Modified phenolic resin composition as well as preparation method, cured film and application thereof

Abstract

The invention belongs to the technical field of high polymer materials, and discloses a modified phenolic resin composition, a preparation method thereof, a cured film and application. The modified phenolic resin composition provided by the invention takes modified phenolic resin with a specific structure as film-forming resin, and the structure of the modified phenolic resin composition comprises a structural unit I consisting of a diphenyl sulfide structure and a fluorene structure and a structural unit II consisting of the diphenyl sulfide structure and a phenol structure; a diphenyl sulfide structure and a fluorene structure are introduced into a modified phenolic resin structure in a special arrangement mode, an organic whole is formed through synergistic cooperation between the diphenyl sulfide structure and the fluorene structure, and the modified phenolic resin composition obtained by compounding the diphenyl sulfide structure with a photosensitizer and a cross-linking agent has excellent heat resistance and mechanical strength after film forming. The method can well meet the requirements of preparation of circuit devices with higher resolution, and has a good application prospect in preparation of semiconductor elements.

Description

Technical Field

[0001] The present invention belongs to the technical field of polymer materials, and in particular relates to a modified phenolic resin composition, a preparation method thereof, a cured film and applications thereof. Background Art

[0002] The semiconductor industry permeates every aspect of society, and photoresist plays a crucial role in the semiconductor device manufacturing process. Photoresist is primarily composed of a photosensitive resin, a photosensitizer, a solvent, and a crosslinker. The photosensitive resin significantly influences the photoresist's adhesion, corrosion resistance, mechanical strength, and other properties.

[0003] At present, the linear phenolic resin commonly used in photoresists is formed by polymerization of formaldehyde and phenol under acidic conditions. It has excellent film-forming photolithography performance and is the most widely used film-forming resin in g-line and i-line photoresists.

[0004] However, with the rapid development of the semiconductor industry and the needs of photolithography technology, ordinary linear phenolic resins have problems such as low glass transition temperature and low mechanical strength, which cannot meet the requirements of higher resolution circuit device preparation and have great limitations. Summary of the Invention

[0005] The first object of the present invention is to solve the problems of low glass transition temperature and mechanical strength of existing linear phenolic resins, and to provide a modified phenolic resin composition.

[0006] The second object of the present invention is to provide a method for preparing the modified phenolic resin composition.

[0007] A third object of the present invention is to provide a cured film.

[0008] A fourth object of the present invention is to provide use of the modified phenolic resin composition or cured film in the preparation of semiconductor devices.

[0009] Specifically, the modified phenolic resin composition provided by the present invention comprises a modified phenolic resin, a photosensitizer, and a crosslinking agent; wherein the modified phenolic resin comprises a structural unit I represented by formula (1) and a structural unit II represented by formula (2):

[0010]

[0011] In formula (1), R1 to R4 are each independently selected from a hydrogen atom, a C1 to C 10 Monovalent aliphatic groups, C1~C 10 R5 and R7 are each independently selected from a hydrogen atom, a C1 to C 10Monovalent aliphatic groups, C1~C 10 one or more monovalent aliphatic groups, m1=1 or 2, m3=1 or 2, 2≤m1+m3≤4; R6 and R8 are each independently selected from one or more of a halogen atom, a carboxyl group, a sulfonic acid group and a hydroxyl group, m2=1, 2 or 3, m4=1, 2 or 3, 2≤m2+m4≤4, and n1≥2;

[0012] In formula (2), R9 and R 11 Each independently selected from hydrogen atom, C1 to C 10 Monovalent aliphatic groups, C1~C 10 One or more monovalent aliphatic groups, m5 = 1 or 2, m7 = 1 or 2, and 2 ≤ m5 + m7 ≤ 4; R 10 and R 12 Each is independently selected from one or more of a halogen atom, a carboxyl group, a sulfonic acid group and a hydroxyl group, m6=1, 2 or 3, m8=1, 2 or 3, 2≤m6+m8≤4; A is a divalent phenol group, and n2≥2.

[0013] Furthermore, A in the structural unit II is a divalent phenol group derived from a phenolic compound having a structure as shown in formula (3):

[0014]

[0015] In formula (3), R 13 is a hydrogen atom, a methyl group, an ethyl group, a propyl group or a hydroxymethyl group; R 14 One or more selected from carboxyl, sulfonic acid, hydroxyl, hydroxymethyl, aldehyde and cyano groups, m9 = 1, 2 or 3, m 10 =0, 1, 2 or 3, and m9+m 10 ≤5.

[0016] Furthermore, the preparation of the modified phenolic resin includes:

[0017] S1, taking a diphenyl sulfide compound represented by the structure of formula (4) and a phenol compound represented by the structure of formula (5) and performing a prepolymerization reaction in the presence of an acid catalyst to obtain a prepolymer;

[0018]

[0019] In formula (4), R 15 and R 16 Each independently selected from hydrogen atom, C1 to C 10 Monovalent aliphatic groups, C1~C 10 One or more monovalent aliphatic groups, m11 =1 or 2, m 12 =1 or 2;

[0020] In formula (5), R 17 is a hydrogen atom, a methyl group, an ethyl group, a propyl group or a hydroxymethyl group, R 18 is absent or selected from one or more of carboxyl, sulfonic acid, hydroxyl, methylol, aldehyde and cyano groups, m 13 =1, 2 or 3, m 14 = 0, 1, 2, or 3;

[0021] S2, taking the diphenyl sulfide compound, the prepolymer and the fluorene compound having a structure as shown in formula (6) and performing a polymerization reaction in the presence of an acid catalyst to obtain the modified phenolic resin;

[0022]

[0023] In formula (6), R 19 ~R 22 Each independently selected from hydrogen atom, C1 to C 10 Monovalent aliphatic groups, C1~C 10 Z1 and Z2 are each independently selected from one of hydroxyl, methoxy, ethoxy, hydroxymethyl and methoxymethyl.

[0024] Furthermore, in the preparation of the modified phenolic resin, the added molar ratio of the diphenyl sulfide compound, the phenol compound and the fluorene compound is (2-4):1:(1-2.5).

[0025] Furthermore, in the preparation of the modified phenolic resin, the diphenyl sulfide compound is 2,2',4,4'-tetrahydroxydiphenyl sulfide.

[0026] Furthermore, in the preparation of the modified phenolic resin, the phenolic compound is selected from one or more of 2,6-bis(hydroxymethyl)-p-cresol, p-cresol and m-cresol.

