Patterned material compositions, patterned films, patterned substrates, semiconductor devices, and methods of making the same

Abstract

The present application belongs to the technical field of semiconductors, and particularly relates to a kind of patterning material composition, patterning film, patterning substrate, semiconductor device and preparation method thereof.Compared with prior art, the present application uses diaryl iodonium salt photo-acid generator, and simultaneously matches organic amine photo-quenching agent, organic acid and radical quencher, etc., uses diaryl iodonium salt to improve the sensitivity of patterning material composition, matches organic amine photo-quenching agent, and simultaneously uses organic acid and radical quencher, which can make the acid production of diaryl iodonium salt more uniform, effectively inhibit the diffusion of photo-acid, and make the distribution in patterning material more uniform, so as to obtain patterning material composition with good resolution, high sensitivity and excellent line width roughness.

Description

Technical Field

[0001] This invention belongs to the field of semiconductor technology, and particularly relates to a patterned material composition, a patterned thin film, a patterned substrate, a semiconductor device, and a method for preparing the same. Background Technology

[0002] Patterning is a critical step in semiconductor manufacturing, used to create intricate patterns on silicon wafers or other substrates. Patterning material compositions are key materials in photolithography processes, and their solubility changes under irradiation with ultraviolet light, electron beams, ion beams, or X-rays.

[0003] The main components of existing patterned material compositions include polymer resins with variable solubility, photoacid generators, solvents, and other additives.

[0004] With the continuous development of the semiconductor manufacturing field, the requirements for the resolution, roughness and sensitivity of patterning material compositions in the patterning process are constantly increasing. Although a lot of research has been carried out in the industry, satisfactory results have not yet been achieved. Summary of the Invention

[0005] In view of this, the technical problem to be solved by the present invention is to provide a patterned material composition, a patterned thin film, a patterned substrate, a semiconductor device, and a method for preparing the same, which simultaneously have high resolution, low roughness and high sensitivity.

[0006] This invention provides a patterned material composition comprising a resin, a photoacid generator, a photoquencher, a first organic acid, and a free radical quencher;

[0007] The photo-induced acid-producing agent includes diaryliodonium salt;

[0008] The light quencher is selected from one or more of alkyl tertiary amines, alkyl tertiary amine salts, aliphatic hydroxy tertiary amines and aliphatic hydroxy tertiary amine salts;

[0009] The free radical quencher is selected from one or more of phenolic compounds, nitrogen oxides, quinone compounds, nitro compounds, nitroso compounds, imine compounds, and nitrosamine compounds;

[0010] The anions in the alkyl tertiary amine salt and the aliphatic hydroxy tertiary amine salt are each independently formed by a second organic acid;

[0011] Furthermore, the content of the alkyl tertiary amine salt and / or aliphatic hydroxy tertiary amine salt in the patterned material composition is 0 when it differs from the content of the first organic acid.

[0012] This invention employs a diaryliodoium salt photoacid generator, combined with organic amine photoquenchers, organic acids, and free radical quenchers. The diaryliodoium salt enhances the sensitivity of the patterned material composition. When combined with organic amine photoquenchers, organic acids, and free radical quenchers, the acid generation by the diaryliodoium salt becomes more uniform, effectively suppressing photoacid diffusion and resulting in a more uniform distribution within the patterned material. This leads to a patterned material composition with good resolution, high sensitivity, and excellent line width roughness.

[0013] Preferably, the patterned material composition comprises, by weight:

[0014] 100 parts by weight of resin;

[0015] Photoacid-producing agent: 0.01~30 parts by weight;

[0016] Light quencher 0.01~5 parts by weight;

[0017] 0-10 parts by weight of the first organic acid;

[0018] Free radical quencher: 0.001 to 3 parts by weight.

[0019] Preferably, the diaryliodonium salt comprises the structure shown in formula (I):

[0020] Formula (I);

[0021] Wherein, R1 and R2 are each independently selected from C1 to C8 alkyl, C1 to C8 alkoxy, C6 to C12 aryl, C6 to C12 arylthio or C6 to C12 aryloxy; x and y represent the number of substituents, each independently selected from integers from 0 to 5;

[0022] And / or, the anion of the diaryliodonium salt is selected from perfluoroalkyl sulfonate.

