CN110989294A - Photosensitive resin composition, photosensitive resin layer, and electronic device - Google Patents
Photosensitive resin composition, photosensitive resin layer, and electronic device Download PDFInfo
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- CN110989294A CN110989294A CN201910924208.5A CN201910924208A CN110989294A CN 110989294 A CN110989294 A CN 110989294A CN 201910924208 A CN201910924208 A CN 201910924208A CN 110989294 A CN110989294 A CN 110989294A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
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- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/008—Azides
- G03F7/0085—Azides characterised by the non-macromolecular additives
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
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Abstract
The invention discloses a photosensitive resin composition, a photosensitive resin layer and an electronic device comprising the photosensitive resin layer, wherein the photosensitive resin composition comprises: (A) an alkali soluble resin; (B) a photosensitive diazoquinone compound; (C) a dissolution controlling agent comprising a first phenolic resin represented by chemical formula 1 and a second phenolic resin represented by chemical formula 2; and (D) a solvent, wherein the first phenolic resin and the second phenolic resin are contained in a weight ratio of 10:90 to 30: 70. In chemical formula 1 and chemical formula 2, each substituent is the same as defined in the specification.
Description
Cross reference to related applications
The present application claims priority and benefit of korean patent application No. 10-2018-0117827, filed by the korean intellectual property office at 10/2/2018, the entire contents of which are incorporated herein by reference.
Technical Field
The present disclosure relates to a photosensitive resin composition, a photosensitive resin layer using the photosensitive resin composition, and an electronic device.
Background
Polyimide resins, polybenzoxazole (polybenzoxazole) resins, and the like having improved heat resistance, electrical characteristics, and mechanical characteristics have been widely used for surface protective layers and interlayer insulating layers used in materials for display device panels and semiconductor devices. These resins are provided as compositions in which their precursors are dissolved in solvents, because of their low solubility in various solvents.
In recent years, the emergence of environmental problems has required countermeasures against the removal of organic (de-organic) solvents, and various types of heat-resistant photosensitive resin materials that can be produced with an aqueous alkali solution in the same manner as photoresists have been proposed.
Among them, a method of using a photosensitive resin composition comprising a mixture of a hydroxypolyamide (hydroxyolyyamide) resin (polybenzoxazole precursor) soluble in an aqueous alkali solution and a photoacid generator such as naphthoquinone diazide (naphthoquinone diazide) compound, the hydroxypolyamide resin being a heat-resistant resin after heat curing, has been proposed.
The photosensitivity mechanism of the photosensitive resin composition utilizes exposure of a photosensitive diazoquinone (diazoquinone) compound to a naphthoquinone diazide compound (i.e., a photosensitive diazoquinone compound) and a Polybenzoxazole (PBO) precursor in an unexposed portion, and thereby converts the photosensitive diazoquinone compound into an indenecarboxylic acid (indenecarboxylic acid) compound to increase the solubility in an aqueous alkali solution. The difference in the dissolution rate between the exposed portions and the unexposed portions can be used to manufacture a relief pattern (relief pattern) composed of the unexposed portions.
The photosensitive resin composition can form a positive relief pattern by exposure to an aqueous alkali solution and development. Further, the thermoset film characteristics can be obtained by heating.
When the cured film is applied to a semiconductor device as a surface protective layer and an interlayer insulating layer, the cured film is required to have high reliability. Although there are many indicators to assess reliability, sensitivity and residual characteristics are particularly important. In addition, the cured relief pattern should have good shape, sufficient alkali solubility, a small amount of residual film upon development, and excellent close contact characteristics with the substrate.
Disclosure of Invention
Embodiments provide a photosensitive resin composition having improved film residue rate, sensitivity, and residue characteristics at the same time.
Another embodiment provides a photosensitive resin layer manufactured using the photosensitive resin composition.
Yet another embodiment provides an electronic device comprising a photosensitive resin layer.
Embodiments provide a photosensitive resin composition, comprising: (A) an alkali soluble resin; (B) a photosensitive diazoquinone compound; (C) a dissolution controlling agent comprising a first phenolic resin represented by chemical formula 1 and a second phenolic resin represented by chemical formula 2; and (D) a solvent, wherein the first phenolic resin and the second phenolic resin are contained in a weight ratio of 10:90 to 30: 70.
[ chemical formula 1]
[ chemical formula 2]
In chemical formula 1 and chemical formula 2,
R1to R3Each independently hydroxyl or substituted or unsubstituted C1 to C5 alkyl,
p, q and r are each independently an integer in the range of 0 to 3, and
a. b and c are each independently a positive integer.
The second phenolic resin may be a block copolymer, an alternative copolymer or a random copolymer.
The dissolution controlling agent may be included in an amount of 0.1 parts by weight to 20 parts by weight based on 100 parts by weight of the alkali-soluble resin.
The alkali-soluble resin may be a polyhydroxyamide (polyhydroxyamide) resin.
The photosensitive resin composition may include 1 to 100 parts by weight of the photosensitive diazoquinone compound, 0.1 to 20 parts by weight of the dissolution-controlling agent, and 100 to 500 parts by weight of the solvent, based on 100 parts by weight of the alkali-soluble resin.