[0027] Furthermore, the fluorene compound is selected from one or more of 9,9-bis(methoxymethyl)fluorene, 9,9-fluorenedimethanol and 3,6-dimethyl-9,9-bis(methoxymethyl)fluorene.

[0028] Furthermore, in the preparation of the modified phenolic resin, the acid catalyst is selected from one or more of hydrochloric acid, benzenesulfonic acid, p-toluenesulfonic acid, oxalic acid and acidic ion exchange resin.

[0029] Furthermore, in the preparation of the modified phenolic resin, based on the total mass of the diphenyl sulfide compound, the phenol compound and the fluorene compound, the total amount of the acid catalyst added in the prepolymerization reaction and the polymerization reaction is 0.5 wt % to 3 wt %.

[0030] Furthermore, in the preparation of the modified phenolic resin, in step S1, the temperature of the prepolymerization reaction is 70° C. to 120° C., and the time is 4 hours to 12 hours.

[0031] Furthermore, in the preparation of the modified phenolic resin, in step S2, the polymerization reaction temperature is 80° C. to 140° C., and the polymerization reaction time is 8 h to 16 h.

[0032] Furthermore, the photosensitizer is a diazonaphthoquinone compound and / or a diaryl onium iodide compound.

[0033] Furthermore, the naphthoquinone diazide compound is selected from one or more of 2,1,4-naphthoquinone diazide-5-sulfonate, 2,3,4,4'-tetrahydroxybenzophenone-2,1,4-naphthoquinone diazide sulfonate and 2,1,4-naphthoquinone diazide sulfonate.

[0034] Furthermore, the diaryl onium iodide salt compound is bis(4-tert-butylphenyl)iodonium perfluoro-1-butanesulfonic acid.

[0035] Furthermore, the cross-linking agent is a melamine compound and / or a glycoluril compound.

[0036] Furthermore, the melamine compound is selected from one or more of hexamethoxymethyl melamine, hexahydroxymethyl melamine and hexaethoxymethyl melamine.

[0037] Furthermore, the glycoluril compound is tetramethoxymethyl glycoluril and / or N,N'-bis(methoxymethyl)urea.

[0038] Furthermore, the modified phenolic resin composition includes a solvent, and the solvent is selected from one or more of propylene glycol methyl ether acetate, propylene glycol methyl ether, ethylene glycol dimethyl ether, anisole, γ-butyrolactone, ethyl lactate, n-heptane and dimethyl sulfoxide.

[0039] Furthermore, based on the total mass of the modified phenolic resin composition, the concentration of the modified phenolic resin is 10wt% to 45wt%, the concentration of the photosensitizer is 0.5wt% to 3wt%, the concentration of the crosslinker is 0.5wt% to 3wt%, and the concentration of the solvent is 49wt% to 89wt%.

[0040] The preparation method of the modified phenolic resin composition provided by the present invention comprises: mixing the modified phenolic resin, a photosensitizer, a crosslinking agent and an optional solvent to obtain the modified phenolic resin composition.

[0041] The cured film provided by the present invention is prepared by thermally curing the modified phenolic resin composition.

[0042] The present invention also provides the use of the modified phenolic resin composition and / or cured film in the preparation of semiconductor elements.

[0043] Beneficial effects:

[0044] The modified phenolic resin composition provided by the present invention uses a modified phenolic resin with a specific structure as a film-forming resin. The structure of the modified phenolic resin includes a structural unit I composed of a diphenyl sulfide structure and a fluorene structure, and a structural unit II composed of a diphenyl sulfide structure and a phenol structure. The diphenyl sulfide structure and the fluorene structure are introduced into the resin structure in a special arrangement to form an organic whole. The synergistic coordination between the diphenyl sulfide structure and the fluorene structure can significantly improve the thermal stability, flexibility, ductility and strength of the obtained modified phenolic resin. The modified phenolic resin composition obtained by compounding the modified phenolic resin composition with a photosensitizer and a crosslinking agent has excellent heat resistance and mechanical strength, can well meet the requirements for preparing higher-resolution circuit devices, and has good application prospects in the preparation of semiconductor elements.

[0045] In some specific embodiments, a two-step method is used to prepare a modified phenolic resin. First, a diphenyl sulfide compound and a phenolic compound are used for a prepolymerization reaction. Then, the prepolymer obtained from the prepolymerization reaction is polymerized with a fluorene compound. This method can control the structure and degree of polymerization of the obtained polymer, so as to ultimately obtain the above-mentioned modified phenolic resin with a special functional group arrangement and a narrow molecular weight distribution. In addition, this preparation method does not require a complex post-processing process, greatly reduces the process complexity, reduces the problems of reduced yield and increased waste liquid caused by the complex post-processing process, and has good application prospects in actual industrial production. DETAILED DESCRIPTION

[0046] Compared with the most commonly used linear phenolic resin in the prior art, the modified phenolic resin composition provided by the present invention has better heat resistance and mechanical strength, meets the requirements for the preparation of higher-resolution circuit devices, and has good application prospects.

[0047] In the present invention, the modified phenolic resin composition uses a modified phenolic resin with a specific structure as a film-forming resin. The structure of the modified phenolic resin specifically includes structural unit I and structural unit II. Structural unit I and structural unit II can be arranged in an irregular random manner or in a periodic alternating manner with a certain regularity. The present invention does not impose any particular limitation on their specific arrangement.

[0048] In the structure of the modified phenolic resin, structural unit I is formed by polymerization of diphenyl sulfide compounds and fluorene compounds, and the specific structure is shown in formula (1):

[0049]

[0050] In formula (1), R1 to R4 are each independently selected from a hydrogen atom, a C1 to C 10 Monovalent aliphatic groups, C1~C 10 R5 and R7 are each independently selected from a hydrogen atom, a C1 to C 10 Monovalent aliphatic groups, C1~C 10 One or more monovalent aliphatic groups, m1 = 1 or 2, m3 = 1 or 2, 2 ≤ m1 + m3 ≤ 4; R6 and R8 are each independently selected from one or more of halogen atoms, carboxyl groups, sulfonic acid groups and hydroxyl groups, m2 = 1, 2 or 3, m4 = 1, 2 or 3, 2 ≤ m2 + m4 ≤ 4, and n1 ≥ 2. 10 Specific examples of monovalent aliphatic groups include, but are not limited to, one or more of -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)CH2CH3, and -(CH2)6CH3. 10 Specific examples of the monovalent aliphatic group include, but are not limited to, one or more of -CH2F, -CH2CH2F, -CH(CH3)CH2(F)CH3, and -C(CH3)2F. Specific examples of the halogen atom include, but are not limited to, one or more of Cl, Br, and I.