[0023] Using the diaryliodonium salt shown in formula (I) as a photoacid generator, it has extremely high acid generation efficiency and can improve the sensitivity of patterned material compositions.

[0024] Preferably, R1 and R2 are each independently selected from C3-C5 alkyl, C3-C5 alkoxy, C6-C10 aryl, C6-C10 arylthio, or C6-C10 aryloxy; x and y are each independently selected from integers from 1 to 3;

[0025] And / or, the perfluoroalkyl sulfonate is selected from trifluoromethanesulfonate or nonafluorobutanesulfonate.

[0026] Preferably, the resin is selected from one or more of polyester resins, epoxy resins, acrylate resins, and polyhydroxystyrene resins;

[0027] And / or, the pKa of the first organic acid and the second organic acid are each independently less than 5;

[0028] And / or, the amount of the first organic acid is at least 0.05 times, preferably at least 0.25 times, and more preferably at least 1 times, the total amount of the alkyl tertiary amine and / or aliphatic hydroxy tertiary amine.

[0029] The use of moderate to strong acidic organic acids, which have significant dissociation capabilities in aqueous solutions, can improve the uniformity of patterned materials, assist free radical quenchers in their function, improve the LWR of the composition, and enhance resolution.

[0030] Preferably, the resin comprises one or more of the following: hydroxystyrene monomer units, acrylate monomer units, styrene monomer units, acrylate monomer units containing alicyclic rings, and acrylate monomer units containing lactones.

[0031] And / or, the diaryliodonium salt is selected from the compounds shown in A1 and / or A2:

[0032] A1; A2;

[0033] And / or, the alkyl tertiary amine is selected from one or more of triethylamine, tri-n-propylamine, triisopropylamine, tri-tert-butylamine, trioctylamine, and trilaurylamine;

[0034] And / or, the aliphatic hydroxy tertiary amine is selected from one or more of N,N-diethylhydroxyamine, N,N-dimethylethanolamine and triethanolamine;

[0035] And / or, the first organic acid and the second organic acid are each independently selected from one or more of salicylic acid, lactic acid and acetic acid;

[0036] And / or, the phenolic compound is selected from 2,6-di-tert-butyl-p-methylphenol and / or p-methylphenol;

[0037] And / or, the nitrogen oxide is selected from 2,2,6,6-tetramethyl-1-piperidine-N-oxy radical and / or 5,5-dimethyl-1-pyrrolline-N-oxide;

[0038] And / or, the quinone compound is selected from p-benzoquinone and / or tetramethylbenzoquinone;

[0039] And / or, the nitro compound is selected from one or more of nitrobenzene, 2,4-dinitrophenol, and 2,4,6-trinitrotoluene;

[0040] And / or, the nitroso compound is selected from nitrosobenzene and / or p-nitrosophenol;

[0041] And / or, the imine compound is selected from benzaldehyde aniline and / or salicylaldehyde o-phenylenediamine;

[0042] And / or, the nitrosamine compound is selected from N-nitrosodiphenylamine and / or N-nitroso-N-phenylnaphthylamine.

[0043] Preferably, it also includes a solvent; the solid content of the patterned material composition is 1% to 50%.

[0044] The solvent is selected from one or more of the following: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, and N-methylpyrrolidone.

[0045] The present invention also provides a patterned thin film formed from the above-described patterned material composition.

[0046] The present invention also provides a patterned substrate, which is prepared using the above-described patterned material composition.

[0047] The present invention also provides a semiconductor device fabricated using the patterned thin film or the patterned substrate described above.

