of claims 1-4, or a photoresist as described in any one of claims 5-10, in a display panel or a semiconductor chip.

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