[0051] In the structural unit I, the positions at which R5, R6, R7, and R8 are bonded to the benzene ring are not limited. R5, R6, R7, and R8 and their bonding relationships may be completely identical, non-completely identical, or completely different between different structural units I. The specific structure of the structural unit I is determined according to the conditions of the monomer polymerization reaction used, and the present invention does not impose any particular limitation thereto.

[0052] In the structure of the modified phenolic resin, structural unit II is formed by polymerization of diphenyl sulfide compounds and phenolic compounds, and the specific structure is shown in formula (2):

[0053]

[0054] In formula (2), R9 and R 11 Each independently selected from hydrogen atom, C1 to C 10 Monovalent aliphatic groups, C1~C 10 One or more monovalent aliphatic groups, m5 = 1 or 2, m7 = 1 or 2, and 2 ≤ m5 + m7 ≤ 4; R 10 and R 12 Each is independently selected from one or more of halogen atoms, carboxyl groups, sulfonic acid groups and hydroxyl groups, m6=1, 2 or 3, m8=1, 2 or 3, 2≤m6+m8≤4; A is a divalent phenol group, and n2≥2. 10 Specific examples of monovalent aliphatic groups include, but are not limited to, one or more of -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)CH2CH3, and -(CH2)6CH3. 10 Specific examples of the monovalent aliphatic group include, but are not limited to, one or more of -CH2F, -CH2CH2F, -CH(CH3)CH2(F)CH3, and -C(CH3)2F. Specific examples of the halogen atom include, but are not limited to, one or more of Cl, Br, and I.

[0055] In the structural unit II, R9 and R 10 、R 11 、R 12 As well as the position of the bond between A and the benzene ring, between different structural units II R9, R 10 、R 11 、R 12 A and its bonding relationship may be completely identical, non-completely identical or completely different. The specific structure of structural unit II is determined according to the conditions of the monomer polymerization reaction, and the present invention does not impose any particular limitation thereto.

[0056] In structural unit II, A is a divalent phenol group derived from a phenolic compound having a structure as shown in formula (3):

[0057]

[0058] In formula (3), R 13 is a hydrogen atom, a methyl group, an ethyl group, a propyl group or a hydroxymethyl group; R 14One or more selected from carboxyl, sulfonic acid, hydroxyl, hydroxymethyl, aldehyde and cyano groups, m9 = 1, 2 or 3, m 10 =0, 1, 2 or 3, and m9+m 10 ≤5.

[0059] In A, R is not restricted 14 , -OH and -CH2R 13 The position of the bond with the benzene ring, between different A R 14 , -OH and -CH2R 13 The bonding relationship thereof may be completely identical, non-completely identical or completely different. The specific structure of A is determined according to the conditions of the monomer polymerization reaction adopted, and the present invention does not impose any particular limitation thereto.

[0060] In formula (1) and formula (2), * represents a position where one structural unit is bonded to another structural unit.

[0061] In the present invention, the method for preparing the modified phenolic resin preferably includes the following steps: S1, performing a prepolymerization reaction on a diphenyl sulfide compound and a phenolic compound in the presence of an acid catalyst to obtain a prepolymer; S2, performing a polymerization reaction on the diphenyl sulfide compound, the prepolymer, and a fluorene compound in the presence of an acid catalyst to obtain the modified phenolic resin. In this step, the diphenyl sulfide compound and the phenolic compound are first reacted to produce a prepolymer having a compound having the structure represented by formula (2) as a main component, and then the fluorene compound is added to react with the prepolymer and the diphenyl sulfide compound to obtain the modified phenolic resin.

[0062] In the preparation of the modified phenolic resin, the structure of the diphenyl sulfide compound is specifically shown in formula (4):

[0063]

[0064] In formula (4), R 15 and R 16 Each independently selected from hydrogen atom, C1 to C 10 Monovalent aliphatic groups, C1~C 10 One or more monovalent aliphatic groups, m 11 =1 or 2, m 12 =1 or 2. Wherein, the C1~C 10 Specific examples of monovalent aliphatic groups include, but are not limited to, one or more of -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)CH2CH3, and -(CH2)6CH3. 10Specific examples of the monovalent aliphatic group include, but are not limited to, one or more of -CH2F, -CH2CH2F, -CH(CH3)CH2(F)CH3, and -C(CH3)2F. Specific examples of the halogen atom include, but are not limited to, one or more of Cl, Br, and I.

[0065] In some specific embodiments, specific examples of the diphenyl sulfide compound include but are not limited to: 2,2',4,4'-tetrahydroxydiphenyl sulfide.

[0066] In the preparation of the modified phenolic resin, the structure of the phenolic compound is specifically shown in formula (5):

[0067]

[0068] In formula (5), R 17 is a hydrogen atom, a methyl group, a methyl group, an ethyl group, a propyl group or a hydroxymethyl group, R 18 is absent or selected from one or more of carboxyl, sulfonic acid, hydroxyl, methylol, aldehyde and cyano groups, m 13 =1, 2 or 3, m 14 =0, 1, 2 or 3.

[0069] In some specific embodiments, specific examples of the phenolic compound include, but are not limited to, one or more of 2,6-bis(hydroxymethyl)-p-cresol, p-cresol, and m-cresol.

[0070] In the preparation of the modified phenolic resin, the structure of the fluorene compound is specifically shown in formula (6):

[0071]

[0072] In formula (6), R 19 ~R 22 Each independently selected from hydrogen atom, C1 to C 10 Monovalent aliphatic groups, C1~C 10 wherein C1 to C2 are selected from the group consisting of monovalent aliphatic groups, Z1 and Z2 are independently selected from the group consisting of hydroxyl, methoxy, ethoxy, hydroxymethyl and methoxymethyl. 10 Specific examples of monovalent aliphatic groups include, but are not limited to, one or more of -CH3, -CH2CH3, -CH2CH2CH3, -CH(CH3)CH2CH3, and -(CH2)6CH3. 10Specific examples of the monovalent aliphatic group include, but are not limited to, one or more of -CH2F, -CH2CH2F, -CH(CH3)CH2(F)CH3, and -C(CH3)2F. Specific examples of the halogen atom include, but are not limited to, one or more of Cl, Br, and I.

