Spin-on carbon composition, semiconductor device and method of manufacturing the same

Abstract

This application discloses a spin-coating carbon composition comprising an aldehyde-substituted benzoxazine resin having the structure of Formula 1, a surfactant, and a solvent. The aldehyde-substituted benzoxazine resin used in this application has a well-defined structure and good heat resistance. The spin-coating carbon composition based on this benzoxazine resin significantly improves the thermal stability of the thin film while maintaining excellent coating performance and etching resistance, providing a new generation of hard mask materials for advanced semiconductor manufacturing. This application also discloses a method for preparing semiconductor devices using this spin-coating carbon composition, and the semiconductor device itself. Formula 1

Description

Technical Field

[0001] This invention relates to the field of microelectronics manufacturing and semiconductor process materials technology, and particularly to a spin-coated carbon material with good thermal stability, specifically a spin-coated carbon composition using aldehyde-substituted benzoxazine resin as the key raw material. Background Technology

[0002] In advanced semiconductor manufacturing processes, spin-coated carbon materials play a crucial role in multilayer lithography. Their functions include wafer surface planarization, high aspect ratio structure filling, and etching masking. As device feature sizes continue to shrink and three-dimensional structures become more complex, increasingly stringent requirements are being placed on the performance of spin-coated carbon materials.

[0003] Currently, most mainstream spin-coated carbon materials are based on phenolic resins, acrylic resins, polyhydroxystyrene, or their derivatives. However, these traditional materials have drawbacks: First, in some advanced processes, spin-coated carbon materials are used in the front-end steps, while the subsequent steps require higher process temperatures, such as PVD / CVD processes, which typically exceed 300°C. Due to the inherent heat resistance of the resin structure, conventional spin-coated carbon materials often struggle to maintain structural stability at these process temperatures. Second, during the thermosetting process of materials like phenolic and acrylic resins, solvent evaporation and cross-linking reactions lead to significant volume shrinkage, causing internal stress in the film, cracking, and poor adhesion to the substrate, thus affecting structural stability.

[0004] Therefore, there is an urgent need in this field to develop a novel spin-coated carbon composition with excellent thermal stability, low curing shrinkage, high etch resistance, and excellent coating performance. Summary of the Invention

[0005] The purpose of this invention is to provide a spin-coating carbon composition based on aldehyde-substituted benzoxazine to overcome the shortcomings of the prior art. This composition aims to simultaneously achieve excellent thermal stability, good resistance to plasma etching, low shrinkage, and good coating performance.

[0006] This application develops a spin-coating carbon composition of aldehyde-substituted benzoxazine. Introducing an aldehyde group into the benzoxazine structure increases the crosslinking density of the material, thereby improving its thermal stability. Simultaneously, utilizing the low curing shrinkage of the benzoxazine resin, the requirements for film dimensional stability are met. With the synergistic use of suitable crosslinking agents, solvents, and surfactants, excellent coating performance and etching resistance are achieved while ensuring the film's excellent thermal stability, providing a new generation of hard mask materials for advanced semiconductor manufacturing.

[0007] A first aspect of this application provides a spin-coated carbon composition comprising an aldehyde-substituted benzoxazine resin having the structure of Formula 1. Formula 1 Wherein, A contains at least one benzene ring fused with an oxazine ring, and is represented by any of the following structures: A-1, A-2, A-3, A-4, A-5, A-6, A-7, A-8, A-9, A-10; R1 is selected from hydrogen, C 1-10 Alkyl, halogen, cyano, C 1-10 ester group, C 1-10 ether group, C 2-10 alkynyl group, C 2-10 One or more of the alkynyl groups; B is an aromatic ring structure containing 1 to 4 benzene rings with a γ valence; When B is substituted, the substituent is selected from C. 1-6 Alkyl, halogen, cyano, C 1-6 One or more of the following groups: ester, ether, alkynyl, propargyl, vinyl, and allyl; n is an integer from 1 to 4; m is an integer between 0 and 4; x is an integer between 1 and 4; y is an integer from 1 to 4, and is greater than or equal to x; Indicates the connection site with -CHO; This indicates the connection site with R1.

[0008] The weight ratio of benzoxazine resin to solvent is (1-30):(60-99).

[0009] Structure of A fused with an oxazine ring It is formed by any of the following structures: , , , , ; in, Indicates the connection site with -CHO; This indicates the connection site with R1.

[0010] According to the spin-coated carbon composition of the first aspect, the aromatic ring structure in B is selected from one or more of benzene, fluorene, and naphthalene; R1 is selected from hydrogen, C 1-4 Alkyl, halogen, cyano, propargyl, vinyl, and allyl groups, preferably hydrogen, methyl, ethyl, propyl, cyano, halogen, or allyl.

[0011] When B has a substituent, the substituent is an acetylenic group; m and n are each an independent integer from 1 to 4, for example, 1, 2, 3 or 4 respectively.

[0012] According to the spin-coated carbon composition of the first aspect, the Mw of the aldehyde-substituted benzoxazine resin having the structure of Formula 1 is 200-10000 g / mol.

[0013] According to the spin-coated carbon composition of the first aspect, the Mw of the aldehyde-substituted benzoxazine resin having the structure of Formula 1 is 250-3000 g / mol.

[0014] According to the spin-coated carbon composition of the first aspect, the content of surfactant in the spin-coated carbon composition is 0.0001-0.1 parts per 100 parts by weight.

[0015] According to the spin-coated carbon composition of the first aspect, the spin-coated carbon composition further includes one or both of a crosslinking agent and an acid-producing agent.

[0016] According to the spin-coated carbon composition of the first aspect, the solvent is selected from one or more of alcohol solvents, ketone solvents, ester solvents, ether solvents, and aromatic hydrocarbon solvents; When the crosslinking agent is present, it is selected from compounds containing methoxymethyl, hydroxymethyl, hydroxyethyl, epoxy, or vinyl groups; and / or When the acid-producing agent is present, it is selected from ionic and / or nonionic compounds.