The photosensitive resin composition may further include the following additives: a dissolution control agent having a different structure than the first phenolic resin and the second phenolic resin, a sensitivity enhancer, a crosslinker, a diacid, an alkanolamine, a leveler, a coupling agent, a surfactant, an epoxy compound, a free radical polymerization initiator, a thermal latent acid generator, or a combination thereof.
Another embodiment provides a photosensitive resin layer manufactured using the photosensitive resin composition.
Another embodiment provides an electronic device comprising a photosensitive resin layer.
Other embodiments of the invention are encompassed by the following detailed description.
The photosensitive resin composition according to the embodiment can simultaneously improve the film residue rate, sensitivity, and residue characteristics by mixing the dissolution controlling agent comprising two different phenol resins in a specific ratio.
Detailed Description
Hereinafter, embodiments of the present invention are described in detail. However, these embodiments are exemplary, the present invention is not limited thereto and the present invention is defined by the scope of the claims.
In the present specification, when a specific definition is not otherwise provided, "alkyl" means C1 to C20 alkyl, "alkenyl" means C2 to C20 alkenyl, "cycloalkenyl" means C3 to C20 cycloalkenyl, "heterocycloalkenyl" means C2 to C20 heterocycloalkenyl, "aryl" means C6 to C20 aryl, "aralkyl" means C7 to C20 aralkyl, "alkylene" means C1 to C20 alkylene, "arylene" means C6 to C20 arylene, "alkylarylene" means C7 to C20 alkylarylene, "heteroarylene" means C5 to C20 heteroarylene, and "alkyleneoxy" means C1 to C20 alkyleneoxy.
In the present specification, when a specific definition is not otherwise provided, "substituted" means that at least one hydrogen atom is replaced by a substituent selected from the group consisting of: halogen atoms (F, Cl, Br, or I), hydroxyl groups, C1 to C20 alkoxy groups, nitro groups, cyano groups, amine groups (amino groups), imino groups (imino groups), azide groups, amidino groups (amidino groups), hydrazine groups (hydrazino groups), hydrazono groups (hydrazono groups), carbonyl groups, carbamoyl groups (carbamyl groups), thiol groups, ester groups, ether groups, carboxyl groups or salts thereof, sulfonic acid groups or salts thereof, phosphoric acid groups or salts thereof, C1 to C20 alkyl groups, C2 to C20 alkenyl groups, C2 to C20 alkynyl groups, C6 to C20 aryl groups, C3 to C20 cycloalkyl groups, C3 to C20 cycloalkenyl groups, C3 to C20 cycloalkynyl groups, C2 to C20 heterocycloalkyl groups, C2 to C20 heterocycloalkenyl groups, C2 to C20 heterocycloalkynyl groups, C5 to C20 heteroaryl groups, or combinations thereof.
In the present specification, when a specific definition is not otherwise provided, "hetero" means that N, O, S and at least one heteroatom of P are contained in the chemical formula.
In the present specification, "(meth) acrylate" means "acrylate" and "methacrylate" when a specific definition is not otherwise provided.
In the present specification, "combination" means mixing or copolymerization when a definition is not otherwise provided. Further, "copolymerization" refers to block copolymerization, alternative copolymerization, or random copolymerization, and "copolymer" refers to block copolymer, alternative copolymer, or random copolymer.
In the present specification, when a specific definition is not otherwise provided, the unsaturated bond includes a bond between other atoms, such as a carbonyl bond or an azo bond, and a polyvalent bond (multi-bond) between carbon-carbon atoms.
In the present specification, when a definition is not otherwise provided, when a chemical bond is not drawn at a position that should be given in a chemical formula, hydrogen is bonded at the position.
In addition, in the present specification, when a definition is not otherwise provided, "＊" means a bonding point (linking point) with the same or different atom or chemical formula.
A photosensitive resin composition according to an embodiment includes: (A) an alkali soluble resin; (B) a photosensitive diazoquinone compound; (C) a dissolution control agent comprising a first phenolic resin and a second phenolic resin; and (D) a solvent, wherein the first phenol resin is a polymer represented by chemical formula 1 and the second phenol resin is a copolymer represented by chemical formula 2, and the first phenol resin and the second phenol resin are included in a weight ratio of 10:90 to 30: 70.
[ chemical formula 1]
[ chemical formula 2]
In chemical formula 1 and chemical formula 2,
R1to R3Each independently hydroxyl or substituted or unsubstituted C1 to C5 alkyl,
p, q and r are each independently an integer in the range of 0 to 3, and
a. b and c are each independently a positive integer.
When used as a protective layer or an insulating layer in a semiconductor or a display device, the photosensitive resin composition according to the embodiment is applied by coating the composition, UV-exposing, developing, and curing the composition. Reliability, particularly, film residue rate, sensitivity, and residue characteristics are very important to process materials, and thus the photosensitive resin composition according to the embodiment may use a dissolution control agent including the first phenolic resin and the second phenolic resin to simultaneously improve sensitivity and residue characteristics while maintaining excellent film residue rate.