[0048] This invention also provides a method for fabricating a semiconductor device, comprising the following steps:

[0049] The above-described patterned material composition is coated onto a substrate to form a film layer on the substrate;

[0050] The film layer is developed using a photomask to form a patterned thin film on the substrate. Attached Figure Description

[0051] Figure 1 This is a scanning electron microscope image of the line pattern prepared in Comparative Example 1 of the present invention;

[0052] Figure 2 This is a scanning electron microscope image of the line pattern prepared in Example 1 of the present invention. Detailed Implementation

[0053] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0054] This invention provides a patterned material composition comprising a resin, a photoacid-generating agent, a photoquencher, a first organic acid, and a free radical quencher; the photoacid-generating agent comprises a diaryliodomonium salt; the photoquencher is selected from one or more of alkyl tertiary amines, alkyl tertiary amine salts, aliphatic hydroxy tertiary amines, and aliphatic hydroxy tertiary amine salts; the free radical quencher is selected from one or more of phenolic compounds, nitrogen oxides, quinone compounds, nitro compounds, nitroso compounds, imine compounds, and nitrosoamine compounds; the anions in the alkyl tertiary amine salt and the aliphatic hydroxy tertiary amine salt are each independently formed by the first organic acid; and the content of the alkyl tertiary amine salt and / or the aliphatic hydroxy tertiary amine salt and the first organic acid in the patterned material composition is 0.

[0055] In one specific embodiment of the present invention, the patterned material composition includes:

[0056] 100 parts by weight of resin;

[0057] Photoacid-producing agent: 0.01~30 parts by weight;

[0058] Light quencher 0.01~5 parts by weight;

[0059] 0-10 parts by weight of the first organic acid;

[0060] Free radical quencher 0.001~3 parts by weight.

[0061] In this invention, the resin can be any resin known to those skilled in the art that can undergo solubility reversal, and there are no special limitations; in a specific embodiment provided by this invention, the resin includes, but is not limited to, one or more of polyester resins, epoxy resins, acrylate resins and polyhydroxystyrene resins.

[0062] In one specific embodiment of the present invention, the resin includes one or more of the following: hydroxystyrene monomer units, acrylate monomer units, styrene monomer units, acrylate monomer units containing alicyclic rings, and acrylate monomer units containing lactones.

[0063] In a specific embodiment of the present invention, the resin comprises hydroxystyrene monomer units, acrylate monomer units, and styrene monomer units; the molar ratio of the hydroxystyrene monomer units, acrylate monomer units, and styrene monomer units is preferably (40~80):(10~30):(10~30), more preferably (45~75):(15~25):(15~25), even more preferably (50~70):(15~25):(15~25), even more preferably (55~65):(18~22):(18~22), and most preferably 60:20:20; the acrylate monomer units are preferably alkyl acrylate monomer units, wherein the number of carbon atoms in the alkyl group is preferably an integer from 1 to 8, more preferably an integer from 2 to 6, even more preferably an integer from 3 to 5, and most preferably 3 or 4.

[0064] In a specific embodiment provided by the present invention, the resin comprises the structure shown in R1-1, R1-2 and R1-3:

[0065] R1-1 R1-2 R1-3

[0066] In another specific embodiment of the present invention, the resin comprises an acrylate monomer unit containing an alicyclic ring and an acrylate monomer unit containing a lactone; the alicyclic ring in the acrylate monomer unit includes, but is not limited to, one or more of five-membered alicyclic rings, six-membered alicyclic rings, and bridged rings; the acrylate monomer unit containing a lactone may also include an alicyclic structure; the molar ratio of the acrylate monomer unit containing an alicyclic ring to the acrylate monomer unit containing a lactone is preferably (2~8):(8~2), more preferably (3~7):(7~3), even more preferably (4~6):(6~4), and most preferably 5:1.

[0067] In one specific embodiment of the present invention, the resin comprises the structure shown in R2-1 and R2-2:

[0068] R2-1 R2-2

[0069] In a specific embodiment of the present invention, the weight-average molecular weight of the resin is preferably 5,000 to 50,000; optionally, the weight-average molecular weight of the resin is 5,000, 6,000, 7,000, 8,000, 9,000, 10,000, 11,000, 13,000, 15,000, 18,000, 20,000, 25,000, 30,000, 35,000, 40,000, 45,000, 50,000 or a range between any two of the above values.

[0070] In one specific embodiment of the present invention, optionally, the content of the photoacid-generating agent in the patterned material composition is 0.01 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.5 parts by weight, 1 part by weight, 3 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight, 14 parts by weight, 15 parts by weight, 16 parts by weight, 17 parts by weight, 18 parts by weight, 19 parts by weight, 20 parts by weight, 21 parts by weight, 22 parts by weight, 23 parts by weight, 24 parts by weight, 25 parts by weight, 26 parts by weight, 27 parts by weight, 28 parts by weight, 29 parts by weight, 30 parts by weight, or any two of the above values.