[0017] According to the spin-coated carbon composition of the first aspect, the solvent is selected from one or more of the following solvents: propylene glycol methyl ether acetate, propylene glycol methyl ether, ethylene glycol methyl ether acetate, diethylene glycol, propylene glycol methyl ether, propylene glycol monoethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, butyl acetate, neopentyl acetate, ethyl lactate, methyl ethyl ketone, methyl isobutyl ketone, γ-butyrolactone, cyclohexanone, dioxane, N , N -Dimethylformamide, N ,N -Dimethylacetamide, dimethyl sulfoxide; The crosslinking agent has one or more of the following structures: , , , , , , , , , , , , , , , , , , , , , , ; The acid-producing agent is selected from one or more of the following: diphenyliodonium trifluoromethanesulfonate, diphenyliodonium camphor sulfonate, diphenyliodonium perfluoro-1-butanesulfonate, diphenyliodonium perfluorooctane sulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, bis(4-tert-butylphenyl)iodonium tetrafluoroborate, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, bis(4-tert-butylphenyl)iodonium perfluoro-1-butane sulfonate, bis(4-tert-butylphenyl)iodonium camphor sulfonate, bis(4-tert-butylphenyl) Iodomonium perfluorooctane sulfonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphor sulfonate, triphenylsulfonium perfluoro-1-butyl sulfonate, triphenylsulfonium perfluorooctane sulfonate, p-tolyldiphenylsulfonium trifluoromethanesulfonate, p-tolyldiphenylsulfonium perfluorooctane sulfonate, p-tolyldiphenylsulfonium perfluoro-1-butane sulfonate, p-tolyldiphenylsulfonium camphor sulfonate, 2,4,6-trimethylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-tert-butylphenyldiphenylsulfonium trifluoromethanesulfonate Salts, 4-phenylphenylthiodiphenylsulfonium hexafluorophosphate, 1-(2-naphthylmethyl)thiodium trifluoromethane sulfonate, 4-hydroxy-1-naphthyldimethylsulfonium trifluoromethane sulfonate, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-) 2-(4-methoxy-1-naphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(benzo[d][1,3]dioxolane-5-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine 5-Triazine, 2-(3,4-dimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(2,4-dimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(2-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-butoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-pentoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine5-Triazine, diphenyl disulfone, di-p-tolyl disulfone, bis(phenylsulfonyl)diazomethane, bis(4-chlorophenylsulfonyl)diazomethane, bis(p-tolylsulfonyl)diazomethane, bis(4-tert-butylphenylsulfonyl)diazomethane, bis(2,4-dimethylmethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, (benzoyl)(phenylsulfonyl)diazomethane, 1-benzoyl-1-phenylmethyl p-toluenesulfonic acid, 2-benzoyl-2-hydroxy-2-phenylethyl p-toluenesulfonic acid, 1,2,3-phenyltriyl trimethanesulfonic acid, 2,6-dinitrobenzoyl p-toluenesulfonic acid, 2-nitrobenzene p-toluenesulfonic acid, 4-nitrobenzene p-toluenesulfonic acid, N -(phenylsulfonyloxy)succinimide, N -(trifluoromethylsulfonyloxy)succinimide, N -(perfluoro-1-butanesulfonic acid) succinimide, N -(perfluorooctane sulfonate) succinimide, N -(perfluoro-1-butanesulfonic acid) phthalimide, N -(trifluoromethylsulfonyloxy)phthalimide, N -(perfluorooctane sulfonic acid) phthalimide, N -(trifluoromethylsulfonyloxy)-5-norbornene-2,3-dicarboxylic imide N -(perfluoro-1-butanesulfonic acid)-5-norbornene-2,3-dicarboxylic acid imide N -(perfluorooctane sulfonic acid)-5-norbornene-2,3-dicarboxylic acid imide N -(trifluoromethylsulfonyloxy)naphthylmethyleneisocyanoyl, N -(perfluoro-1-butanesulfonic acid)naphthyleneimide, N -(perfluorooctane sulfonic acid)naphthylene imide, N-(10-Camphorsulfonyloxy)naphthaleneximide, ammonium trifluoromethanesulfonate, ammonium perfluorobutanesulfonate, Ad-TFBS[4-adamantanecarboxy-1,1,2,2-tetrafluorobutanesulfonic acid]ammonium, AdOH-TFBS[3-hydroxy-4-adamantanecarboxy-1,1,2,2-tetrafluorobutanesulfonic acid]ammonium, Ad-DFMS[(adamantane-methoxycarbonyl)-difluoromethanesulfonic acid], AdOH-DFMS[3-hydroxyadamantyl-methoxycarbonyl)-difluoromethanesulfonic acid]ammonium, DHC-TFB SS[4-dehydrocholic acid-1,1,2,2-tetrafluorobutanesulfonic acid]ammonium, ODOT-DFMS[hexahydro-4,7-epoxyisobenzofuran-1(3H)-one, 6-(2,2'-difluoro-2-sulfonate acetate)]ammonium, tetrabutylammonium perfluorobutanesulfonate, p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid ethyl ester, trifluoroacetic acid pyridinium salt, hydroxyp-toluenesulfonic acid pyridinium salt, phthalimide derivatives and benzenesulfonamide derivatives, polyhalomethanes, benzyl halides; and / or The surfactant is selected from one or more of the following: acrylic surfactants, silicone surfactants, fluorocarbon surfactants, and polyoxyethylene surfactants.

[0018] According to the spin-coating carbon composition of the first aspect, the spin-coating carbon composition comprises, by weight: 1-30 parts of aldehyde-substituted benzoxazine resin having the structure of Formula 1 0-5 parts of crosslinking agent 0-2 parts of acid-producing agent Surfactant 0.0001-0.1 parts Solvent 60-99 parts.

[0019] A second aspect of this application provides a semiconductor manufacturing method, the semiconductor manufacturing method comprising: forming a spin-coated carbon hard mask using a spin-coated carbon composition of the first aspect.

[0020] A third aspect of this application provides a semiconductor device manufactured using the method of the second aspect.

[0021] The spin-coated carbon composition of this application has, but is not limited to, the following beneficial effects: The spin-coating carbon composition provided by this invention brings about significant technological progress, and its beneficial effects are specifically reflected in the following four aspects: 1. Excellent heat resistance and high-temperature stability: After curing, the benzoxazine resin forms a rigid cross-linked network rich in aromatic heterocycles. Combined with the high-temperature cross-linking structure achieved by the aldehyde group, this results in an extremely high thermal decomposition temperature. This allows the prepared spin-coated carbon material to maintain its chemical structure, mechanical properties, and pattern shape stability during subsequent high-temperature processes such as physical deposition, chemical vapor deposition, and ion implantation. It will not soften, flow, thermally degrade, or experience performance degradation, thus ensuring the reliability of the entire manufacturing process.