Hereinafter, each component is specifically described.
(C) Dissolution control agent
The dissolution control agent comprises two different types of phenolic resins. The phenolic resin includes a first phenolic resin represented by chemical formula 1 and a second phenolic resin represented by chemical formula 2, thereby improving sensitivity and residue characteristics while maintaining an excellent film residue rate.
In chemical formulas 1 and 2, a, b, and c refer to a mole number and may be an integer of 1 to 1,000, for example, 1 to 500. That is, the second phenolic resin may be a copolymer in which the structural unit represented by chemical formula 2a and the structural unit represented by chemical formula 2b are contained in a molar ratio of b: c.
[ chemical formula 2a ]
[ chemical formula 2b ]
In chemical formula 2a and chemical formula 2b,
R2and R3Each independently of the others, hydroxy or substituted or unsubstituted C1 to C5 alkyl, and
q and r are independently integers in the range of 0 to 3.
For example, chemical formula 1 may be represented by chemical formula 1-1, and chemical formula 2 may be represented by chemical formula 2-1.
[ chemical formula 1-1]
[ chemical formula 2-1]
In chemical formula 1-1 and chemical formula 2-1,
R1to R3Each independently hydroxyl or substituted or unsubstituted C1 to C5 alkyl,
p, q and r are each independently an integer in the range of 0 to 3, and
a. b and c are each independently a positive integer.
The first phenolic resin and the second phenolic resin are included in a weight ratio of 10:90 to 30: 70. When the first phenol resin and the second phenol resin are included in the weight ratio range, it is easy to control the dissolution rate of TMAH, which will be described later, and simultaneously improve the sensitivity and the residual characteristics while maintaining an excellent film residual rate. When the content of the first phenol resin relative to the second phenol resin is too small (for example, the first phenol resin: the second phenol resin ═ 5:95), the dissolution rate of TMAH becomes too fast and the film residual rate is uncontrollable, and likewise, when the content of the first phenol resin relative to the second phenol resin is too large (for example, the first phenol resin: the second phenol resin ═ 35:65), the dissolution rate of TMAH is too slow, the sensitivity is difficult to control, and accordingly, the residue within the pattern may not be improved.
For example, the dissolution control agent may be included in an amount of 0.1 to 20 parts by weight, such as 1 to 15 parts by weight, such as 3 to 12 parts by weight, based on 100 parts by weight of the alkali-soluble resin. When the dissolution controlling agent is in the range, excellent sensitivity, resolution and residue removing property of the photosensitive resin composition can be ensured, and a high-sensitivity pattern is formed after curing, and at the same time, heat resistance of the insulating layer can be improved.
(A) Alkali soluble resin
The alkali-soluble resin may be a polyhydroxyamide resin, a polyimide resin, a bisphenol a resin, a bisphenol F resin, (meth) acrylate resin, or a combination thereof.
The polyhydroxyamide resin may include a structural unit represented by chemical formula 4, and the polyimide resin may include a structural unit represented by chemical formula 5.
[ chemical formula 4]
In the chemical formula 4, the first and second organic solvents,
X1is a substituted or unsubstituted tetravalent C6 to C30 aromatic organic radical,
X2is a substituted or unsubstituted divalent C6 to C30 aromatic organic radical,
Y1and Y2Each independently a substituted or unsubstituted C6 to C30 aromatic organic radical, a substituted or unsubstituted divalent C1 to C30 aliphatic organic radical, or a substituted or unsubstituted divalent C3 to C30 cycloaliphatic organic radical, and
m1 is an integer from 2 to 1000, m2 is an integer from 0 to 500, and m1/(m1+ m2) > 0.5.
[ chemical formula 5]
In the chemical formula 5, the first and second organic solvents,
X3is a substituted or unsubstituted divalent C6 to C30 aromatic organic radical, a substituted or unsubstituted divalent C1 to C30 aliphatic organic radical, or a substituted or unsubstituted divalent C3 to C30 esterA cyclic organic group, and
Y3is a substituted or unsubstituted tetravalent C6 to C30 aromatic organic radical, a substituted or unsubstituted tetravalent C1 to C30 aliphatic organic radical, or a substituted or unsubstituted tetravalent C3 to C30 cycloaliphatic organic radical.
In chemical formula 4, X1May be an aromatic organic group and may be a moiety derived from an aromatic diamine.