[0071] This invention uses diaryliodonium salt as a photoacid-generating agent, which has extremely high acid-generating efficiency and can improve the sensitivity of patterned material compositions; in a specific embodiment provided by this invention, the diaryliodonium salt includes the structure shown in formula (I):

[0072] Formula (I);

[0073] R1 and R2 are each preferably C1-C8 alkyl, C1-C8 alkoxy, C6-C12 aryl, C6-C12 arylthio, or C6-C12 aryloxy; more preferably C2-C6 alkyl, C2-C6 alkoxy, C6-C12 aryl, C6-C12 arylthio, or C6-C12 aryloxy; even more preferably C3-C5 alkyl, C3-C5 alkoxy, C6-C10 aryl, C6-C10 arylthio, or C6-C10 aryloxy; and most preferably C4 alkyl, C4 alkoxy, phenyl, phenylthio, or phenoxy.

[0074] x and y represent the number of substituents, and each is preferably an integer from 0 to 5; more preferably an integer from 1 to 4, even more preferably an integer from 1 to 3, and most preferably 1 or 2.

[0075] The present invention does not impose any special restrictions on the anion of the diaryliodomonium salt. In a specific embodiment provided by the present invention, the anion of the diaryliodomonium salt is preferably perfluoroalkyl sulfonate, more preferably trifluoromethanesulfonate or nonafluorobutyrate.

[0076] Although diaryliodonium salts have extremely high acid production efficiency, which can improve the sensitivity of patterned material compositions, the large amount of acid produced by iodonium salts results in a long photoacid diffusion length and uneven distribution, making it difficult to obtain patterns with better line width and roughness. This invention solves the above problems by combining a photoquencher, a first organic acid, and a free radical quencher.

[0077] In one specific embodiment of the present invention, the diaryliodonium salt is selected from compounds shown in A1 and / or A2:

[0078] A1; A2.

[0079] In a specific embodiment of the present invention, the content of the light quencher in the patterned material composition is preferably 0.01 parts by weight, 0.05 parts by weight, 0.1 parts by weight, 0.2 parts by weight, 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, 1 part by weight, 1.2 parts by weight, 1.5 parts by weight, 1.8 parts by weight, 2 parts by weight, 2.2 parts by weight, 2.5 parts by weight, 2.8 parts by weight, 3 parts by weight, 3.2 parts by weight, 3.5 parts by weight, 3.8 parts by weight, 4 parts by weight, 4.2 parts by weight, 4.5 parts by weight, 4.8 parts by weight, 5 parts by weight, or any two of the above values.

[0080] This invention uses one or more of alkyl tertiary amines, alkyl tertiary amine salts, aliphatic hydroxy tertiary amines, and aliphatic hydroxy tertiary amine salts as light quenchers.

[0081] In one specific embodiment of the present invention, the alkyl tertiary amine includes, but is not limited to, one or more of triethylamine, tri-n-propylamine, triisopropylamine, tri-tert-butylamine, trioctylamine, and trilauramine; the aliphatic hydroxy tertiary amine includes, but is not limited to, one or more of N,N-diethylhydroxyamine, N,N-dimethylethanolamine, and triethanolamine.

[0082] In a specific embodiment of the present invention, the alkyl tertiary amine salt is formed by the above-mentioned alkyl tertiary amine and a second organic acid; the aliphatic hydroxy tertiary amine salt is formed by the above-mentioned aliphatic hydroxy tertiary amine and a second organic acid; the anions in the alkyl tertiary amine salt and the aliphatic hydroxy tertiary amine salt are each independently formed by the second organic acid; the pKa of the second organic acid is preferably less than 5; specifically, the second organic acid includes, but is not limited to, one or more of salicylic acid, lactic acid and acetic acid.