[0022] 2. Low curing shrinkage and excellent dimensional stability: Benzoxazine resin is cured through ring-opening polymerization of a cyclic structure. This reaction mechanism itself has near-zero volume shrinkage during curing, achieving good dimensional stability. Simultaneously, it effectively avoids problems such as poor surface smoothness and interface debonding caused by uneven shrinkage.

[0023] 3. High carbon content and excellent etching resistance: First, the benzoxazine resin with a polycyclic benzene ring structure used in this application has a high intrinsic carbon content (typically >70%). Second, this resin can form a highly dense polymer network during curing, thus endowing it with extremely high etching resistance to plasma. Experiments show that, compared with traditional phenolic resins, spin-coated carbon films prepared with it have better etching resistance and can be used as high-performance hard mask layers.

[0024] 4. Good coating performance: Due to the small molecular structure of the selected benzoxazine resin (molecular weight 200-10000 g / mol, preferably 250-3000 g / mol), good coating uniformity can be achieved. Attached Figure Description

[0025] Figure 1 The synthesis example 1 is shown. 1 H-NMR spectrum.

[0026] Figure 2 The thermogravimetric curves of Example 1 are shown in comparison with those of Comparative Examples 1 and 2. Detailed Implementation

[0027] The present application will now be described in further detail with reference to the accompanying drawings and embodiments. Through these descriptions, the features and advantages of the present application will become clearer and more apparent.

[0028] The term “exemplary” as used herein means “serving as an example, embodiment, or illustration.” Any embodiment illustrated herein as “exemplary” is not necessarily to be construed as superior to or better than other embodiments. Although various aspects of embodiments are shown in the accompanying drawings, the drawings are not necessarily drawn to scale unless specifically indicated otherwise.

[0029] Furthermore, the technical features involved in the different embodiments of this application described below can be combined with each other as long as they do not conflict with each other.

[0030] This application provides a spin-coated carbon composition comprising an aldehyde-substituted benzoxazine resin having the structure of Formula 1. Formula 1.

[0031] Wherein, A contains at least one benzene ring fused with an oxazine ring, and is represented by any of the following structures: A-1, A-2, A-3, A-4, A-5, A-6, A-7, A-8, A-9, A-10.

[0032] According to one specific embodiment, the structure of A fused with an oxazine ring... It is formed by any of the following structures: , , , , .

[0033] in, Indicates the connection site with -CHO; This indicates the connection site with R1.

[0034] R1 is selected from hydrogen, C 1-10 Alkyl, halogen, cyano, C 1-10 ester group, C 1-10 ether group, C 2-10 alkenyl, C 2-10 One or more of the alkynyl groups; for example, they can be hydrogen, C 1-4 Alkyl, halogen, cyano, propargyl, vinyl, and allyl groups.

[0035] R1 may or may not exist, and it may exist on the benzene ring or on a non-benzene ring. Therefore, m is an integer from 0 to 4, for example, it can be 0, 1, 2, 3 or 4.

[0036] In the structure of Formula 1, the aldehyde group (-CHO) can be located on the benzene ring or on a non-benzene ring. n is the number of aldehyde groups on each ring structure A in Formula 1. Specifically, n can be an integer from 1 to 4, for example, 1, 2, 3 or 4.

[0037] x represents the number of benzoxazine structures linked to a single B group in a single molecule. Specifically, x can be an integer from 1 to 4, for example, 1, 2, 3 or 4.

[0038] B represents an aromatic ring structure containing 1 to 4 benzene rings with a valence of y. Here, y is an integer from 1 to 4, and is greater than or equal to x.

[0039] When B is substituted, the substituent is selected from C. 1-6 Alkyl, halogen, cyano, C 1-6 ester group, C 1-6 ether group, C 2-6 One or more of alkynyl, propynyl, vinyl, and allyl. According to a specific embodiment, when B is substituted, the substituent is selected from one or more of C1, C2, C3, C4, C5, C6 alkyl, halogen, cyano, ester, ether, alkynyl, propargyl, vinyl, and allyl. For example, the substituent may be ethynyl.

[0040] According to one specific embodiment, B may be selected from phenyl, naphthyl, or fluorenyl, particularly acetylenyl-substituted phenyl.

[0041] The spin-coating carbon composition provided in this application includes one or more resins, and at least one benzoxazine resin with an aldehyde-substituted structure of Formula 1. By introducing aldehyde groups into the benzoxazine compound, this application increases the crosslinking density of the material. After curing through ring-opening polymerization of the cyclic structure, a rigid crosslinked network rich in aromatic heterocycles is formed, exhibiting near-zero volume shrinkage. This achieves good dimensional stability and effectively improves problems such as poor surface smoothness and interfacial debonding caused by uneven shrinkage.

[0042] In some specific embodiments, the aldehyde-substituted benzoxazine resin having the structure of Formula 1 has a carbon content greater than 70%.

[0043] In some specific embodiments, the carbon content of the aldehyde-substituted benzoxazine resin having the structure of Formula 1 can be a range of 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80%, 82%, 85%, 88%, 90%, 82%, 95%, 97%, 99%, or any two of these.

[0044] The high-carbon-content benzoxazine resin used in this application can form a highly dense polymer network during the curing process, thus exhibiting extremely high etch resistance to plasma and serving as a high-performance hard mask layer.

[0045] In one embodiment, the Mw of the aldehyde-substituted benzoxazine resin having the structure of Formula 1 is 200-10000 g / mol, preferably 250-3000 g / mol.

[0046] In some specific embodiments, the Mw of the aldehyde-substituted benzoxazine resin having the structure of Formula 1 can be in the range of 200 g / mol, 250 g / mol, 300 g / mol, 400 g / mol, 450 g / mol, 500 g / mol, 550 g / mol, 600 g / mol, 650 g / mol, 700 g / mol, 800 g / mol, 900 g / mol, 1000 g / mol, 1200 g / mol, 1500 g / mol, 1800 g / mol, 2000 g / mol, 2200 g / mol, 2500 g / mol, 2800 g / mol, 3000 g / mol, 4000 g / mol, 5000 g / mol, 6000 g / mol, 7000 g / mol, 8000 g / mol, 9000 g / mol, 10000 g / mol, or any two of these ranges. This application achieves good coating uniformity by controlling the molecular weight (Mw) of the benzoxazine resin within the above-mentioned range. When Mw is greater than 3000, especially greater than 10000, the coating uniformity of the spin-coated carbon composition will be poor due to the excessively large molecular weight.