Examples of the aromatic diamine may be at least one selected from the group consisting of: 3,3 '-diamino-4, 4' -dihydroxybiphenyl, 4 '-diamino-3, 3' -dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl) propane, bis (4-amino-3-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3, 3-hexafluoropropane, 2-bis (4-amino-3-hydroxyphenyl) -1,1,1,3,3, 3-hexafluoropropane, 2-bis (3-amino-4-hydroxy-5-trifluoromethylphenyl) hexafluoropropane, 2, 2-bis (3-amino-4-hydroxy-6-trifluoromethylphenyl) hexafluoropropane, 2-bis (3-amino-4-hydroxy-2-trifluoromethylphenyl) hexafluoropropane, 2-bis (4-amino-3-hydroxy-5-trifluoromethylphenyl) hexafluoropropane, 2-bis (4-amino-3-hydroxy-6-trifluoromethylphenyl) hexafluoropropane, 2-bis (4-amino-3-hydroxy-2-trifluoromethylphenyl) hexafluoropropane, 2-bis (3-amino-4-hydroxy-5-pentafluoroethylphenyl) hexafluoropropane, 2- (3-amino-4-hydroxy-5-trifluoromethylphenyl) hexafluoropropane 2- (3-amino-4-hydroxy-5-pentafluoroethylphenyl) hexafluoropropane, 2- (3-amino-4-hydroxy-5-trifluoromethylphenyl) -2- (3-hydroxy-4-amino-5-trifluoromethylphenyl) hexafluoropropane, 2- (3-amino-4-hydroxy-5-trifluoromethylphenyl) -2- (3-hydroxy-4-amino-6-trifluoromethylphenyl) hexafluoropropane, 2- (3-amino-4-hydroxy-5-trifluoromethylphenyl) -2- (3-hydroxy-4-amino-2-trifluoromethylphenyl) hexafluoropropane, and a pharmaceutically acceptable salt thereof, 2- (3-amino-4-hydroxy-2-trifluoromethylphenyl) -2- (3-hydroxy-4-amino-5-trifluoromethylphenyl) hexafluoropropane and 2- (3-amino-4-hydroxy-6-trifluoromethylphenyl) -2- (3-hydroxy-4-amino-5-trifluoromethylphenyl) hexafluoropropane, but are not limited thereto.
X1Examples of (b) may be a functional group represented by chemical formula 6 or chemical formula 7, but are not limited thereto.
[ chemical formula 6]
[ chemical formula 7]
In chemical formula 6 and chemical formula 7,
A1is a single bond, O, CO, CR47R48、SO2Or S, wherein R47And R48Each independently a hydrogen atom or a substituted or unsubstituted C1 to C30 alkyl group, specifically a C1 to C30 fluoroalkyl group,
R50to R52Each independently a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 carboxyl group, a hydroxyl group, or a thiol group, and
n10 is an integer from 0 to 2, with the proviso that n11 and n12 are each independently an integer from 0 to 3.
X2Examples of (b) may be a functional group represented by chemical formula 8 or chemical formula 10, but are not limited thereto.
[ chemical formula 8]
[ chemical formula 10]
In chemical formula 8 and chemical formula 10,
R53、R55and R56Each independently substituted or unsubstituted C1 to C30 alkyl,
n13 is an integer from 0 to 4, n15 and n16 are each independently an integer from 0 to 3, and
A2is a single bond, O, CR47R48CO, CONH, S or SO2Wherein R is47And R48Each independently a hydrogen atom or a substituted or unsubstituted C1 to C30 alkyl group, specifically a C1 to C30 fluoroalkyl group.
In chemical formula 4, Y1And Y2Each may independently be a divalent aromatic organic group, a divalent aliphatic organic group, or a divalent cycloaliphatic organic group, and may be part of a dicarboxylic acid or part of a dicarboxylic acid derivative. Specifically, Y1And Y2Each may independently be a divalent aromatic organic radical or a divalent cycloaliphatic organic radical.
Specific examples of dicarboxylic acid derivatives may be 4,4'-oxydibenzoyl chloride (4,4' -oxydibenzoyl chloride), diphenoxydicarbonyl dichloride (diphenoxydicarbonyl dichloride), bis (phenylcarbonyl chloride) sulfone (bis (phenylcarbonyl chloride) sulfone), bis (phenylcarbonyl chloride) ether (bis (phenylcarbonyl chloride) ether), bis (phenylcarbonyl chloride) phenone (bis (phenylcarbonyl chloride) phenone), phthaloyl dichloride (phenyldichloride), terephthaloyl dichloride (terphthaloyl dichloride), isophtaloyl dichloride (isophtaloyl dichloride), dicarbonyl dichloride (dicarbonyl dichloride), diphenoxydibenzotriazole (diphenoxydibenzotriazole), or a combination thereof, but are not limited thereto.
Y1And Y2Examples of (b) may be functional groups represented by chemical formulas 8 to 10, but are not limited thereto.
[ chemical formula 8]
[ chemical formula 9]
[ chemical formula 10]
In chemical formulas 8 to 10,
R53to R56Each independently substituted or unsubstituted C1 to C30 alkyl,
n13 and n14 are each independently an integer of 0 to 4, n15 and n16 are each independently an integer of 0 to 3, and
A2is a single bond, O, CR47R48CO, CONH, S or SO2Wherein R is47And R48Each independently a hydrogen atom or a substituted or unsubstituted C1 to C30 alkyl group, specifically a C1 to C30 fluoroalkyl group.
In chemical formula 5, X3Is a divalent aromatic organic radical, a divalent aliphatic organic radical or a divalent cycloaliphatic organic radical. Specifically, X3Is a divalent aromatic organic radical or a divalent cycloaliphatic organic radical.
Specifically, X3May be a moiety derived from an aromatic diamine, an alicyclic diamine, or a silicon diamine. In this context, the aromatic diamine, the alicyclic diamine, and the silicon diamine may be used alone or in combination of two or more.
