WO2016152656A1 - 感光性樹脂組成物 - Google Patents
感光性樹脂組成物 Download PDFInfo
- Publication number
- WO2016152656A1 WO2016152656A1 PCT/JP2016/058175 JP2016058175W WO2016152656A1 WO 2016152656 A1 WO2016152656 A1 WO 2016152656A1 JP 2016058175 W JP2016058175 W JP 2016058175W WO 2016152656 A1 WO2016152656 A1 WO 2016152656A1
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- WIPO (PCT)
- Prior art keywords
- photosensitive resin
- general formula
- acid
- film
- resin composition
- Prior art date
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- WQKAIZJFJDLUTB-UHFFFAOYSA-N Nc1cc(C(Nc2cc(C(C(F)(F)F)(C(F)(F)F)c(cc3NC(c4cc(N)ccc4)=O)ccc3O)ccc2O)=O)ccc1 Chemical compound Nc1cc(C(Nc2cc(C(C(F)(F)F)(C(F)(F)F)c(cc3NC(c4cc(N)ccc4)=O)ccc3O)ccc2O)=O)ccc1 WQKAIZJFJDLUTB-UHFFFAOYSA-N 0.000 description 1
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- H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
- H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
- H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
- H01L23/5329—Insulating materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/10—Organic polymers or oligomers
- H10K85/151—Copolymers
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
- H10K71/20—Changing the shape of the active layer in the devices, e.g. patterning
- H10K71/231—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers
- H10K71/233—Changing the shape of the active layer in the devices, e.g. patterning by etching of existing layers by photolithographic etching
Definitions
- the present invention relates to a photosensitive resin composition. More specifically, the present invention relates to a positive photosensitive resin composition suitable for a surface protective film on the surface of a semiconductor element, an interlayer insulating film, an insulating layer of an organic electroluminescent element, and the like.
- Resins typified by polyimide and polybenzoxazole have excellent heat resistance and electrical insulation, and are therefore used for surface protective films of semiconductor elements, interlayer insulating films, insulating layers of organic electroluminescent elements, and the like.
- surface protective films of semiconductor elements interlayer insulating films, insulating layers of organic electroluminescent elements, and the like.
- surface protection films, interlayer insulating films, and the like are required to have a resolution of several ⁇ m level. Therefore, in such applications, a positive photosensitive polyimide resin composition and a positive photosensitive polybenzoxazole resin composition that can be finely processed are often used.
- a semiconductor element is formed on a substrate, and a passivation film typified by Si or SiN is formed thereon to form a resin film to protect the surface of the semiconductor element.
- a resin film is applied on the passivation film, and then heated and dried using a hot plate or the like, and a pattern is formed through exposure and development. After forming the pattern of the resin film, a high temperature treatment process by curing is performed.
- a general configuration of a semiconductor device having a bump electrode has a metal wiring for the purpose of rewiring on a pattern resin film on an electrode pad of a semiconductor chip, and a pattern resin film as an insulating layer between the metal wirings. Has an electrode pad and a bump electrode thereon.
- a method of forming a bump electrode there is a method of forming a bump electrode by applying a flux to an electrode pad of a metal wiring, mounting a solder ball, and performing a reflow process to fuse the bump.
- the protective film and insulating film are exposed to the high temperature of reflow with the flowed flux in contact with them, so stress such as chemical stress or thermal stress is applied by the flux, and after reflow, between the metal wiring and the resin film Peeling may occur and reliability may be reduced. Therefore, when a semiconductor having a bump electrode made of a resin film is used, the adhesion between the resin composition and the metal wiring is very important.
- copper has been increasingly used as a metal wiring member from the viewpoint of cost and electrical characteristics, so it is very important to improve the adhesion to copper.
- lead-free solder that does not contain lead has been used from the viewpoint of environmental protection. However, lead-free solder has a high melting point, which increases the reflow temperature. Adhesiveness that can withstand the above high temperatures is required.
- Japanese Unexamined Patent Publication No. 2014-178471 Japanese Unexamined Patent Publication No. 2007-187710 Japanese Unexamined Patent Publication No. 2015-26033 Japanese Unexamined Patent Publication No. 2013-250566 Japanese Unexamined Patent Publication No. 2011-065167
- the flux is applied to the electrode pad portion of the metal wiring formed by the pattern resin film made of the resin composition, and reflow treatment is performed. Therefore, adhesion between the resin composition and the metal wiring is required.