[0047] In one embodiment, the spin-coated carbon composition further includes one or both of a crosslinking agent and an acid-producing agent.

[0048] In one embodiment, the solvent is selected from one or more of alcohol solvents, ketone solvents, ester solvents, ether solvents, and aromatic hydrocarbon solvents.

[0049] In one embodiment, the solvent is selected from one or more of the following solvents: propylene glycol methyl ether acetate, propylene glycol methyl ether, ethylene glycol methyl ether acetate, diethylene glycol, propylene glycol methyl ether, propylene glycol monoethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, butyl acetate, neopentyl acetate, ethyl lactate, methyl ethyl ketone, methyl isobutyl ketone, γ-butyrolactone, cyclohexanone, dioxane, N , N -Dimethylformamide, N , N- Dimethylacetamide, dimethyl sulfoxide; preferably propylene glycol methyl ether acetate or diethylene glycol methyl ether, cyclohexanone, methyl isobutyl ketone, OK73 (a mixture of 70% propylene glycol monomethyl ether and 30% propylene glycol monomethyl ether acetate), ethyl lactate.

[0050] The aforementioned crosslinking agent is a compound containing methoxymethyl, hydroxymethyl, hydroxyethyl, epoxy, or vinyl groups. According to one specific embodiment, the crosslinking agent has one or more of the following structures: , , , , , , , , , , , , , , , , , , , , , , .

[0051] The acid-generating agents mentioned above are selected from ionic and / or nonionic compounds. Specifically, the acid-generating agents are selected from one or more of the following: diphenyliodonium trifluoromethanesulfonate, diphenyliodonium camphor sulfonate, diphenyliodonium perfluoro-1-butanesulfonate, diphenyliodonium perfluorooctane sulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, bis(4-tert-butylphenyl)iodonium tetrafluoroborate, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, bis(4-tert-butylphenyl)iodonium perfluoro-1-butane sulfonate, bis(4-tert-butylphenyl)iodonium camphor sulfonate, bis(4-tert-butylphenyl)iodonium perfluorooctane sulfonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium Onyx camphor sulfonate, triphenylsulfonium perfluoro-1-butyl sulfonate, triphenylsulfonium perfluorooctane sulfonate, p-tolyl diphenylsulfonium trifluoromethane sulfonate, p-tolyl diphenylsulfonium perfluorooctane sulfonate, p-tolyl diphenylsulfonium perfluoro-1-butane sulfonate, p-tolyl diphenylsulfonium camphor sulfonate, 2,4,6-trimethylphenyl diphenylsulfonium trifluoromethane sulfonate, 4-tert-butylphenyl diphenylsulfonium trifluoromethane sulfonate, 4-phenylphenylthiodiphenylsulfonium hexafluorophosphate, 1-(2-naphthylmethyl)thiol onyx trifluoromethane sulfonate, 4-hydroxy-1-naphthyldimethylsulfonium trifluoromethane sulfonate, 2-methyl-4,6-bis(trichloromethyl)-1 3,5-triazine, 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxy-1-naphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(benzo[d][1,3]dioxolane-5-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-dimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(2,4-dimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(2-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-butoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-pentoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine5-Triazine, diphenyl disulfone, di-p-tolyl disulfone, bis(phenylsulfonyl)diazomethane, bis(4-chlorophenylsulfonyl)diazomethane, bis(p-tolylsulfonyl)diazomethane, bis(4-tert-butylphenylsulfonyl)diazomethane, bis(2,4-dimethylmethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, (benzoyl)(phenylsulfonyl)diazomethane, 1-benzoyl-1-phenylmethyl p-toluenesulfonic acid, 2-benzoyl-2-hydroxy-2-phenylethyl p-toluenesulfonic acid, 1,2,3-phenyltriyl trimethanesulfonic acid, 2,6-dinitrobenzoyl p-toluenesulfonic acid, 2-nitrobenzene p-toluenesulfonic acid, 4-nitrobenzene p-toluenesulfonic acid, N -(phenylsulfonyloxy)succinimide, N -(trifluoromethylsulfonyloxy)succinimide, N-(perfluoro-1-butanesulfonic acid)succinimide, N -(perfluorooctane sulfonate) succinimide, N -(perfluoro-1-butanesulfonic acid) phthalimide, N -(trifluoromethylsulfonyloxy)phthalimide, N -(perfluorooctane sulfonic acid) phthalimide, N -(trifluoromethylsulfonyloxy)-5-norbornene-2,3-dicarboxylic imide N -(perfluoro-1-butanesulfonic acid)-5-norbornene-2,3-dicarboxylic acid imide N -(perfluorooctane sulfonic acid)-5-norbornene-2,3-dicarboxylic acid imide N -(trifluoromethylsulfonyloxy)naphthylmethyleneisocyanoyl, N -(perfluoro-1-butanesulfonic acid)naphthyleneimide, N -(perfluorooctane sulfonic acid)naphthylene imide, N-(10-Camphorsulfonyloxy)naphthaleneximide, ammonium trifluoromethanesulfonate, ammonium perfluorobutanesulfonate, Ad-TFBS[4-adamantanecarboxyl-1,1,2,2-tetrafluorobutanesulfonic acid]ammonium, AdOH-TFBS[3-hydroxy-4-adamantanecarboxyl-1,1,2,2-tetrafluorobutanesulfonic acid]ammonium, Ad-DFMS[(adamantane-methoxycarbonyl)-difluoromethanesulfonic acid], AdOH-DFMS[3-hydroxyadamantyl-methoxycarbonyl)-difluoromethanesulfonic acid]ammonium, DHC-T FBSS [4-dehydrocholic acid-1,1,2,2-tetrafluorobutanesulfonic acid]ammonium, ODOT-DFMS [hexahydro-4,7-epoxyisobenzofuran-1(3H)-one, 6-(2,2'-difluoro-2-sulfonate acetate)]ammonium, tetrabutylammonium perfluorobutanesulfonate, p-toluenesulfonic acid pyridine salt, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid ethyl ester, trifluoroacetic acid pyridine salt, hydroxyp-toluenesulfonic acid pyridine salt, phthalimide derivatives and benzenesulfonamide derivatives, polyhalogenated methanes, benzyl halides.