Examples of the aromatic diamine may be 3,4' -diaminodiphenyl ether, 4' -diaminodiphenyl ether, 3,4' -diaminodiphenyl methane, 4' -diaminodiphenyl sulfone, 4' -diaminodiphenyl sulfide, benzidine, m-phenylenediamine, p-phenylenediamine, 1, 5-naphthalenediamine, 2, 6-naphthalenediamine, bis [4- (4-aminophenoxy) phenyl ] sulfone, bis (3-aminophenoxyphenyl) sulfone, bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl ] ether, 1, 4-bis (4-aminophenoxy) benzene or a combination thereof, which contains an aromatic ring substituted with an alkyl group or a halogen, but is not limited thereto.
Examples of the alicyclic diamine may be 1, 2-cyclohexyl diamine, 1, 3-cyclohexyl diamine, or a combination thereof, but are not limited thereto.
Examples of the silicon diamine may be bis (4-aminophenyl) dimethylsilane, bis (4-aminophenyl) tetramethylsiloxane, bis (p-aminophenyl) tetramethyldisiloxane, bis (γ -aminopropyl) tetramethyldisiloxane, 1, 4-bis (γ -aminopropyldimethylsilyl) benzene, bis (4-aminobutyl) tetramethyldisiloxane, bis (γ -aminopropyl) tetraphenyldisiloxane, 1, 3-bis (aminopropyl) tetramethyldisiloxane, or a combination thereof, but are not limited thereto.
In chemical formula 5, Y3Is a tetravalent aromatic organic radical, a tetravalent aliphatic organic radical or a tetravalent cycloaliphatic organic radical. Specifically, Y3Is a tetravalent aromatic organic radical or a tetravalent cycloaliphatic organic radical.
Y3May be a moiety derived from an aromatic acid dianhydride or an alicyclic acid dianhydride. Herein, the aromatic acid dianhydride and the alicyclic acid dianhydride may be used alone or in combination of two or more.
Examples of the aromatic acid dianhydride may be benzophenone tetracarboxylic dianhydride (benzophenone tetracarboxylic dianhydride) such as pyromellitic dianhydride; benzophenone-3, 3',4,4' -tetracarboxylic dianhydride and the like; oxydiphthalic anhydrides (e.g., 4' -oxydiphthalic anhydride); biphenyltetracarboxylic dianhydrides (e.g. 3,3',4,4' -biphenyltetracarboxylic dianhydride); (hexafluoroisopropylidene) diphthalic anhydride (e.g., 4' - (hexafluoroisopropylidene) diphthalic anhydride); naphthalene-1, 4,5, 8-tetracarboxylic dianhydride; 3,4,9,10-perylenetetracarboxylic dianhydride (3,4,9,10-perylenetetracarboxylic dianhydride) and the like, but is not limited thereto.
Examples of the alicyclic acid dianhydride may be 1,2,3, 4-cyclobutanetetracarboxylic dianhydride, 1,2,3, 4-cyclopentanetetracarboxylic dianhydride, 5- (2, 5-dioxatetrahydrofuryl) -3-methyl-cyclohexane-1, 2-dicarboxylic anhydride, 4- (2, 5-dioxatetrahydrofuran-3-yl) -tetralin-1,2-dicarboxylic anhydride (4- (2, 5-dioxatetrahydrofuran-3-yl) -tetralin-1,2-dicarboxylic anhydride), bicyclooctene-2, 3,5, 6-tetracarboxylic dianhydride, bicyclooctene-1, 2,4, 5-tetracarboxylic dianhydride and the like, but are not limited thereto.
For example, the alkali-soluble resin may be a polyhydroxyamide resin.
The alkali soluble resin can have a weight average molecular weight (Mw) of 3,000 to 300,000 g/mole, and specifically 5,000 to 30,000 g/mole. When the alkali-soluble resin has a weight average molecular weight (Mw) within the range, a sufficient film residual rate can be obtained in a non-exposed portion during development with an aqueous alkali solution, and effective patterning can be performed.
(B) Photosensitive diazoquinone compound
The photosensitive diazoquinone compound may be a compound having a 1, 2-benzoquinone diazide structure or a 1, 2-naphthoquinone diazide structure.
The photosensitive diazoquinone compound may include at least one selected from the group consisting of compounds represented by chemical formula 11 and chemical formulae 13 to 15, but is not limited thereto.
[ chemical formula 11]
In the chemical formula 11, the first and second,
R31to R33Each independently a hydrogen atom or a substituted or unsubstituted alkyl group, and specifically CH3,
D1To D3Each independently is OQ, wherein Q is hydrogen, a functional group represented by chemical formula 12a or a functional group represented by chemical formula 12b, with the proviso that Q cannot be hydrogen at the same time, and
n31 to n33 are each independently an integer from 1 to 5.
[ chemical formula 12a ]
[ chemical formula 12b ]
[ chemical formula 13]
In the chemical formula 13, the first and second carbon atoms are represented by,
R34is a hydrogen atom or substituted or notA substituted alkyl group,
D4to D6Each independently is OQ, wherein Q may be the same as defined in chemical formula 11, and
n34 to n36 are each independently an integer from 1 to 5.