[0073] In some specific embodiments, specific examples of the fluorene compound include, but are not limited to, one or more of 9,9-bis(methoxymethyl)fluorene, 9,9-fluorenedimethanol, and 3,6-dimethyl-9,9-bis(methoxymethyl)fluorene.

[0074] In the preparation of the modified phenolic resin, the diphenyl sulfide compound in step S2 can be the diphenyl sulfide compound added in step S1 but not reacted and retained in the prepolymer, or can be the diphenyl sulfide compound added separately in step S2. The present invention does not impose any particular limitation on the specific addition method.

[0075] In the preparation of the modified phenolic resin, the added molar ratio of the diphenyl sulfide compound, the phenol compound and the fluorene compound is preferably (2-4):1:(1-2.5), specifically 2:1:1, 2.5:1:1.5, 2.5:1:2, 3:1:2, 4:1:2.5 or any value therebetween.

[0076] In the preparation of modified phenolic resin, the acid catalyst refers to the acid catalyst that can provide H + A type of substance that reduces the activation energy of prepolymerization and polymerization reactions, thereby accelerating the reaction process, is a type of reagent commonly used in the preparation of phenolic resins, and the present invention does not impose any particular limitation on it.

[0077] In some specific embodiments, specific examples of the acid catalyst include, but are not limited to, one or more of hydrochloric acid, benzenesulfonic acid, p-toluenesulfonic acid, oxalic acid, and acidic ion exchange resin.

[0078] In the preparation of the modified phenolic resin, the acid catalyst in step S2 can be the acid catalyst added in step S1 and retained in the prepolymer, or it can be an acid catalyst added separately in step S2. The present invention does not impose any particular limitation on the specific addition method.

[0079] In the preparation of the modified phenolic resin, based on the total mass of the diphenyl sulfide compound, the phenol compound and the fluorene compound, the total amount of the acid catalyst added in the prepolymerization reaction and the polymerization reaction is preferably 0.5wt% to 3wt%, specifically 0.5wt%, 0.8wt%, 1wt%, 1.2wt%, 1.4wt%, 1.8wt%, 2wt%, 2.3wt%, 2.7wt%, 3wt% or any value therebetween.

[0080] In the preparation of the modified phenolic resin, in step S1, the conditions of the prepolymerization reaction specifically include a temperature of preferably 70°C to 120°C, specifically 70°C, 73°C, 75°C, 78°C, 80°C, 83°C, 85°C, 90°C, 95°C, 100°C, 110°C, 120°C or any value therebetween; and a time of preferably 4h to 12h, specifically 4h, 4.5h, 5h, 5.3h, 6h, 7h, 9h, 10h, 12h or any value therebetween.

[0081] In the preparation of the modified phenolic resin, in step S2, the conditions of the polymerization reaction specifically include a temperature of preferably 80°C to 140°C, specifically 80°C, 85°C, 90°C, 95°C, 100°C, 110°C, 125°C, 130°C, 140°C or any value therebetween; and a time of preferably 8h to 16h, specifically 8h, 8.4h, 8.6h, 9h, 10h, 12h, 14h, 16h or any value therebetween.

[0082] In the present invention, the modified phenolic resin composition comprises a photosensitizer, a crosslinking agent and an optional solvent.

[0083] Specifically, the photosensitizer refers to a type of substance that can absorb light of a specific wavelength and transition from a ground state to an excited state, thereby promoting a photochemical reaction in the substrate through energy transfer, charge transfer, or direct participation in a chemical reaction. It is a type of reagent commonly used in photoresists and is not particularly limited in the present invention. Specific examples include, but are not limited to, diazonaphthoquinone compounds and / or diaryl onium iodide compounds.

[0084] In some specific embodiments, the naphthoquinone diazide compound is preferably selected from one or more of 2,1,4-naphthoquinone diazide-5-sulfonate, 2,3,4,4'-tetrahydroxybenzophenone-2,1,4-naphthoquinone diazide sulfonate and 2,1,4-naphthoquinone diazide sulfonate.

[0085] In some specific embodiments, the diaryl onium iodide salt compound is preferably bis(4-tert-butylphenyl)iodonium perfluoro-1-butanesulfonic acid.

[0086] Specifically, the crosslinking agent refers to a type of substance that can promote the formation of covalent bonds between modified phenolic resin molecular chains through chemical reactions, thereby constructing a three-dimensional network structure. It is a type of reagent commonly used in photoresists. The present invention does not impose any special restrictions on it. Specific examples include but are not limited to: melamine compounds and / or glycoluril compounds.

[0087] In some specific embodiments, the melamine compound is preferably selected from one or more of hexamethoxymethyl melamine, hexahydroxymethyl melamine and hexaethoxymethyl melamine.

[0088] In some specific embodiments, the glycoluril compound is preferably tetramethoxymethyl glycoluril and / or N,N'-bis(methoxymethyl)urea.

[0089] Specifically, the solvent is a type of reagent commonly used in photoresist, and the present invention does not impose any particular limitation on it. Specific examples include but are not limited to: one or more of propylene glycol methyl ether acetate, propylene glycol methyl ether, ethylene glycol dimethyl ether, anisole, γ-butyrolactone, ethyl lactate, n-heptane and dimethyl sulfoxide.

[0090] In the present invention, based on the total mass of the modified phenolic resin composition, the concentration of the modified phenolic resin is preferably 10wt% to 45wt%, specifically 10wt%, 13wt%, 15wt%, 18wt%, 20wt%, 25wt%, 30wt%, 35wt%, 40wt%, 45wt% or any value therebetween; the concentration of the photosensitizer is preferably 0.5wt% to 3wt%, specifically 0.5wt%, 0.8wt%, 0.9wt%, 1wt%, 1.3wt%, 1.5wt%, 2wt%, 2.5wt%, 3 wt% or any value therebetween; the concentration of the cross-linking agent is preferably 0.5wt% to 3wt%, specifically 0.5wt%, 0.7wt%, 0.9wt%, 1.1wt%, 1.5wt%, 1.9wt%, 2.5wt%, 2.9wt%, 3wt% or any value therebetween; the concentration of the solvent is preferably 49wt% to 89wt%, specifically 49wt%, 50wt%, 53wt%, 58wt%, 60wt%, 67wt%, 70wt%, 80wt%, 85wt%, 89wt% or any value therebetween.

[0091] The present invention also provides a method for preparing the modified phenolic resin composition. The method specifically comprises: mixing the modified phenolic resin, a photosensitizer, a crosslinking agent and an optional solvent to obtain the modified phenolic resin composition.