[0052] The surfactants mentioned above are selected from one or more of the following: acrylic surfactants, silicone surfactants, fluorocarbon surfactants, and polyoxyethylene surfactants.

[0053] In one embodiment, the spin-coated carbon composition comprises, by weight: 1-30 parts of aldehyde-substituted benzoxazine resin having the structure of Formula 1 0-5 parts of crosslinking agent 0-2 parts of acid-producing agent Surfactant 0.0001-0.1 parts Solvent 60-99 parts.

[0054] In some specific embodiments, the weight of the aldehyde-substituted benzoxazine resin having the structure of Formula 1 in every 100 parts by weight of the spin-coated carbon composition may be 1 part, 2 parts, 3 parts, 5 parts, 8 parts, 10 parts, 12 parts, 15 parts, 18 parts, 20 parts, 22 parts, 25 parts, 28 parts, 30 parts, or any combination thereof.

[0055] In some specific embodiments, the weight of crosslinking agent in every 100 parts by weight of the spin-coated carbon composition can be 0.05 parts, 0.1 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.8 parts, 1.0 parts, 1.5 parts, 2.0 parts, 2.5 parts, 3.0 parts, 3.5 parts, 4.0 parts, 4.5 parts, 5.0 parts, or any combination thereof.

[0056] In some specific embodiments, the weight of the acid-generating agent in every 100 parts by weight of the spin-coated carbon composition can be 0.01 parts, 0.03 parts, 0.05 parts, 0.07 parts, 0.1 parts, 0.15 parts, 0.2 parts, 0.3 parts, 0.4 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, 1.0 parts, 1.2 parts, 1.5 parts, 1.7 parts, 2.0 parts, or any combination thereof.

[0057] In some specific embodiments, the amount of additives included in every 100 parts by weight of the spin-coating carbon composition can be 0.0001 parts, 0.0005 parts, 0.0008 parts, 0.001 parts, 0.002 parts, 0.003 parts, 0.005 parts, 0.007 parts, 0.01 parts, 0.02 parts, 0.03 parts, 0.04 parts, 0.05 parts, 0.06 parts, 0.07 parts, 0.08 parts, 0.09 parts, 0.1 parts, or any combination thereof.

[0058] In some specific embodiments, the solvent-containing parts in 100 parts by weight of the spin-coating carbon composition may be 60, 62, 65, 68, 70, 72, 75, 78, 80, 82, 85, 88, 90, 92, 95, 99, or any combination thereof.

[0059] This application also provides a semiconductor manufacturing method, including: forming a spin-coated carbon hard mask using the aforementioned spin-coated carbon composition.

[0060] This application further provides a semiconductor device manufactured using the aforementioned method.

[0061] This invention does not impose any special restrictions on the source of any raw materials; unless otherwise specified, they are all conventional products that can be obtained commercially.

[0062] In the following preparation examples: Mw value testing: A GILLENT 1100 gel permeation chromatography instrument, USA; chromatographic grade THF as the mobile phase; test temperature: 35°C; solvent flow rate: 1.0 mL / min; standard: polystyrene (PS).

[0063] Carbon content test: The cured resin powder was tested by an elemental analyzer (Flash Smart CHNS / O). It was burned in a high-temperature reaction tube at 1000°C. The carbon was completely converted into CO2. After chromatographic separation, the carbon content was quantified by a thermal conductivity detector (TCD).

[0064] The following examples are provided to further illustrate the present invention.

[0065] Synthesis example 1 Under a nitrogen atmosphere, paraformaldehyde (3.03 g, 0.1 mol) and aniline (4.65 g, 0.05 mol) were stirred in 1,4-dioxane (50 mL) for 2 h. Then, p-hydroxybenzaldehyde (6.11 g, 0.05 mol) was added to the reaction system. The mixture was stirred at 80°C for another 6 h. The solution was cooled to room temperature, and deionized water was added to precipitate the precipitate. The precipitate was filtered and dried to obtain the solid product benzoxazine resin A1, with a yield of 83.1%. The Mw of the obtained benzoxazine resin A1 was 460 g / mol, and the carbon content was 76%. Proton NMR characterization (see [link to NMR spectrum]). Figure 1 ), 1 H NMR (DMSO) 9.79 (CHO), 4.77 (Ar-CH2-N), 5.60 (O-CH2-N), 6.49–7.96 (Ar-H).

[0066] The structure of benzoxazine resin A1 is as follows: .

[0067] Synthesis example 2 Using the same synthetic method as in Synthesis Example 1, except that p-hydroxybenzaldehyde was replaced with 6-hydroxy-2-naphthaldehyde (8.60 g, 0.05 mol), benzoxazine resin A2 was obtained in 79.2% yield. The resulting benzoxazine resin A2 had an Mw of 521 g / mol and a carbon content of 79%.

[0068] The structure of benzoxazine resin A2 is as follows: .

[0069] Synthesis example 3 Using the same synthetic method as in Synthesis Example 1, except that p-hydroxybenzaldehyde was replaced with 4-(4-formylphenyl)phenol (9.91 g, 0.05 mol), benzoxazine resin A3 was obtained in 82.6% yield. The resulting benzoxazine resin A3 had an Mw of 641 g / mol and a carbon content of 80%.

[0070] The structure of benzoxazine resin A3 is as follows: .

[0071] Synthesis example 4 Using the same synthetic method as in Synthesis Example 1, except that p-hydroxybenzaldehyde was replaced with 3-(4-hydroxy-phenoxy)-benzaldehyde (10.77 g, 0.05 mol), benzoxazine resin A4 was obtained in 80.2% yield. The resulting benzoxazine resin A4 had an Mw of 593 g / mol and a carbon content of 76%.

[0072] The structure of benzoxazine resin A4 is as follows: .

[0073] Synthesis example 5 Using the same synthetic method as in Synthesis Example 1, except that aniline was replaced with 2-naphthylamine (7.16 g, 0.05 mol), benzoxazine resin A5 was obtained in 81.2% yield. The resulting benzoxazine resin A5 had an Mw of 509 g / mol and a carbon content of 79%.