[ chemical formula 14]
In the chemical formula 14, the first and second,
A3is CO or CR500R501Wherein R is500And R501Each independently is a substituted or unsubstituted alkyl group,
D7to D10Each independently a hydrogen atom, a substituted or unsubstituted alkyl group, OQ, or NHQ, wherein Q is the same as defined in chemical formula 11,
n37, n38, n39 and n40 are each independently an integer of 1 to 4, and
n37+ n38 and n39+ n40 are each independently integers less than or equal to 5,
with the proviso that at least one of D7-D10 is OQ, and one aromatic ring contains one to three OQ, and the other aromatic ring contains one to four OQ.
[ chemical formula 15]
In the chemical formula 15, the first and second compounds,
R35to R42Each independently a hydrogen atom or a substituted or unsubstituted alkyl group,
n41 and n42 are each independently an integer of 1 to 5, and specifically 2 to 4, and
q is the same as defined in chemical formula 11.
The photosensitive diazoquinone compound may be contained in an amount of 1 part by weight to 100 parts by weight, for example, 5 parts by weight to 50 parts by weight, based on 100 parts by weight of the alkali-soluble resin. When the photosensitive diazoquinone compound is contained within the above range, a pattern is well formed without a residue from exposure, and a film thickness loss during development can be prevented and thus a good pattern can be obtained.
(D) Solvent(s)
The photosensitive resin composition may include a solvent capable of easily dissolving each of the following components: alkali-soluble resins, photosensitive diazoquinone compounds, dissolution control agents comprising a first phenolic resin and a second phenolic resin, and the like.
The solvent may be an organic solvent, specifically, N-methyl-2-pyrrolidone, γ -butyrolactone, N-dimethylacetamide, dimethylsulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl-1, 3-butylene glycol acetate, 1, 3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxy propionate, or a combination thereof, but is not limited thereto.
The solvent may be appropriately selected according to the process of forming the photosensitive resin layer, such as spin coating, slot die coating, and the like.
The solvent may be included in an amount of 100 parts by weight to 500 parts by weight, for example, 100 parts by weight to 400 parts by weight, based on 100 parts by weight of the alkali-soluble resin. When the solvent is included within the range, the coating layer may have a sufficient thickness, and excellent solubility and coating characteristics are improved.
(F) Other additives
The photosensitive resin composition according to the embodiment may further include other additives.
The photosensitive resin composition may contain the following additives: a dissolution control agent having a different structure from the first phenolic resin and the second phenolic resin, a sensitivity enhancer, a crosslinking agent, a diacid (such as malonic acid), an alkanolamine (such as 3-amino-1, 2-propanediol), a leveling agent, a coupling agent, a surfactant, an epoxy compound, a radical polymerization initiator, a thermal latent acid generator, or a combination thereof, in order to prevent strain of the film during coating, to improve leveling characteristics, or to prevent residue generation due to non-development. The amount of additive used can be controlled depending on the desired properties.
For example, the coupling agent may have reactive substituents such as vinyl, carboxyl, methacryloxy, isocyanate, epoxy, and the like groups to improve the close contact characteristics with the substrate.
Examples of the coupling agent may be trimethoxysilylbenzoic acid, gamma-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, gamma-isocyanatopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, β - (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, and the like, and may be used alone or in the form of a mixture of two or more.
The coupling agent may be used in an amount of 0.01 to 10 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the coupling agent is contained within the range, the close contact property, the storage ability and the like are improved.
For example, a surfactant is added to prevent strain of a film thickness or improve developability, and the surfactant may include a fluorine-based surfactant and/or a silicone-based surfactant.
Examples of the fluorine-based surfactant may be commercially available fluorine-based surfactants such as those of BM chemical company (BMChemie Inc.)
And
megaface (Megaface) F of Dainippon ink chemical industries, Inc. (Dainippon ink Kagaku Kogyo Co., Ltd.)
Megaffei F
Megaffei F
Megaffei F
And Megoffes F
Fowler-Nordheim (FULORAD) of Sumitomo 3M Co., Ltd
Fowler radde
Fowler radde
And Fowler-red
Soulon (SURFON) of Glass corporation of Japan (Asahi Glass Co., Ltd.)
Cable dragon
Cable dragon
Cable dragon
And a cable dragon
Of Toray Silicone Co., Ltd (Toray Silicone Co., Ltd.)
And
and the like.
The silicone based surfactant may be BYK (BYK) -307, BYK-333, BYK-361N, BYK-051, BYK-052, BYK-053, BYK-067A, BYK-077, BYK-301, BYK-322, BYK-325 and the like, which are commercially available from BYK chemistry.
The surfactant may be used in an amount of 0.001 to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the surfactant is included in the range, coating uniformity may be ensured, strain may not be generated and wetting on an ITO substrate or a glass substrate is improved.