[0092] In the present invention, the method of mixing the modified phenolic resin, photosensitizer, crosslinking agent and optional solvent is a technical means commonly used in the prior art. Those skilled in the art can make adaptive choices according to actual needs, and the present invention does not impose any special limitation thereto.

[0093] The present invention also provides a cured film, which is prepared by thermally curing the modified phenolic resin composition.

[0094] In the present invention, the conditions for thermal curing include a temperature of preferably 180°C to 250°C, specifically 180°C, 190°C, 200°C, 210°C, 220°C, 230°C, 240°C, 250°C or any value therebetween; a time of preferably 20min to 50min, specifically 20min, 25min, 30min, 35min, 40min, 45min, 50min or any value therebetween.

[0095] The present invention also provides the use of the modified phenolic resin composition or cured film in the preparation of semiconductor elements.

[0096] The embodiments of the present invention are described in detail below. The examples of the embodiments are intended to explain the present invention and are not to be construed as limiting the present invention. Where specific techniques or conditions are not specified in the embodiments, they are performed according to the techniques or conditions described in the literature in this area or according to the product specifications. Reagents or instruments used that do not specify the manufacturer are all conventional products that can be obtained commercially.

[0097] Preparation Example 1

[0098] This preparation example is used to illustrate the preparation of a modified phenolic resin R1, which specifically includes:

[0099] S1. To a 0.5 L three-necked flask equipped with a Dean-Stark water trap, a condenser and a stirring device, 75.081 g (0.3 mol) of 2,2',4,4'-tetrahydroxydiphenyl sulfide, 16.819 g (0.1 mol) of 2,6-bis(hydroxymethyl)-p-cresol, 117.332 g of a 50 wt% PGME solution and 2.933 g of a 2.5 wt% oxalic acid solution were added, and nitrogen was continuously introduced for protection. The mixture was refluxed at 110 ° C with continuous stirring for 8 h, and then cooled to room temperature to obtain a prepolymer R1'.

[0100] S2. Add 25.432 g (0.1 mol) of 9,9-bis(methoxymethyl)fluorene to the prepolymer R1', continue to introduce nitrogen protection, reflux reaction at 130°C with continuous stirring for 12 hours, and cool to room temperature to obtain product R1.

[0101] S3. Take product R1 and 250g of 50wt% PGME solution, mix them and put them into a dropping funnel. Under high-speed stirring, uniformly add 6L of ultrapure water to precipitate the resin powder, filter and vacuum dry it to obtain modified phenolic resin R1.

[0102] The modified phenolic resin R1 obtained in this preparation example had a weight average molecular weight of 9000 and a PDI of 2.4 as measured by gel permeation chromatography.

[0103] Preparation Example 2

[0104] This preparation example is used to illustrate the preparation of a modified phenolic resin R2, which specifically includes:

[0105] S1. To a 0.5 L three-necked flask equipped with a Dean-Stark water trap, a condenser and a stirring device, 75.081 g (0.3 mol) of 2,2',4,4'-tetrahydroxydiphenyl sulfide, 25.229 g (0.15 mol) of 2,6-bis(hydroxymethyl)-p-cresol, 125.742 g of a 50 wt% PGME solution and 3.144 g of a 2.5 wt% oxalic acid solution were added, and nitrogen was continuously introduced for protection. The mixture was refluxed at 110 ° C with continuous stirring for 8 h, and then cooled to room temperature to obtain a prepolymer R2'.

[0106] S2. Add 25.432 g (0.1 mol) of 9,9-bis(methoxymethyl)fluorene to the prepolymer R2', continue to introduce nitrogen protection, reflux the reaction at 130°C with continuous stirring for 12 hours, and cool to room temperature to obtain product R2.

[0107] S3. Take product R2 and 377g of 50wt% PGME solution, mix them and put them into a dropping funnel. Under high-speed stirring, uniformly add 7.5L of ultrapure water to precipitate the resin powder, filter and vacuum dry it to obtain modified phenolic resin R2.

[0108] The modified phenolic resin R2 obtained in this preparation example had a weight average molecular weight of 9700 and a PDI of 2.6 as measured by gel permeation chromatography.

[0109] Preparation Example 3

[0110] This preparation example is used to illustrate the preparation of a modified phenolic resin R3, which specifically includes:

[0111] S1. To a 0.5 L three-necked flask equipped with a Dean-Stark water trap, a condenser and a stirring device, 100.108 g (0.4 mol) of 2,2',4,4'-tetrahydroxydiphenyl sulfide, 16.819 g (0.1 mol) of 2,6-bis(hydroxymethyl)-p-cresol, 142.359 g of a 50 wt% PGME solution and 3.560 g of a 2.5 wt% oxalic acid solution were added, and nitrogen was continuously introduced for protection. The mixture was refluxed at 110° C. with continuous stirring for 8 h, and then cooled to room temperature to obtain a prepolymer R3'.

[0112] S2. Add 25.432 g (0.1 mol) of 9,9-bis(methoxymethyl)fluorene to the prepolymer R3', continue to introduce nitrogen protection, reflux the reaction at 130°C with continuous stirring for 12 hours, and cool to room temperature to obtain product R3.

[0113] S3. Take product R3 and 427.077 g of 50 wt% PGME solution, mix them and put them into a dropping funnel. Under high-speed stirring, uniformly add 8.5 L of ultrapure water to precipitate the resin powder, filter and vacuum dry it to obtain modified phenolic resin R3.

[0114] The modified phenolic resin R3 obtained in this preparation example had a weight average molecular weight of 8000 and a PDI of 2.7 as measured by gel permeation chromatography.

[0115] Preparation Example 4

[0116] This preparation example is used to illustrate the preparation of a modified phenolic resin R4, which specifically includes:

[0117] S1. To a 0.5 L three-necked flask equipped with a Dean-Stark water trap, a condenser and a stirring device, 75.081 g (0.3 mol) of 2,2',4,4'-tetrahydroxydiphenyl sulfide, 10.814 g (0.1 mol) of p-cresol, 111.327 g of a 50 wt% PGME solution and 2.783 g of a 2.5 wt% oxalic acid solution were added, and nitrogen was continuously introduced for protection. The mixture was refluxed at 110 ° C with continuous stirring for 8 h, and then cooled to room temperature to obtain a prepolymer R4'.

[0118] S2. Add 25.432 g (0.1 mol) of 9,9-bis(methoxymethyl)fluorene to the prepolymer R4', continue to introduce nitrogen protection, reflux reaction at 130°C with continuous stirring for 12 hours, and cool to room temperature to obtain product R4.