[0074] The structure of benzoxazine resin A5 is as follows: .

[0075] Synthesis example 6 Using the same synthetic method as in Synthesis Example 1, except that aniline was replaced with 3-aminophenylacetylene (5.86 g, 0.05 mol), benzoxazine resin A6 was obtained in 82.4% yield. The resulting benzoxazine resin A6 had an Mw of 497 g / mol and a carbon content of 78%.

[0076] The structure of benzoxazine resin A6 is as follows: .

[0077] Synthesis Example 7 Using the same synthetic method as in Synthesis Example 1, aniline was replaced with 1,5-diaminonaphthalene (3.96 g, 0.025 mol), and p-hydroxybenzaldehyde was replaced with 6-hydroxy-2-naphthaldehyde (8.60 g, 0.05 mol) to obtain benzoxazine resin A7 in 77.5% yield. The resulting benzoxazine resin A7 had an Mw of 1012 g / mol and a carbon content of 79%.

[0078] The structure of benzoxazine resin A7 is as follows: .

[0079] Synthesis example 8 Using the same synthetic method as in Synthesis Example 1, aniline was replaced with 9,9-bis(4-aminophenyl)fluorene (8.71 g, 0.025 mol), and p-hydroxybenzaldehyde was replaced with 2,4-dihydroxybenzaldehyde (3.45 g, 0.025 mol) to obtain benzoxazine resin A8 in 73.9% yield. The resulting benzoxazine resin A8 had an Mw of 2933 g / mol and a carbon content of 79%.

[0080] The structure of benzoxazine resin A8 is as follows: .

[0081] Synthesis example 9 Using the same synthetic method as in Synthesis Example 1, except that p-hydroxybenzaldehyde was replaced with 4-hydroxym-phthalaldehyde (7.51 g, 0.05 mol), benzoxazine resin A9 was obtained in 70.1% yield. The resulting benzoxazine resin A9 had an Mw of 502 g / mol and a carbon content of 72%.

[0082] The structure of benzoxazine resin A9 is as follows: .

[0083] Comparative Synthesis Example 1 Using the same synthetic method as in Synthesis Example 1, except that p-hydroxybenzaldehyde was replaced with phenol (4.71 g, 0.05 mol), a non-aldehyde-substituted benzoxazine resin R1 was obtained in 82.4% yield. The obtained benzoxazine resin R1 had an Mw of 397 g / mol and a carbon content of 79%.

[0084] The structure of benzoxazine resin R1 is as follows: .

[0085] Comparative Synthesis Example 2 In a 1 L four-necked flask equipped with a stirrer, condenser, constant-pressure dropping funnel, and thermometer, 1 mol of phenol and 100 mL of ethylene glycol methyl ether were added. Stirring was started, and the temperature was set to 60°C. 0.82 mol of 37% formaldehyde aqueous solution was added dropwise. The temperature was raised to 120°C, and 10 g of a 10% (w / w) oxalic acid solution in ethylene glycol methyl ether was slowly added dropwise to the flask. The reaction was allowed to proceed for 8 h. 200 g of ethanol was added to the polymer, and then the reactant solution was added dropwise to 5 L of cold water with stirring to precipitate a white flake. The filter cake was filtered and dried in a 45°C oven for 24 h to obtain linear phenolic resin R2. Its Mw = 3454 g / mol, PDI = 3.67, and carbon content was 78%.

[0086] The structure of linear phenolic resin R2 is as follows: .

[0087] Example The spin-coated carbon composition is composed of resin, crosslinking agent, acid-generating agent, additive, and solvent obtained from the synthesis examples and comparative synthesis examples, as shown in Table 1. It is prepared according to the mass parts in Table 2, shaken on a shaker for 24 h to allow them to fully dissolve, and filtered twice through a 0.2 μm pore size filter to obtain the spin-coated carbon composition.

[0088] Table 1

[0089] Table 2

[0090] The spin-coated carbon composition prepared above was subjected to performance testing, and the testing methods are as follows: 1. Evaluation of coating film thickness uniformity The spin-coated carbon composition was spin-coated onto a 4-inch silicon wafer at 1500 rpm, and then baked on a hot plate at 250°C for 1 minute to form a spin-coated carbon coating. The thickness of the carbon coating was measured using an ellipsometry (Woollam RC2). Thickness measurements were taken from a crosshair pattern on the silicon wafer, with thickness values ​​at 0.8 cm intervals from the midpoint, for a total of 9 points. Uniformity RU% = [(Max-Min)] / (2*Ave)*100% (Max is the maximum film thickness, Min is the minimum film thickness, and Ave is the average film thickness). Generally, a lower RU% indicates a more uniform coating and better coating performance.

[0091] 2. Evaluation of variable temperature heat resistance The spin-coated carbon composition was spin-coated onto a 4-inch silicon wafer at 1500 rpm, and then baked on a hot plate at 250°C for 60 seconds to form a spin-coated carbon coating. After cooling, the film was scraped off with a doctor blade to obtain a solid powder. Thermogravimetric analysis (TGA-55) was used for heat resistance testing. Under a nitrogen atmosphere, the heating rate was 10 °C / min, and the temperature range was 40–400 °C. The sample mass loss rate was measured and denoted as W. Loss-A %, recorded in Table 3.

[0092] It is generally believed that the lower the mass loss rate, the stronger the heat resistance.

[0093] Figure 2 A comparison graph of the thermogravimetric curves of Example 1, Comparative Examples 1 and 2 is shown. As can be seen from the graph, when heated to 400°C, the mass loss rate of Example 1 was 8.1%, which is better than the 11.2% of Comparative Example 1 and far better than the 40.4% of Comparative Example 2. Generally speaking, the thermal stability of benzoxazine resin (Comparative Example 1) is better than that of linear phenolic resin (Comparative Example 2), and the thermal stability is further improved after introducing aldehyde groups into the benzoxazine resin (Example 1).

[0094] 3. Evaluation of isothermal heat resistance The isothermal heat resistance test employed the same sample preparation method and instrumentation as the variable-temperature test. Under a nitrogen atmosphere, the sample was rapidly heated from room temperature to 400°C at a heating rate of 30 °C / min, and then held at 400°C for 20 min. The sample mass loss rate was measured and denoted as W. Loss-B %, recorded in Table 3.