- Patent Document 1 describes improvement in resistance to reflow treatment by a resin composition containing a phenol resin and a heterocyclic compound, but the pattern processability is greatly reduced by the deterioration of the photosensitizer by the heterocyclic compound.
- Patent Document 2 discloses that a resin composition containing a polyimide precursor and a heterocyclic compound can realize prevention of sensitivity reduction after standing after exposure.
- Patent Documents 3 to 5 disclose that a salt of a heterocyclic compound and a strong acid is used for the purpose of lowering the curing temperature of the polybenzoxazole precursor or the polyimide precursor. There was no mention of improvement.
- an object of the present invention is to provide a photosensitive resin composition that can improve the adhesion between a patterned cured film after reflow treatment and a metal wiring while being highly sensitive in a patterned cured film of a semiconductor device. To do.
- the photosensitive resin composition of the present invention has the following constitution. That is, (a-1) an alkali-soluble resin containing at least one selected from a resin having a structure represented by the following general formula (1) as a main component, (a-2) a polyimide, and a copolymer thereof. And (c) a photosensitive resin composition comprising a compound having a structure represented by the following general formula (2) as a main component.
- R 1 and R 2 may be the same or different and each represents a divalent to octavalent organic group having 2 or more carbon atoms.
- R 3 and R 4 are the same or different.
- R 5 , R 6 and R 7 may be the same or different, and are a hydrogen atom or a monovalent organic group having 1 or more carbon atoms, R 5 , R 6 and R 7. At least one of them represents a monovalent organic group having 1 or more carbon atoms.
- the present invention provides a positive photosensitive resin composition that can improve the adhesion between a patterned cured film after reflow treatment and a metal wiring while being highly sensitive in a patterned cured film of a semiconductor device.
- FIG. 1 is a schematic cross-sectional view of a semiconductor device having a resin film and metal wiring according to the present invention.
- the photosensitive resin composition of the present invention is selected from (a-1) a resin whose main component is a structure represented by the general formula (1) described later, (a-2) a polyimide, and copolymers thereof. And (c) a compound having as a main component a structure represented by the general formula (2) described later.
- a resin having a structure represented by the general formula (1) as a main component, and (a-2) a polyimide may be used singly or in combination, or may be used by copolymerization. Good.
- a resin having a structure represented by the following general formula (1) as a main component can be a polymer having an imide ring, an oxazole ring, or other cyclic structure by heating or an appropriate catalyst.
- Preferable examples include polyamic acid and polyamic acid ester of polyimide precursor, polyhydroxyamide of polybenzoxazole precursor, and the like. Due to the annular structure, the heat resistance and solvent resistance are dramatically improved.
- the main component means having n structural units of the structure represented by the general formula (1) in an amount of 50 mol% or more of the structural units of the polymer.
- R 1 and R 2 may be the same or different and each represents a divalent to octavalent organic group having 2 or more carbon atoms.
- R 3 and R 4 are the same or different. It may be hydrogen or an organic group having 1 to 20 carbon atoms, n is an integer of 10 to 100,000, m and f are each independently an integer of 0 to 2, and p and q are each independently 0 to 4 Indicates an integer, where m + q ⁇ 0 and p + q ⁇ 0.)
- R 1 represents a divalent to octavalent organic group having 2 or more carbon atoms and represents an acid structural component.
- acids in which R 1 is divalent include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, diphenyl ether dicarboxylic acid, naphthalenedicarboxylic acid, and bis (carboxyphenyl) propane, and aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid and adipic acid. And so on.
- Examples of the acid in which R 1 becomes trivalent include tricarboxylic acids such as trimellitic acid and trimesic acid.
- Examples of the acid in which R 1 is tetravalent include tetracarboxylic acids such as pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, and diphenyl ether tetracarboxylic acid.
- the acid which has hydroxyl groups such as a hydroxyphthalic acid and a hydroxy trimellitic acid, can also be mentioned. Two or more of these acid components may be used as the acid comprising R 1, but it is preferable to contain 40 mol% or more of dicarboxylic acid from the viewpoint of pattern processability.
- R 1 preferably contains an aromatic ring from the viewpoint of heat resistance, and more preferably a divalent or trivalent organic group having 6 to 30 carbon atoms from the viewpoint of pattern processability.
- R 1 (COOR 3 ) m (OH) p in the general formula (1) is phenylene (—C 6 H 4 —) or divalent biphenyl (—C 6 H 4 C 6 H 4 —).