[0119] S3. Take product R4 and 222.654g of 50wt% PGME solution, mix them and put them into a dropping funnel. Under high-speed stirring, uniformly add 5.5L of ultrapure water to precipitate the resin powder, filter and vacuum dry it to obtain modified phenolic resin R4.

[0120] The modified phenolic resin R4 obtained in this preparation example had a weight average molecular weight of 8500 and a PDI of 2.8 as measured by gel permeation chromatography.

[0121] Preparation Example 5

[0122] This preparation example is used to illustrate the preparation of a modified phenolic resin R5, which specifically includes:

[0123] S1. To a 0.5 L three-necked flask equipped with a Dean-Stark water trap, a condenser and a stirring device, 75.081 g (0.3 mol) of 2,2',4,4'-tetrahydroxydiphenyl sulfide, 10.814 g (0.1 mol) of p-cresol, 109.925 g of a 50 wt% PGME solution and 2.783 g of a 2.5 wt% oxalic acid solution were added, and nitrogen was continuously introduced for protection. The mixture was refluxed at 110° C. with continuous stirring for 8 h, and then cooled to room temperature to obtain a prepolymer R5'.

[0124] S2. Add 24.03 g (0.1 mol) of 9-(methoxymethyl)-9H-fluorene-9-methanol to the prepolymer R5', continue to introduce nitrogen protection, reflux the reaction at 130°C with continuous stirring for 12 hours, and cool to room temperature to obtain product R5.

[0125] S3. Take product R5 and 219.85g of 50wt% PGME solution, mix them and put them into a dropping funnel. Under high-speed stirring, add them dropwise into 5.5L of ultrapure water at a uniform rate to precipitate the resin powder, filter and vacuum dry it to obtain modified phenolic resin R5.

[0126] The modified phenolic resin R5 obtained in this preparation example had a weight average molecular weight of 9500 and a PDI of 2.5 as measured by gel permeation chromatography.

[0127] Comparative Preparation Example 1

[0128] This comparative preparation example is used to illustrate the preparation of a phenolic resin R6, which specifically includes:

[0129] S1. To a 0.5 L three-necked flask equipped with a Dean-Stark water trap, a condenser and a stirring device, 137.64 g (1.25 mol) of resorcinol, 81.162 g (1 mol) of a 37 wt% formaldehyde aqueous solution and 2.515 g of a 1.5 wt% oxalic acid solution were added, and nitrogen was continuously introduced for protection. The reaction was refluxed at 80 ° C with continuous stirring for 8 h, and then cooled to room temperature to obtain product R6.

[0130] S2. Take product R6 and 450g of 50wt% PGME solution, mix them and put them into a dropping funnel. Under high-speed stirring, add them dropwise into 5.5L of ultrapure water at a uniform rate to precipitate the resin powder, filter and vacuum dry it to obtain phenolic resin R6.

[0131] The weight average molecular weight of the phenolic resin R6 obtained in this comparative preparation example was measured by gel permeation chromatography to be 7000, and the PDI was 2.5.

[0132] Comparative Preparation Example 2

[0133] This comparative preparation example uses the method provided in Preparation Example 1 to prepare modified phenolic resin R7, except that 9,9-bis(methoxymethyl)fluorene is not introduced as a reaction monomer. The preparation specifically includes:

[0134] S1. To a 0.5L three-necked flask equipped with a Dean-Stark water trap, a condenser and a stirring device, 75.081g (0.3mol) of 2,2',4,4'-tetrahydroxydiphenyl sulfide, 16.819g (0.1mol) of 2,6-bis(hydroxymethyl)-p-cresol, 91.9g of a 50wt% PGME solution and 2.3g of a 2.5wt% oxalic acid solution were added, and nitrogen was continuously introduced for protection. The reaction was refluxed at 110°C with continuous stirring for 8h, and then cooled to room temperature to obtain product R7.

[0135] S2. Take product R7 and 185g of 50wt% PGME solution, mix them and put them into a dropping funnel. Under high-speed stirring, add them dropwise into 2.2L of ultrapure water at a uniform rate to precipitate the resin powder, filter and vacuum dry it to obtain modified phenolic resin R7.

[0136] The modified phenolic resin R7 obtained in this comparative preparation example was measured by gel permeation chromatography to have a weight average molecular weight of 7500 and a PDI of 3.0.

[0137] Comparative Preparation Example 3

[0138] This comparative preparation example uses the method provided in Preparation Example 1 to prepare modified phenolic resin R8, except that an equal molar amount of resorcinol is used instead of 2,2',4,4'-tetrahydroxydiphenyl sulfide as a reaction monomer. The preparation specifically includes:

[0139] S1. To a 0.5 L three-necked flask equipped with a Dean-Stark water trap, a condenser and a stirring device, 33.033 g (0.3 mol) of resorcinol, 16.819 g (0.1 mol) of 2,6-bis(hydroxymethyl)-p-cresol, 75.284 g of a 50 wt% PGME solution and 1.882 g of a 2.5 wt% oxalic acid solution were added, and nitrogen was continuously introduced for protection. The mixture was refluxed at 110° C. with continuous stirring for 8 h, and then cooled to room temperature to obtain a prepolymer R8'.

[0140] S2. Add 25.432 g (0.1 mol) of 9,9-bis(methoxymethyl)fluorene to the prepolymer R8', continue to introduce nitrogen protection, reflux reaction at 130° C. with continuous stirring for 12 h, and cool to room temperature to obtain product R8.

[0141] S3. Take product R8 and 150g of 50wt% PGME solution, mix them and put them into a dropping funnel. Under high-speed stirring, uniformly drop them into 2L of ultrapure water to precipitate the resin powder, filter and vacuum dry it to obtain modified phenolic resin R8.

[0142] The modified phenolic resin R8 obtained in this preparation example had a weight average molecular weight of 8300 and a PDI of 2.7 as measured by gel permeation chromatography.

[0143] Comparative Preparation Example 4

[0144] This comparative preparation example is used to illustrate the preparation of a modified phenolic resin R9, which specifically includes:

[0145] S1. To a 0.5L three-necked flask equipped with a Dean-Stark water trap, a condenser and a stirring device, 75.081g (0.3mol) of 2,2',4,4'-tetrahydroxydiphenyl sulfide, 16.819g (0.1mol) of 2,6-bis(hydroxymethyl)-p-cresol, 25.432g (0.1mol) of 9,9-bis(methoxymethyl)fluorene, 117.332g of a 50wt% PGME solution and 2.933g of a 2.5wt% oxalic acid solution were added, and nitrogen was continuously introduced for protection. The reaction was refluxed at 110°C with continuous stirring for 16h, and then cooled to room temperature to obtain product R9.