[0083] In one specific embodiment of the present invention, optionally, the content of the first organic acid in the patterned material composition is 0 parts by weight, 0.1 parts by weight, 0.2 parts by weight, 0.3 parts by weight, 0.39 parts by weight, 0.4 parts by weight, 0.5 parts by weight, 0.6 parts by weight, 0.7 parts by weight, 0.8 parts by weight, 0.9 parts by weight, 1 part by weight, 1.1 parts by weight, 1.2 parts by weight, 1.3 parts by weight, 1.4 parts by weight, 1.5 parts by weight, 1.6 parts by weight, 1.7 parts by weight, 1.8 parts by weight, 1.9 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, 3.5 parts by weight, 4 parts by weight, 4.5 parts by weight, 5 parts by weight, 5.5 parts by weight, 6 parts by weight, 6.5 parts by weight, 7 parts by weight, 7.5 parts by weight, 8 parts by weight, 8.5 parts by weight, 9 parts by weight, 9.5 parts by weight, 10 parts by weight, or any two of the above values.

[0084] In one specific embodiment of the present invention, the pKa of the first organic acid is preferably less than 5; specifically, the first organic acid includes, but is not limited to, one or more of salicylic acid, lactic acid, and acetic acid. By adding the first organic acid, the free radical quencher can be assisted in its function, improving the LWR of the composition and increasing the resolution.

[0085] In a specific embodiment of the present invention, when the light quencher includes alkyl tertiary amines and / or aliphatic hydroxy tertiary amines, the content of the first organic acid in the patterned material composition is not 0; specifically, the amount of the first organic acid is more than 0.05 times the total amount of alkyl tertiary amines and / or aliphatic hydroxy tertiary amines, preferably more than 0.25 times, and more preferably more than 1 times.

[0086] In one specific embodiment of the present invention, the amount of the first organic acid is 0.05 to 5 times the total amount of alkyl tertiary amines and / or aliphatic hydroxy tertiary amines; optionally, the amount of the first organic acid is 0.05 times, 0.1 times, 0.2 times, 0.3 times, 0.4 times, 0.5 times, 0.6 times, 0.7 times, 0.8 times, 0.9 times, 1 time, 1.2 times, 1.5 times, 1.8 times, 2 times, 2.2 times, 2.5 times, 2.8 times, 3 times, 3.2 times, 3.5 times, 3.8 times, 4 times, 4.2 times, 4.5 times, 4.8 times, 5 times, or any two of the above values.

[0087] In one specific embodiment of the present invention, optionally, the content of the free radical quencher in the patterned material composition is 0.001 parts by weight, 0.005 parts by weight, 0.01 parts by weight, 0.03 parts by weight, 0.05 parts by weight, 0.08 parts by weight, 0.1 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 1 part by weight, 1.5 parts by weight, 2 parts by weight, 2.5 parts by weight, 3 parts by weight, or any two of the above values.

[0088] In this invention, the free radical quencher is one or more selected from phenolic compounds, nitrogen oxides, quinone compounds, nitro compounds, nitroso compounds, imine compounds, and nitrosamine compounds. In a specific embodiment provided by this invention, the free radical quencher preferably includes one or more selected from benzene rings, heterocycles, and alicyclic rings. Specifically, the phenolic compound includes, but is not limited to, 2,6-di-tert-butyl-p-methylphenol (BHT) and / or p-methylphenol (MEHQ); the nitrogen oxide includes, but is not limited to, 2,2,6,6-tetramethyl-1-piperidine-N-oxygen radical (TEM). The compounds include, but are not limited to, p-benzoquinone and / or tetramethylbenzoquinone; the nitro compounds include, but are not limited to, one or more of nitrobenzene, 2,4-dinitrophenol and 2,4,6-trinitrotoluene; the nitroso compounds include, but are not limited to, nitrosobenzene and / or p-nitrosophenol; the imine compounds include, but are not limited to, benzaldehyde aniline and / or salicylaldehyde o-phenylenediamine; the nitrosamine compounds include, but are not limited to, N-nitrosodiphenylamine and / or N-nitroso-N-phenylnaphthylamine.

[0089] In one specific embodiment of the present invention, the patterned material composition includes:

[0090] 100 parts by weight of resin;

[0091] 6 parts by weight of photoacid-producing agent;

[0092] Light quencher: 0.5-1.2 parts by weight;

[0093] 0-1.2 parts by weight of the first organic acid;

[0094] 0.01~0.1 parts by weight of free radical quencher.