- Divalent diphenyl ether (—C 6 H 4 OC 6 H 4 —), divalent diphenyl hexafluoropropane (—C 6 H 4 C (CF 3 ) 2 C 6 H 4 —), divalent diphenylpropane ( —C 6 H 4 C (CH 3 ) 2 C 6 H 4 —), divalent diphenyl sulfone (—C 6 H 4 SO 2 C 6 H 4 —), those having up to 2 carboxyl groups substituted on them, etc. Can be mentioned. In addition, the following structures may be mentioned, but not limited to these.
- R 2 represents a divalent to octavalent organic group having 2 or more carbon atoms and represents a structural component of diamine. Among these, those having an aromatic ring are preferred from the viewpoint of the heat resistance of the resulting resin. Specific examples of diamines containing R 2 include bis (amino-hydroxy-phenyl) hexafluoropropane having a fluorine atom, diaminodihydroxypyrimidine, diaminodihydroxypyridine, hydroxy-diamino-pyrimidine having no fluorine atom.
- Diaminophenol, dihydroxybenzidine, diaminobenzoic acid, diaminoterephthalic acid and the like, and those in which R 2 (COOR 4 ) f (OH) q in the general formula (1) has the structure shown below are included. However, it is not limited to these. Two or more of these diamines may be used.
- other diamines may be used instead of the diamine, and other diamines may be copolymerized.
- examples of such other diamines include phenylenediamine, diaminodiphenyl ether, aminophenoxybenzene, diaminodiphenylmethane, diaminodiphenylsulfone, bis (trifluoromethyl) benzidine, bis (aminophenoxyphenyl) propane, bis (aminophenoxyphenyl) sulfone And compounds in which at least a part of hydrogen atoms of these aromatic rings are substituted with alkyl groups or halogen atoms, aliphatic cyclohexyldiamine, methylenebiscyclohexylamine, hexamethylenediamine, and the like.
- the content of these other diamine residues is preferably 1 to 40 mol% of the diamine residues from the viewpoint of solubility in an alkaline developer.
- R 3 and R 4 in the general formula (1) may be the same or different and each represents hydrogen or a monovalent organic group having 1 to 20 carbon atoms.
- R 3 and R 4 are preferably organic groups, but hydrogen is preferable from the viewpoint of solubility in an alkaline aqueous solution.
- hydrogen atoms and organic groups can be mixed.
- a preferred range is that 10 to 90 mol% of each of R 3 and R 4 is a hydrogen atom.
- R 3 and R 4 have 20 or less carbon atoms, solubility in an alkaline aqueous solution can be maintained.
- R 3 and R 4 preferably contain at least one hydrocarbon group having 1 to 16 carbon atoms, and the others are preferably hydrogen atoms.
- m and f represent the number of carboxyl groups and ester groups, and each independently represents an integer of 0 to 2.
- m and f are preferably 0 from the viewpoint of pattern processability.
- p and q each independently represent an integer of 0 to 4, and m + q ⁇ 0 and p + q ⁇ 0. From the standpoint of improving the heat resistance and mechanical properties by closing and curing the resin composition by heat treatment, it is necessary that m + q ⁇ 0. From the viewpoint of solubility in an aqueous alkali solution, it is necessary that p + q ⁇ 0.
- n represents the number of repeating structural units of the resin and is an integer of 10 to 100,000. If n is 10 or more, the solubility of the resin in the alkaline aqueous solution does not become excessive, the contrast between the exposed portion and the unexposed portion becomes good, and a desired pattern can be formed. On the other hand, if n is 100,000 or less, a decrease in the solubility of the resin in the alkaline aqueous solution can be suppressed, and a desired pattern can be formed by dissolving the exposed portion. From the viewpoint of the solubility of the resin in an alkaline aqueous solution, n is preferably 1,000 or less, and more preferably 100 or less. Further, n is preferably 20 or more from the viewpoint of improving the elongation.
- N in the general formula (1) is the weight average molecular weight (Mw) of the resin having the structure represented by the general formula (1) as a main component, gel permeation chromatography (GPC), light scattering method, X-ray small angle scattering. It can be easily calculated from the value obtained by the method.
- an aliphatic group having a siloxane structure may be copolymerized with R 1 and / or R 2 in the general formula (1) as long as the heat resistance is not lowered.
- the diamine component include those obtained by copolymerizing 1 to 10 mol% of bis (3-aminopropyl) tetramethyldisiloxane, bis (p-amino-phenyl) octamethylpentasiloxane, and the like.