[0095] It is generally believed that the lower the mass loss rate, the stronger the heat resistance.

[0096] 4. Evaluation of Shrinkage and High-Temperature Film Thickness Retention The composition sample was spin-coated onto a 4-inch silicon wafer at 1500 rpm, and then baked on a hot plate at 150°C for 90 seconds to completely remove the solvent. The thickness of the carbon coating was measured using an ellipsometry and recorded as T0. The coated silicon wafer was then placed back on a hot plate at 250°C and baked for 90 seconds to fully cure. The thickness of the carbon coating was measured again using an ellipsometry and recorded as T1. The film shrinkage rate C is then calculated. S %=[(T0-T1) / T0]×100%. (C S (The lower the percentage, the smaller the shrinkage). The coated silicon wafer was then placed back on a hot plate at 400°C for 90 seconds. The thickness of the carbon coating was then measured using an ellipsometry and denoted as T2. The high-temperature film thickness retention rate C is then calculated. H % = [T2 / T1] × 100%, and the results are listed in Table 3.

[0097] It is generally believed that low curing shrinkage and high film thickness retention are beneficial to the stability of device structure.

[0098] 5. Evaluation of Etching Resistance The composition sample was spin-coated onto a 4-inch silicon wafer at 1500 rpm, and then baked on a hot plate at 250°C for 60 s to form a spin-coated carbon coating. The etching rate of the spin-coated carbon coating was measured using an etching machine (ICP HAASRODE-E200A) with CF4 gas as the etching gas. The dry etching rates of the spin-coated carbon coatings prepared in the examples and comparative examples were compared. The dry etching rate ratios were calculated and are listed in Table 3. The calculation formula is as follows: Dry etching rate ratio = (etching rate of the example) / (etching rate of Comparative Example 2) The test results are shown in Table 3 below: Table 3

[0099] As shown in Table 3, the spin-coated carbon materials formulated with aldehyde-substituted benzoxazine resin (Examples 1-9) exhibit significant advantages over those formulated with aldehyde-free benzoxazine resin (Comparative Example 1) and linear phenolic resin (Comparative Example 2) in terms of heat resistance, shrinkage, high-temperature film thickness retention, and etching resistance, while maintaining good coating uniformity. This is because benzoxazine resin itself exhibits low shrinkage, high crosslinking density, and no small molecule release during curing; furthermore, the introduction of aldehyde groups further enhances the crosslinking density and overall strength of the material, thereby improving its heat resistance and etching resistance. Specifically, Comparative Example 1 used benzoxazine resin R1 without aldehyde substitution. With other components in the spin-coated carbon composition identical to those in Example 1, Example 1 exhibited significantly better coating performance, heat resistance, shrinkage, high-temperature film thickness retention, and etching resistance than Comparative Example 1. This demonstrates that by introducing aldehyde groups into the benzoxazine resin, this application can effectively improve the performance of the spin-coated carbon composition. In summary, the spin-coated carbon composition based on aldehyde-substituted benzoxazine resin in this application, while maintaining excellent coating performance, can significantly improve the thermal stability and etching resistance of the thin film, providing a new generation of hard mask materials for advanced semiconductor manufacturing.

[0100] The present application has been described above with reference to preferred embodiments; however, these embodiments are merely exemplary and illustrative. Various substitutions and modifications can be made to the present application based on these embodiments, all of which fall within the protection scope of the present application.

Claims

1. A spin-coated carbon composition, characterized in that, The spin-coated carbon composition comprises an aldehyde-substituted benzoxazine resin having the structure of Formula 1, a surfactant, and a solvent. Formula 1 Wherein, A contains at least one benzene ring fused with an oxazine ring, and is represented by any of the following structures: A-1， A-2， A-3， A-4， A-5， A-6， A-7， A-8， A-9， A-10； R1 is selected from hydrogen, C 1-10 Alkyl, halogen, cyano, C 1-10 ester group, C 1-10 ether group, C 2-10 alkenyl, C 2-10 One or more of the alkynyl groups; B is an aromatic ring structure containing 1 to 4 benzene rings with a γ valence; When B is substituted, the substituent is selected from C. 1-6 Alkyl, halogen, cyano, C 1-6 ester group, C 1-6 ether group, C 2-6 One or more of alkynyl and vinyl groups; n is an integer from 1 to 4; m is an integer between 0 and 4; x is an integer between 1 and 4; y is an integer from 1 to 4, and is greater than or equal to x; Indicates the connection site with -CHO; Indicates the connection site with R1; The weight ratio of the benzoxazine resin to the solvent is (1-30):(60-99).

2. The spin-coated carbon composition according to claim 1, characterized in that, It is formed by any of the following structures: ， ， ， ， ； in, Indicates the connection site with -CHO; This indicates the connection site with R1.

3. The spin-coated carbon composition according to claim 1, characterized in that, The aromatic ring structure in B is selected from one or more of benzene, fluorene, and naphthalene; R1 is selected from hydrogen, C 1-4 Alkyl, halogen, cyano, propargyl, vinyl, and allyl; and When B is substituted, the substituent is an ethynyl group; m and n are each an independent integer from 1 to 4.

4. The spin-coated carbon composition according to claim 1, characterized in that, The Mw of the aldehyde-substituted benzoxazine resin having the structure of Formula 1 is 200-10000 g / mol.

5. The spin-coated carbon composition according to claim 4, characterized in that, The Mw of the aldehyde-substituted benzoxazine resin having the structure of Formula 1 is 250-3000 g / mol.

6. The spin-coated carbon composition according to claim 1, characterized in that, Based on 100 parts by weight of the spin-coated carbon composition, the content of the surfactant is 0.0001-0.1 parts.

7. The spin-coated carbon composition according to claim 6, characterized in that, The spin-coated carbon composition also includes one or both of a crosslinking agent and an acid-producing agent.

8. The spin-coated carbon composition according to claim 7, characterized in that, The solvent is selected from one or more of alcohol solvents, ketone solvents, ester solvents, ether solvents, and aromatic hydrocarbon solvents; When the crosslinking agent is present, it is selected from compounds containing methoxymethyl, hydroxymethyl, hydroxyethyl, epoxy, or vinyl groups; and / or When the acid-producing agent is present, it is selected from ionic and / or nonionic compounds.