The photosensitive resin composition may further comprise an epoxy compound for improving the close contact force and the like as an additive. The epoxy compound may be an epoxy novolac acrylate resin, an o-cresol novolac epoxy resin, a phenol novolac epoxy resin, a tetramethyl biphenyl epoxy resin, a bisphenol a epoxy resin, an alicyclic epoxy resin, or a combination thereof.
When further comprising an epoxy compound, a radical polymerization initiator such as a peroxide initiator or an azobis type initiator may be further comprised.
The epoxy compound may be used in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the epoxy compound is included in the range, storage capacity, close contact force, and other characteristics can be improved.
The photosensitive resin composition may further comprise a thermal latent acid generator. Examples of thermal latent acid generators may be: arylsulfonic acids such as p-toluenesulfonic acid or benzenesulfonic acid; perfluoroalkylsulfonic acids, such as trifluoromethanesulfonic acid or trifluorobutanesulfonic acid; alkylsulfonic acids, such as methanesulfonic acid, ethanesulfonic acid or butanesulfonic acid; or a combination thereof, but is not limited thereto.
The thermal latent acid generator is a catalyst for the dehydration reaction and the cyclization reaction of the polybenzoxazole precursor (i.e., the phenolic hydroxyl group-containing polyamide), and therefore the cyclization reaction proceeds smoothly even if the curing temperature is lowered.
In addition, the photosensitive resin composition according to the embodiment may further include predetermined amounts of other additives such as an antioxidant, a stabilizer, and the like, unless the characteristics are degraded.
Another embodiment provides a photosensitive resin layer manufactured by exposing, developing and curing the photosensitive resin composition.
Another embodiment provides an electronic device comprising a photosensitive resin layer.
The electronic device may be a semiconductor device.
The method for producing the photosensitive resin layer is as follows.
(1) Coating and layer formation
A photosensitive resin composition having a desired thickness is coated on a substrate subjected to a predetermined pretreatment, such as a glass substrate or an ITO substrate, using a spin coating or slit coating method, a roll coating method, a screen printing method, an applicator method, and the like. Subsequently, the coated substrate is heated at a temperature ranging from 70 ℃ to 150 ℃ for 1 minute to 10 minutes, thereby removing the solvent and forming a layer.
(2) Exposure method
After a mask having a predetermined shape is placed to form a desired pattern, the obtained photosensitive resin layer is irradiated with active rays of 200 nm to 500 nm. The irradiation is performed by using a light source such as a mercury lamp having a low pressure, a high pressure or an ultrahigh pressure, a metal halide lamp, an argon laser and the like. X-rays, electron beams, and the like may also be used as necessary.
The exposure dose differs depending on the type of each component of the composition, the combination ratio thereof, and the dry film thickness, but when a high-pressure mercury lamp is used, the exposure dose is less than or equal to 500 millijoules per square centimeter (mJ/cm)2) (according to 365 nm sensor).
(3) Development
In the developing method, after the exposure step, the exposed portion is dissolved and removed by using a developing solution to leave only the non-exposed portion to obtain a pattern.
(4) Post-processing (Post-process) process
The image pattern obtained by the development in the above process is post-heated to obtain a pattern having improved heat resistance, light resistance, close contact property, crack resistance, chemical resistance, high strength, and storage stability. For example, after development, the pattern can be heated in a convection oven at 250 ℃ for 1 hour.
Hereinafter, the present invention is described in more detail with reference to examples. However, these examples should not be construed in any way as limiting the scope of the invention.
(examples)
(Synthesis of alkali-soluble resin)
12.4 grams of 2, 2-bis (3-amino-4-hydroxyphenyl) -1,1,1,3,3, 3-hexafluoropropane were dissolved in 125 grams of N-methyl-2-pyrrolidone (NMP) in a four-necked flask equipped with a stirrer, temperature controller, nitrogen syringe and condenser with nitrogen passing therethrough.
When the solid was completely dissolved, 4.2 g of pyridine was added thereto as a catalyst, and, while the temperature was maintained at 0 ℃ to 5 ℃, a solution prepared by dissolving 9.4 g of 4,4' -oxybenzoyl chloride in 100 g of NMP was slowly added thereto in a dropwise manner for 30 minutes. When the addition was completed, the obtained mixture was reacted at 0 to 5 ℃ for 1 hour, and after increasing the temperature to room temperature, the reaction was performed for one hour.
Subsequently, 1.1 g of 5-norbornene-2, 3-dicarboxylic anhydride (5-norbomene-2, 3-dicarboxylic anhydride) was added thereto, and the obtained mixture was stirred at 70 ℃ for 24 hours, thereby completing the reaction. The reaction mixture was put into a solution of water/methanol 10/1 (volume ratio) to generate a precipitate, and the precipitate was filtered, sufficiently washed, and dried under vacuum at 80 ℃ for 24 hours or more, thereby obtaining a polyhydroxyamide resin.
(polymerization of dissolution-controlling agent)
Polymerization example 1: a first phenolic resin
1.00 moles of m-cresol, 1.50 moles of p-cresol, 1.25 moles of salicylic acid, 0.002 moles of p-toluenesulfonic acid 1 hydrate, and 100 grams of propylene glycol monomethyl ether were mixed and stirred at 70 ℃ in a 1.0 liter flask to obtain a mixed solution (reaction solution). The obtained reaction solution was heated to 120 ℃ in an oil bath. The reaction solution was constantly stirred at 120 ℃ for 5 hours and then cooled to 60 ℃. When the reaction is complete, a mixture of water and methanol is used to remove the acid.