[0146] S2. Take product R9 and 250g of 50wt% PGME solution, mix them and put them into a dropping funnel. Under high-speed stirring, add 6L of ultrapure water at a uniform rate to precipitate resin powder, filter and vacuum dry it to obtain modified phenolic resin R9.

[0147] The modified phenolic resin R9 obtained in this preparation example was measured by gel permeation chromatography to have a weight average molecular weight of 12,000 and a PDI of 3.5.

[0148] It should be noted that the test conditions used in the gel permeation chromatography in the above preparation examples and comparative preparation examples remain consistent.

[0149] Example 1

[0150] This example illustrates a modified phenolic resin composition. The preparation of the composition includes: mixing 35 parts by mass of the modified phenolic resin R1 provided in Preparation Example 1, 2 parts by mass of 2,3,4,4'-tetrahydroxybenzophenone-2,1,4-diazonaphthoquinone sulfonate, 3 parts by mass of tetramethoxymethyl glycoluril, and 60 parts by mass of propylene glycol methyl ether, and filtering the mixture multiple times through a 0.22 μm filter to obtain a modified phenolic resin composition.

[0151] Example 2

[0152] The modified phenolic resin composition provided in this embodiment is substantially the same as that in Example 1, except that the modified phenolic resin R2 provided in Preparation Example 2 is used in equal parts by mass to replace the modified phenolic resin R1 provided in Preparation Example 1. Other conditions are the same to obtain a modified phenolic resin composition.

[0153] Example 3

[0154] The modified phenolic resin composition provided in this embodiment is substantially the same as that in Example 1, except that the modified phenolic resin R3 provided in Preparation Example 3 is used in equal parts by mass to replace the modified phenolic resin R1 provided in Preparation Example 1. Other conditions are the same to obtain a modified phenolic resin composition.

[0155] Example 4

[0156] The modified phenolic resin composition provided in this embodiment is substantially the same as that in Example 1, except that the modified phenolic resin R4 provided in Preparation Example 4 is used in equal parts by mass to replace the modified phenolic resin R1 provided in Preparation Example 1. Other conditions are the same to obtain a modified phenolic resin composition.

[0157] Example 5

[0158] The modified phenolic resin composition provided in this embodiment is substantially the same as that in Example 1, except that the modified phenolic resin R5 provided in Preparation Example 5 is used in equal parts by mass to replace the modified phenolic resin R1 provided in Preparation Example 1. Other conditions are the same to obtain a modified phenolic resin composition.

[0159] Comparative Example 1

[0160] The modified phenolic resin composition provided in this comparative example is substantially the same as that in Example 1, except that the modified phenolic resin R1 provided in Preparation Example 1 is replaced by the phenolic resin R6 provided in Comparative Preparation Example 1 in equal parts by mass, and other conditions are the same to obtain a modified phenolic resin composition.

[0161] Comparative Example 2

[0162] The modified phenolic resin composition provided in this comparative example is substantially the same as that in Example 1, except that the modified phenolic resin R7 provided in Comparative Preparation Example 2 is used in place of the modified phenolic resin R1 provided in Preparation Example 1 in equal parts by mass, and other conditions are the same to obtain a modified phenolic resin composition.

[0163] Comparative Example 3

[0164] The modified phenolic resin composition provided in this comparative example is substantially the same as that in Example 1, except that the modified phenolic resin R8 provided in Comparative Preparation Example 3 is used in equal parts by mass to replace the modified phenolic resin R1 provided in Preparation Example 1. Other conditions are the same to obtain a modified phenolic resin composition.

[0165] Comparative Example 4

[0166] The modified phenolic resin composition provided in this comparative example is substantially the same as that in Example 1, except that the modified phenolic resin R9 provided in Comparative Preparation Example 4 is used in equal parts by mass to replace the modified phenolic resin R1 provided in Preparation Example 1, and other conditions are the same to obtain a modified phenolic resin composition.

[0167] Test Case

[0168] This test example is used to illustrate the performance of the modified phenolic resin composition provided in the above embodiments and comparative examples. The test specifically includes:

[0169] (1) A wafer coated with silicon dioxide was used as the substrate and the surface was coated with silicon dioxide at a temperature of 0.015 g / cm 2 The modified phenolic resin compositions were uniformly coated on the surface of the silicon dioxide layer of the wafer in an amount of 1000 nm, and then heated and baked at 130° C. for 3 minutes, and then cured at 220° C. for 30 minutes to obtain a photoresist film.

[0170] (2) Using a 3% hydrofluoric acid aqueous solution, the photoresist film is peeled off from the wafer and dried to obtain a sample to be tested; and the peeling and drying conditions and sizes of each sample to be tested are the same.

[0171] (3) GB / T 1040.3-2006 was used to test the tensile strength and elongation at break of the samples, and ASTM E1356-23 was used to test the Tg value of the samples. The results are shown in Table 1.

[0172] Table 1.

[0173] Samples to be tested Tensile strength (MPa) Elongation at break (%) Tg(℃) Example 1 110 31 165 Example 2 117 33 170 Example 3 95 26 180 Example 4 102 27 160 Example 5 105 28 168 Comparative Example 1 65 13 145 Comparative Example 2 80 17 160 Comparative Example 3 88 19 151 Comparative Example 4 101 15 163

[0174] As shown in the test results in Table 1, compared with Comparative Examples 1 to 4, the modified phenolic resin compositions provided by Examples 1 to 5 of the present invention have better mechanical strength and heat resistance after curing into films, can better meet the use requirements of environments with complex temperature changes, are in line with the development trend of the semiconductor industry and the development requirements of photolithography processes, and have good application prospects.

[0175] Although the embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and are not to be construed as limitations on the present invention. A person skilled in the art may change, modify, replace and modify the above embodiments within the scope of the present invention without departing from the principles and purpose of the present invention.