9. The spin-coated carbon composition according to claim 8, characterized in that, The solvent is selected from one or more of the following solvents: propylene glycol methyl ether acetate, propylene glycol methyl ether, ethylene glycol methyl ether acetate, diethylene glycol, propylene glycol methyl ether, propylene glycol monoethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, butyl acetate, neopentyl acetate, ethyl lactate, methyl ethyl ketone, methyl isobutyl ketone, γ-butyrolactone, cyclohexanone, dioxane, N , N -Dimethylformamide, N , N -Dimethylacetamide, dimethyl sulfoxide; The crosslinking agent has one or more of the following structures: ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ， ； The acid-producing agent is selected from one or more of the following: diphenyliodonium trifluoromethanesulfonate, diphenyliodonium camphor sulfonate, diphenyliodonium perfluoro-1-butanesulfonate, diphenyliodonium perfluorooctane sulfonate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, bis(4-tert-butylphenyl)iodonium tetrafluoroborate, bis(4-tert-butylphenyl)iodonium hexafluorophosphate, bis(4-tert-butylphenyl)iodonium trifluoromethanesulfonate, bis(4-tert-butylphenyl)iodonium perfluoro-1-butanesulfonate, bis(4-tert-butylphenyl) Iodomon camphor sulfonate, bis(4-tert-butylphenyl)iodomon perfluorooctane sulfonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium camphor sulfonate, triphenylsulfonium perfluoro-1-butyl sulfonate, triphenylsulfonium perfluorooctane sulfonate, p-tolyl diphenylsulfonium trifluoromethanesulfonate, p-tolyl diphenylsulfonium perfluorooctane sulfonate, p-tolyl diphenylsulfonium perfluoro-1-butane sulfonate, p-tolyl diphenylsulfonium camphor sulfonate, 2,4,6-trimethylphenyl diphenylsulfonium trifluoromethane sulfonate, 4-tert-butylphenyl diphenylsulfonium trifluoromethane sulfonate, 4-phenylbenzene Thiodiphenylsulfonium hexafluorophosphate, 1-(2-naphthylmethyl)thiosulfonium trifluoromethane sulfonate, 4-hydroxy-1-naphthyldimethylsulfonium trifluoromethane sulfonate, 2-methyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methyl) (O-1-naphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(benzo[d][1,3]dioxolane-5-yl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-dimethoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(2,4-dimethoxystyryl)-4,6 -bis(trichloromethyl)-1,3,5-triazine, 2-(2-methoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-butoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-pentoxystyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, diphenyl disulfone, di-p-tolyl disulfone, bis(phenylsulfonyl)diazomethane, bis(4-chlorophenylsulfonyl)diazomethane, bis(p-tolylsulfonyl)diazomethane, bis(4-tert-butylphenylsulfonyl)diazomethane, bis(2,4-Dimethylbenzyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, (benzoyl)(phenylsulfonyl)diazomethane, 1-benzoyl-1-phenylmethyl p-toluenesulfonic acid, 2-benzoyl-2-hydroxy-2-phenylethyl p-toluenesulfonic acid, 1,2,3-phenyltriyl trimethanesulfonic acid, 2,6-dinitrobenzoyl p-toluenesulfonic acid, 2-nitrobenzene p-toluenesulfonic acid, 4-nitrobenzene p-toluenesulfonic acid, N -(phenylsulfonyloxy)succinimide, N -(trifluoromethylsulfonyloxy)succinimide, N -(perfluoro-1-butanesulfonic acid) succinimide, N -(perfluorooctane sulfonate) succinimide, N -(perfluoro-1-butanesulfonic acid) phthalimide, N -(trifluoromethylsulfonyloxy)phthalimide, N -(perfluorooctane sulfonic acid) phthalimide, N -(trifluoromethylsulfonyloxy)-5-norbornene-2,3-dicarboxylic imide N -(perfluoro-1-butanesulfonic acid)-5-norbornene-2,3-dicarboxylic acid imide N -(perfluorooctane sulfonic acid)-5-norbornene-2,3-dicarboxylic acid imide N -(trifluoromethylsulfonyloxy)naphthylmethyleneisocyanoyl, N -(perfluoro-1-butanesulfonic acid)naphthyleneimide, N -(perfluorooctane sulfonic acid)naphthylene imide, N -(10-Camphorsulfonyloxy)naphthaleneximide, ammonium trifluoromethanesulfonate, ammonium perfluorobutanesulfonate, Ad-TFBS[4-adamantanecarboxy-1,1,2,2-tetrafluorobutanesulfonic acid]ammonium, AdOH-TFBS[3-hydroxy-4-adamantanecarboxy-1,1,2,2-tetrafluorobutanesulfonic acid]ammonium, Ad-DFMS[(adamantane-methoxycarbonyl)-difluoromethanesulfonic acid], AdOH-DFMS[3-hydroxyadamantyl-methoxycarbonyl)-difluoromethanesulfonic acid]ammonium, DHC-TFB SS[4-dehydrocholic acid-1,1,2,2-tetrafluorobutanesulfonic acid]ammonium, ODOT-DFMS[hexahydro-4,7-epoxyisobenzofuran-1(3H)-one, 6-(2,2'-difluoro-2-sulfonate acetate)]ammonium, tetrabutylammonium perfluorobutanesulfonate, p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid ethyl ester, trifluoroacetic acid pyridinium salt, hydroxyp-toluenesulfonic acid pyridinium salt, phthalimide derivatives and benzenesulfonamide derivatives, polyhalomethanes, benzyl halides; and / or The surfactant is selected from one or more of the following: acrylic surfactants, silicone surfactants, fluorocarbon surfactants, and polyoxyethylene surfactants.

10. The spin-coated carbon composition according to any one of claims 7 to 9, characterized in that, The spin-coated carbon composition comprises, by weight: 1-30 parts of aldehyde-substituted benzoxazine resin having the structure of Formula 1 0-5 parts of crosslinking agent 0-2 parts of acid-producing agent Surfactant 0.0001-0.1 parts Solvent 60-99 parts.

11. A method for manufacturing a semiconductor device, characterized in that, The semiconductor device manufacturing method includes: forming a spin-coated carbon hard mask using the spin-coated carbon composition according to any one of claims 1 to 10.

12. A semiconductor device, characterized in that, The semiconductor device is manufactured using the method of claim 11.

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