- a terminal blocking agent can be reacted with the terminal of the resin whose main component is the structure represented by the general formula (1).
- a monoamine having a functional group such as a hydroxyl group, carboxyl group, sulfonic acid group, thiol group, vinyl group, ethynyl group, allyl group, acid anhydride, acid chloride, monocarboxylic acid.
- the dissolution rate of the resin in the alkaline aqueous solution can be adjusted to a preferred range.
- the content of the end-capping agent such as monoamine, acid anhydride, acid chloride, monocarboxylic acid is preferably 5 to 50 mol% with respect to the total amine component.
- the end-capping agent introduced into the resin can be easily detected by the following method. For example, by dissolving a resin into which an end-capping agent has been introduced in an acidic solution and decomposing it into an amine component and an acid anhydride component, which are constituent units of the resin, this is analyzed by gas chromatograph (GC) or NMR measurement.
- GC gas chromatograph
- NMR nuclear magnetic resonance
- the sealant can be easily detected.
- PPC pyrolysis gas chromatography
- infrared spectrum and 13 C-NMR spectrum measurement.
- the resin whose main component is the structure represented by the general formula (1) is synthesized by the following method.
- the resin whose main component is the structure represented by the general formula (1) is a polyamic acid or a polyamic acid ester, for example, a tetracarboxylic dianhydride and a diamine compound at a low temperature, and a monoamino compound used for end-capping are used.
- a dehydrating condensing agent such as dicyclohexylcarbodiimide (DCC) is reacted with an acid and a bisaminophenol compound or monoamino compound is added thereto, or a bisaminophenol compound or monoamino added with a tertiary amine such as pyridine.
- DCC dicyclohexylcarbodiimide
- the resin having the structure represented by the general formula (1) as a main component is polymerized by the above method, it is poured into a large amount of water or a methanol / water mixture, precipitated, filtered and dried, It is desirable to isolate. By this precipitation operation, unreacted monomers and oligomer components such as dimers and trimers are removed, and film properties after thermosetting are improved.
- the polyimide (a-2) of the present invention is a polymer having an imide ring by heating a polyimide precursor or by an appropriate catalyst. Due to the annular structure, the heat resistance and solvent resistance are dramatically improved.
- the polyimide has a structural unit represented by the following general formula (3).
- Y 1 represents an aromatic diamine residue having 1 to 4 aromatic rings.
- Examples of the preferred structure of the diamine residue constituting Y 1 include divalent residues of the following compounds: bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino- 4-hydroxyphenyl) sulfone, bis (3-amino-4-hydroxyphenyl) propane, bis (3-amino-4-hydroxyphenyl) methylene, bis (3-amino-4-hydroxyphenyl) ether, bis (3- Hydroxyl group-containing diamines such as amino-4-hydroxy) biphenyl and bis (3-amino-4-hydroxyphenyl) fluorene, sulfonic acid-containing diamines such as 3-sulfonic acid-4,4′-diaminodiphenyl ether, and dimercaptophenylenediamine Thiol group-containing diamine such as 3,4'-diaminodiphenyl Ether, 4,4'
- the polyimide (a-2) of the present invention has a structural unit represented by the following general formula (4).
- Y 2 represents a diamine residue having at least two alkylene glycol units in the main chain.
- it is a diamine compound residue containing at least two ethylene glycol chains or propylene glycol chains in one molecule, more preferably a diamine compound residue having a structure not containing an aromatic ring. .
- the diamine containing ethylene glycol chain and propylene glycol chain is Jeffamine KH-511, Jeffamine ED-600, Jeffamine ED-900, Jeffamine ED-2003, and the diamine containing ethylene glycol chain is Jeffamine EDR. -148, Jeffermin EDR-176 (trade name, manufactured by HUNTSMAN) and the like, but are not limited thereto.
- X 1 represents a tetracarboxylic acid residue having 1 to 4 aromatic rings.
- X 2 represents a tetracarboxylic acid residue having 1 to 4 aromatic rings.
- X 1 and X 2 may be the same or different, and preferred structures thereof include pyromellitic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4′-biphenyl.