[0095] In one specific embodiment of the present invention, the patterned material composition preferably further includes a solvent; the solid content of the patterned material composition is preferably 1% to 50%; optionally, the solid content of the patterned material composition is 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50% or any two of the above values.

[0096] In a specific embodiment of the present invention, the solvent preferably includes, but is not limited to, one or more of the following: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether (PGME), diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol propyl ether acetate, propylene glycol, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone (CYC), cycloheptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate (EL), butyl lactate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone (GBL), and N-methylpyrrolidone.

[0097] In one specific embodiment of the present invention, to improve the overall performance of the composition, the composition may further include other additives, which may be one or more of leveling agents and surfactants. The addition of leveling agents and surfactants can improve the uniformity of the coated film. The content of other additives in the composition can be adjusted according to actual needs.

[0098] This invention employs a diaryliodoium salt photoacid generator, combined with organic amine photoquenchers, organic acids, and free radical quenchers. The diaryliodoium salt enhances the sensitivity of the patterned material composition. When combined with organic amine photoquenchers, organic acids, and free radical quenchers, the acid generation by the diaryliodoium salt becomes more uniform, effectively suppressing photoacid diffusion and resulting in a more uniform distribution within the patterned material. This leads to a patterned material composition with good resolution, high sensitivity, and excellent linewidth roughness (LWR).

[0099] The present invention also provides a patterned thin film formed from the above-described patterned material composition.

[0100] The present invention also provides a patterning method, comprising the following steps: transferring the above-mentioned patterning material composition onto the surface of a substrate to form a coating, and then exposing and developing it with a mask to obtain a patterned thin film.

[0101] In one specific embodiment of the present invention, the composition is transferred to the substrate surface to form a coating by spin coating and / or coating diffusion methods.

[0102] The present invention also provides a patterned substrate formed using the above-described patterned composition. This patterned substrate can be used in the fabrication of electronic components such as chips, improving the precision and quality of device fabrication, thereby enhancing the performance of the electronic components.

[0103] In one specific embodiment of the present invention, the method for preparing a patterned substrate includes: forming a patterned thin film on a substrate, and transferring the pattern of the patterned thin film onto the substrate to obtain a patterned substrate. The process for forming the patterned thin film can be found in the preceding description and will not be repeated here.

[0104] The present invention also provides a semiconductor device employing the patterned thin film described above or the patterned substrate described above. Due to the use of the patterned thin film or patterned substrate provided by the present invention, the semiconductor device exhibits high precision.

[0105] In one specific embodiment of the present invention, the semiconductor device includes a structure obtained by etching or electron injection of a patterned substrate.

[0106] In one specific embodiment of the present invention, the semiconductor device is a structure obtained by etching or electron injection onto a patterned substrate with a silicon wafer as the substrate.

[0107] In one specific embodiment of the present invention, there is no limitation on the specific type of semiconductor device, which may include integrated circuit devices such as chips. During chip fabrication, other functional layers can be fabricated after the aforementioned patterning process is completed.

[0108] The present invention also provides a method for fabricating a semiconductor device, comprising: coating the above-mentioned patterned composition onto a substrate to form a film layer on the substrate; and developing the film layer by means of a photomask to form a patterned thin film on the substrate.

[0109] In a specific embodiment of the present invention, after forming a patterned thin film on a substrate, the above-mentioned semiconductor device fabrication method further includes: etching or electron-injecting the patterned substrate to form a pattern on the surface of the patterned substrate, thereby forming the structure required for the semiconductor device on the surface of the substrate, and obtaining the semiconductor device.

[0110] To further illustrate the present invention, the following detailed description, in conjunction with embodiments, describes a patterned material composition, a patterned thin film, a patterned substrate, a semiconductor device, and a method for preparing the same.

[0111] All reagents used in the following examples are commercially available.

[0112] Examples 1-10 and Comparative Examples 1-6

[0113] The formulation of the patterned material composition is shown in Table 1. Resin R1 is composed of R1-1, R1-2 and R1-3, with a molar ratio of R1-1, R1-2 and R1-3 of 60:20:20. The weight-average molecular weight of resin R1 is 15000. Resin R2 is composed of R2-1 and R2-2, with a molar ratio of R2-1 and R2-2 of 50:50. The weight-average molecular weight of resin R2 is 8000.