Polymerization example 2: second phenolic resin
1.00 moles of m-cresol, 1.50 moles of p-cresol, 0.50 moles of salicylic acid, 0.75 moles of formaldehyde, 0.002 moles of p-toluenesulfonic acid 1 hydrate, and 100 grams of propylene glycol monomethyl ether were mixed and stirred at 70 ℃ in a 1.0 liter flask to dissolve the solids and obtain a mixed solution (reaction solution). The obtained reaction solution was heated to 120 ℃ in an oil bath. The reaction solution was constantly stirred at 120 ℃ for 5 hours and then cooled to 60 ℃. When the reaction is complete, a mixture of water and methanol is used to remove the acid.
(preparation of photosensitive resin composition)
Examples 1 to 4 and comparative examples 1 to 4
100 g of the polyhydroxyamide resin was dissolved in 300 g of Gamma Butyrolactone (GBL) solvent, and 30 g of a photosensitive diazoquinone compound (MIPHOTO TPD425, Miwon Commercial co., Ltd.), a first phenol resin and a second phenol resin in the weight ratio shown in table 1 were dissolved therein, and then stirred until the solution became homogeneous under yellow light. Next, the resultant solution was filtered with a 0.20 μm fluororesin filter to obtain a photosensitive resin composition.
[ Table 1]
| Weight ratio of | A first phenolic resin | Second phenolic resin |
| Example 1 | 10 | 90 |
| Example 2 | 15 | 85 |
| Example 3 | 20 | 80 |
| Example 4 | 30 | 70 |
| Comparative example 1 | 0 | 100 |
| Comparative example 2 | 5 | 95 |
| Comparative example 3 | 35 | 65 |
| Comparative example 4 | 100 | 0 |
Evaluation of
The photosensitive resin compositions according to examples 1 to 4 and comparative examples 1 to 4 were coated on aluminum deposition wafers, respectively, and heated (cured) on a heating plate at 120 ℃ for 4 minutes to form cured films 10 μm thick. The cured films were evaluated for film residue rate, sensitivity, and residue characteristics, and the results are shown in table 2.
(evaluation 1: film residue ratio)
The difference in thickness before/after development was calculated as% to obtain a film residue ratio.
(evaluation 2: sensitivity)
After development, the exposure dose showing a pattern size of 7 μm was calculated as the sensitivity.
(evaluation 3: residue (scum)))
-O: after development, no composition remained in the perforation pattern.
-X: after development, the composition remains in the perforation pattern.
[ Table 2]
Referring to table 1, the photosensitive resin composition according to the embodiment of the present invention can simultaneously improve sensitivity and residual characteristics and maintain an excellent film residual rate by using a first phenolic resin including a structural unit represented by chemical formula 1 and a second phenolic resin including a structural unit represented by chemical formula 2 as a dissolution control agent at a predetermined ratio.
While the invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not to be limited to the disclosed embodiments, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. The above-described embodiments are therefore to be understood as illustrative and not restrictive in any way.
Claims (8)
1. A photosensitive resin composition comprising:
(A) an alkali soluble resin;
(B) a photosensitive diazoquinone compound;
(C) a dissolution controlling agent including a first phenol resin represented by chemical formula 1 and a second phenol resin represented by chemical formula 2; and
(D) a solvent, a water-soluble organic solvent,
wherein the first phenolic resin and the second phenolic resin are contained in a weight ratio of 10:90 to 30: 70:
[ chemical formula 1]
[ chemical formula 2]
Wherein, in chemical formula 1 and chemical formula 2,
R1to R3Each independently hydroxyl or substituted or unsubstituted C1 to C5 alkyl,
p, q and r are each independently an integer in the range of 0 to 3, and
a. b and c are each independently a positive integer.
2. The photosensitive resin composition according to claim 1, wherein the second phenolic resin is a block copolymer, a substitution copolymer, or a random copolymer.
3. The photosensitive resin composition according to claim 1, wherein the dissolution controlling agent is contained in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the alkali-soluble resin.
4. The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin is a polyhydroxyamide resin.
5. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition comprises
Based on 100 parts by weight of the alkali-soluble resin,
1 to 100 parts by weight of the photosensitive diazoquinone compound,
0.1 to 20 parts by weight of the dissolution controlling agent, and
100 to 500 parts by weight of the solvent.
6. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition further comprises the following additives: a dissolution control agent having a different structure than the first phenolic resin and the second phenolic resin, a sensitivity enhancer, a crosslinker, a diacid, an alkanolamine, a leveler, a coupling agent, a surfactant, an epoxy compound, a free radical polymerization initiator, a thermal latent acid generator, or a combination thereof.
7. A photosensitive resin layer produced using the photosensitive resin composition as described in any one of claims 1 to 6.
8. An electronic device comprising the photosensitive resin layer according to claim 7.
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