Claims

1. A modified phenolic resin composition, characterized in that, The modified phenolic resin composition comprises a modified phenolic resin, a photosensitizer and a crosslinking agent; wherein the modified phenolic resin comprises a structural unit I represented by formula (1) and a structural unit II represented by formula (2): In formula (1), R1 to R4 are each independently selected from a hydrogen atom, a C1 to C 10 Monovalent aliphatic groups, C1~C 10 R5 and R7 are each independently selected from a hydrogen atom, a C1 to C 10 Monovalent aliphatic groups, C1~C 10 one or more monovalent aliphatic groups, m1=1 or 2, m3=1 or 2, 2≤m1+m3≤4; R6 and R8 are each independently selected from one or more of a halogen atom, a carboxyl group, a sulfonic acid group and a hydroxyl group, m2=1, 2 or 3, m4=1, 2 or 3, 2≤m2+m4≤4, and n1≥2; In formula (2), R9 and R 11 Each independently selected from hydrogen atom, C1 to C 10 Monovalent aliphatic groups, C1~C 10 One or more monovalent aliphatic groups, m5 = 1 or 2, m7 = 1 or 2, and 2 ≤ m5 + m7 ≤ 4; R 10 and R 12 Each is independently selected from one or more of a halogen atom, a carboxyl group, a sulfonic acid group and a hydroxyl group, m6=1, 2 or 3, m8=1, 2 or 3, 2≤m6+m8≤4; A is a divalent phenol group, and n2≥2.

2. The modified phenolic resin composition according to claim 1, wherein A in the structural unit II is a divalent phenol group derived from a phenolic compound having a structure as shown in formula (3): In formula (3), R 13 is a hydrogen atom, a methyl group, an ethyl group, a propyl group or a hydroxymethyl group; R 14 One or more selected from carboxyl, sulfonic acid, hydroxyl, hydroxymethyl, aldehyde and cyano groups, m9 = 1, 2 or 3, m 10 =0, 1, 2 or 3, and m9+m 10 ≤5.

3. The modified phenolic resin composition according to claim 1, wherein The preparation of the modified phenolic resin comprises: S1, taking a diphenyl sulfide compound represented by the structure of formula (4) and a phenol compound represented by the structure of formula (5) and performing a prepolymerization reaction in the presence of an acid catalyst to obtain a prepolymer; In formula (4), R 15 and R 16 Each independently selected from hydrogen atom, C1 to C 10 Monovalent aliphatic groups, C1~C 10 One or more monovalent aliphatic groups, m 11 =1 or 2, m 12 =1 or 2; In formula (5), R 17 is a hydrogen atom, a methyl group, an ethyl group, a propyl group or a hydroxymethyl group, R 18 is absent or selected from one or more of carboxyl, sulfonic acid, hydroxyl, methylol, aldehyde and cyano groups, m 13 =1, 2 or 3, m 14 = 0, 1, 2, or 3; S2, taking the diphenyl sulfide compound, the prepolymer and the fluorene compound having a structure as shown in formula (6) and performing a polymerization reaction in the presence of an acid catalyst to obtain the modified phenolic resin; In formula (6), R 19 ~R 22 Each independently selected from hydrogen atom, C1 to C 10 Monovalent aliphatic groups, C1~C 10 Z1 and Z2 are each independently selected from one of hydroxyl, methoxy, ethoxy, hydroxymethyl and methoxymethyl.

4. The modified phenolic resin composition according to claim 3, wherein In the preparation of the modified phenolic resin, the added molar ratio of the diphenyl sulfide compound, the phenol compound and the fluorene compound is (2-4):1:(1-2.5); Optionally, the diphenyl sulfide compound is 2,2',4,4'-tetrahydroxy diphenyl sulfide; Optionally, the phenolic compound is selected from one or more of 2,6-bis(hydroxymethyl)-p-cresol, p-cresol and m-cresol; Optionally, the fluorene compound is selected from one or more of 9,9-bis(methoxymethyl)fluorene, 9,9-fluorenedimethanol and 3,6-dimethyl-9,9-bis(methoxymethyl)fluorene.

5. The modified phenolic resin composition according to claim 3, wherein In the preparation of the modified phenolic resin, the acid catalyst is selected from one or more of hydrochloric acid, benzenesulfonic acid, p-toluenesulfonic acid, oxalic acid and acidic ion exchange resin; Optionally, based on the total mass of the diphenyl sulfide compound, the phenol compound and the fluorene compound, the total amount of the acid catalyst added in the prepolymerization reaction and the polymerization reaction is 0.5 wt % to 3 wt %.

6. The modified phenolic resin composition according to claim 1, wherein In step S1, the prepolymerization reaction temperature is 70°C to 120°C, and the time is 4h to 12h; Optionally, in step S2, the polymerization reaction temperature is 80° C. to 140° C., and the time is 8 h to 16 h.

7. The modified phenolic resin composition according to claim 1, wherein The photosensitizer is a diazonaphthoquinone compound and / or a diaryl onium iodide compound; Optionally, the diazonaphthoquinone compound is selected from one or more of 2,1,4-diazonaphthoquinone-5-sulfonate, 2,3,4,4'-tetrahydroxybenzophenone-2,1,4-diazonaphthoquinone sulfonate and 2,1,4-diazonaphthoquinone sulfonate; Optionally, the diaryl onium iodide salt compound is bis(4-tert-butylphenyl)iodonium perfluoro-1-butanesulfonic acid; Optionally, the cross-linking agent is a melamine compound and / or a glycoluril compound; Optionally, the melamine compound is selected from one or more of hexamethoxymethyl melamine, hexahydroxymethyl melamine and hexaethoxymethyl melamine; Optionally, the glycoluril compound is tetramethoxymethyl glycoluril and / or N,N'-bis(methoxymethyl)urea; Optionally, the modified phenolic resin composition includes a solvent, and the solvent is selected from one or more of propylene glycol methyl ether acetate, propylene glycol methyl ether, ethylene glycol dimethyl ether, anisole, γ-butyrolactone, ethyl lactate, n-heptane and dimethyl sulfoxide; Optionally, based on the total mass of the modified phenolic resin composition, the concentration of the modified phenolic resin is 10wt% to 45wt%, the concentration of the photosensitizer is 0.5wt% to 3wt%, the concentration of the crosslinking agent is 0.5wt% to 3wt%, and the concentration of the solvent is 49wt% to 89wt%.

8. The method for preparing the modified phenolic resin composition according to any one of claims 1 to 7, characterized in that: The preparation method comprises: mixing the modified phenolic resin, a photosensitizer, a crosslinking agent and an optional solvent to obtain the modified phenolic resin composition.

9. A cured film, characterized in that The cured film is prepared by thermally curing the modified phenolic resin composition according to any one of claims 1 to 7.

10. Use of the modified phenolic resin composition according to any one of claims 1 to 7 or the cured film according to claim 9 in the preparation of semiconductor devices.

Images