[0114] The structure of photoacid-producing agent A3 is shown below:

[0115] A3.

[0116] The light quenchers B1 are triethanolamine, B2 are trioctylamine, and B3 are trioctylamine salicylate salt.

[0117] The organic acids C1 is salicylic acid, C2 is lactic acid, C3 is acetic acid, and C4 is tertivalic acid.

[0118] The free radical quenchers are BHT for D1, MEHQ for D2, and TEMPO for D3.

[0119] According to the formulation in Table 1, each component was dissolved in a solvent to obtain a patterned material composition in a homogeneous solution state.

[0120] Table 1. Formulation composition of Examples 1-10 and Comparative Examples 1-6

[0121]

[0122] The formulations shown in the table above were spin-coated onto a 12-inch silicon wafer (spin-coating speed 1500 rpm, coating thickness 240 nm). The wafers were baked at 110°C for 90 s to remove the solvent, then exposed using an exposure machine (exposure wavelength 248 nm). After exposure, the wafers were baked at 135°C for 90 s, and then developed in a 2.38% TMAH developer to obtain line patterns. Sensitivity and LWR were evaluated using scanning electron microscopy (CD-SEM) as follows, and the results are shown in Table 2. The CD-SEM image of the line pattern prepared in Comparative Example 1 is shown below. Figure 1 As shown, the scanning electron microscope image of the line pattern prepared in Example 1 is obtained as follows. Figure 2 As shown.

[0123] Sensitivity: Determine the optimal exposure BE (mJ / cm²) for an LS pattern with a resolution of 150 nm, i.e., a linewidth of 150 nm and a period of 300 nm. 2 This value is defined as sensitivity. The smaller the value, the higher the sensitivity.

[0124] LWR: For an LS pattern obtained by irradiation with the optimal exposure (BE), the dimensions at 32 points along the long side of the line are measured. The standard deviation of these measurements is calculated as three times the LWR. The smaller this value, the lower the roughness of the pattern and the more uniform the line width.

[0125] Table 2 Sensitivity and LWR Evaluation Results

[0126]

[0127] As can be seen from Comparative Examples 1 and 4, using diaryliodonium salt as a photoacid generator significantly improves the sensitivity of the composition, but increases the LWR value and worsens the linewidth uniformity.

[0128] As can be seen from Comparative Examples 1 and 2, although the addition of organic acids or free radical quenchers can improve the sensitivity and linewidth uniformity of the composition, the improvement is limited.

[0129] In Comparative Example 5, the amount of organic acid was about 0.01 times that of the quencher, resulting in a higher LWR value. In contrast, in Examples 1 and 2, the amounts of organic acid were 1 time and 0.27 times that of the quencher, respectively, leading to lower LWR values. In Example 3, the amount of organic acid was 0.05 times that of the quencher. Compared to Examples 1 and 2, the LWR value increased as the amount of organic acid decreased, but it was still lower than that of Comparative Example 5.

[0130] According to the test results in Table 2, it can be found that the photoresist in the comparative example has a high LWR or low sensitivity, which is a poor performance. However, in the examples, the photoresist has high sensitivity and low LWR, which is a good performance.

[0131] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A patterned material composition, characterized in that, Including resins, photoacid generators, photoquenchers, primary organic acids and free radical quenchers; The photo-induced acid-producing agent is a diaryliodonium salt; The light quencher is selected from one or more of alkyl tertiary amines, alkyl tertiary amine salts, aliphatic hydroxy tertiary amines, and aliphatic hydroxy tertiary amine salts; The free radical quencher is selected from one or more of phenolic compounds, nitrogen oxides, quinone compounds, nitro compounds, nitroso compounds, imine compounds, and nitrosamine compounds; The anions in the alkyl tertiary amine salt and the aliphatic hydroxy tertiary amine salt are each independently formed by a second organic acid; Furthermore, the content of the alkyl tertiary amine salt and / or aliphatic hydroxy tertiary amine salt in the patterned material composition is 0 when it differs from the content of the first organic acid. The diaryl iodine salt comprises the structure shown in formula (I): Equation (I); Wherein, R1 and R2 are each independently selected from C1 to C8 alkyl, C1 to C8 alkoxy, C6 to C12 aryl, C6 to C12 arylthio or C6 to C12 aryloxy; x and y represent the number of substituents, each independently selected from integers from 0 to 5; The anion of the diaryliodomonium salt is selected from perfluoroalkyl sulfonate groups; The pKa of the first organic acid and the second organic acid are each independently less than 5.

2. The patterned material composition according to claim 1, wherein, by weight, the patterned material composition comprises: 100 parts by weight of resin; Photoacid-producing agent: 0.01~30 parts by weight; Light quencher 0.01~5 parts by weight; 0-10 parts by weight of the first organic acid; Free radical quencher: 0.001 to 3 parts by weight.

3. The patterned material composition according to claim 1 or 2, characterized in that, R1 and R2 are each independently selected from C3-C5 alkyl, C3-C5 alkoxy, C6-C10 aryl, C6-C10 arylthio or C6-C10 aryloxy; x and y are each independently selected from integers from 1 to 3; And / or, the perfluoroalkyl sulfonate is selected from trifluoromethanesulfonate or nonafluorobutanesulfonate.

4. The patterned material composition according to claim 1 or 2, characterized in that, The resin is selected from one or more of polyester resins, epoxy resins, acrylate resins, and polyhydroxystyrene resins; And / or, the amount of the first organic acid is more than 0.05 times the total amount of the alkyl tertiary amine and / or aliphatic hydroxy tertiary amine.

5. The patterned material composition according to claim 1 or 2, characterized in that, The resin comprises one or more of the following: hydroxystyrene monomer units, acrylate monomer units, styrene monomer units, acrylate monomer units containing alicyclic rings, and acrylate monomer units containing lactones. And / or, the diaryliodonium salt is selected from the compounds shown in A1 and / or A2: A1; A2; And / or, the alkyl tertiary amine is selected from one or more of triethylamine, tri-n-propylamine, triisopropylamine, tri-tert-butylamine, trioctylamine, and trilaurylamine; And / or, the aliphatic hydroxy tertiary amine is selected from one or more of N,N-diethylhydroxyamine, N,N-dimethylethanolamine and triethanolamine; And / or, the first organic acid and the second organic acid are each independently selected from one or more of salicylic acid, lactic acid and acetic acid; And / or, the phenolic compound is selected from 2,6-di-tert-butyl-p-methylphenol and / or p-methylphenol; And / or, the nitrogen oxide is selected from 2,2,6,6-tetramethyl-1-piperidine-N-oxy radical and / or 5,5-dimethyl-1-pyrrolline-N-oxide; And / or, the quinone compound is selected from p-benzoquinone and / or tetramethylbenzoquinone; And / or, the nitro compound is selected from one or more of nitrobenzene, 2,4-dinitrophenol, and 2,4,6-trinitrotoluene; And / or, the nitroso compound is selected from nitrosobenzene and / or p-nitrosophenol; And / or, the imine compound is selected from benzaldehyde aniline and / or salicylaldehyde o-phenylenediamine; And / or, the nitrosamine compound is selected from N-nitrosodiphenylamine and / or N-nitroso-N-phenylnaphthylamine.

6. The patterned material composition according to claim 2, characterized in that, It also includes a solvent; the solid content of the patterned material composition is 1% to 50%; The solvent is selected from one or more of the following: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, cycloheptanone, 4-methyl-2-pentanol, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, 2-heptanone, methoxycyclopentane, anisole, γ-butyrolactone, and N-methylpyrrolidone.

7. A patterned thin film, characterized in that, Formed from the patterned material composition according to any one of claims 1 to 6.

8. A patterned substrate, characterized in that, It is prepared using the patterned material composition according to any one of claims 1 to 6.

9. A semiconductor device, characterized in that, It is prepared using the patterned thin film of claim 7 or the patterned substrate of claim 8.

10. A method for fabricating a semiconductor device, characterized in that, Includes the following steps: The patterned material composition according to any one of claims 1 to 6 is coated on a substrate to form a film layer on the substrate; The film layer is developed using a photomask to form a patterned thin film on the substrate.

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