- Tetracarboxylic acid 2,2 ′, 3,3′-biphenyltetracarboxylic acid, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid, 2,2 ′, 3,3′-benzophenone tetracarboxylic acid, 2 , 2-bis (3,4-dicarboxyphenyl) hexafluoropropane, 2,2-bis (2,3-dicarboxyphenyl) hexafluoropropane, 1,1-bis (3,4-dicarboxyphenyl) ethane 1,1-bis (2,3-dicarboxyphenyl) ethane, bis (3,4-dicarboxyphenyl) methane, bis (2,3-dicarboxyphenyl) methane, bis (3,4-dicar Xylphenyl) sulfone, bis (3,4-dicarboxyphenyl) ether, 1,2,5,6-naphthalenetetrac
- the polyimide (a-2) of the present invention was obtained by reacting a tetracarboxylic acid to be a tetracarboxylic acid residue represented by X 1 or X 2 and a diamine to be a diamine residue represented by Y 1 or Y 2 .
- Polyamic acid can be obtained by dehydration and ring closure by heating or chemical treatment such as acid or base.
- the (a-2) polyimide of the present invention may not be partially ring-closed, and preferably has an imidization ratio of 85% or more, more preferably 90% or more.
- the imidization rate is 85% or more, film shrinkage due to dehydration and ring closure that occurs when imidization is performed by heating, and generation of warpage can be suppressed.
- the (a-2) polyimide of the present invention may be composed of only the structural units of the general formulas (3) and (4), or may be a copolymer or a mixture with other structural units.
- the ratio of the structural unit represented by the general formula (3) to the structural unit represented by the general formula (4) is 30:70 to 90:10, and is 50:50 to 90:10. It is preferable that the ratio is 60:40 to 80:20.
- the content of the portion of the structural unit represented by the general formula (3) and the general formula (4) is preferably 50% by mass or more, and more preferably 70% by mass or more of the entire resin.
- the (a-2) polyimide of the present invention preferably has a fluorine atom in the structural unit.
- the fluorine atom imparts water repellency to the surface of the film during alkali development, and soaking in from the surface can be suppressed.
- the fluorine atom content in the component (a-2) is preferably 10% by mass or more, and preferably 20% by mass or less from the viewpoint of maintaining solubility in an aqueous alkali solution.
- an aliphatic group having a siloxane structure may be copolymerized.
- the diamine component include bis (3-aminopropyl) tetramethyldisiloxane and bis (p-aminophenyl) octamethylpentasiloxane.
- the resin as the component (a-2) has an end-capping agent such as monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound at the main chain terminal It is preferable to seal with.
- Acid anhydrides, monocarboxylic acids, monoacid chloride compounds, monoactive ester compounds used as end-capping agents are phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride Acid anhydrides such as 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-8-carboxynaphthalene, 1 -Hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-hydroxy-4-carboxynaphthalene, 1-hydroxy-3-carboxynaphthalene, 1-hydroxy-2- Mosquito Boxynaphthalene, 1-mercapto-8-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-
- phthalic anhydride maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, acid anhydrides such as 3-hydroxyphthalic anhydride, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxy Naphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, 3,4-diethynylbenzoic acid, 3,5-diethynyl Benzo Monocarboxylic acids such as these, and monoacid chlor
- Monoamine is more preferably used as the end-capping agent, and preferable monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy.
- a diamine residue having an alkylene glycol unit in the main chain of Y 2 as a structural unit represented by the general formula (4) is represented by the following general formula (5).
- a diamine residue having a structure is preferable. Since it is a diamine residue having a structure represented by the general formula (5), it has a low elastic modulus, a small warpage, and a high flexibility, so that the elongation is improved and the heat resistance is also excellent.
- R 8 and R 9 represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and a plurality of R 8 in the same residue may be the same or different. Represents an integer of 2 to 50.
- the positive photosensitive resin composition of the present invention may contain (b) a phenol resin.
- (B) The phenol resin is obtained by polycondensing phenols and aldehydes by a known method. You may contain combining 2 or more types of phenol resins.
- phenols include phenol, o-cresol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3 , 5-trimethylphenol, 3,4,5-trimethylphenol and the like.
- phenol, m-cresol, p-cresol, 2,3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol or 2,3,5-trimethylphenol are preferable. Two or more of these phenols may be used in combination.
- the resin having a phenolic hydroxyl group preferably includes an m-cresol residue or a cresol novolak resin containing an m-cresol residue and a p-cresol residue.
- the molar ratio of m-cresol residue to p-cresol residue (m-cresol residue / p-cresol residue, m / p) in the cresol novolak resin is preferably 1.8 or more. If it is this range, the moderate solubility to an alkali developing solution will be shown, and favorable sensitivity will be obtained. More preferably, it is 4 or more.
- aldehydes include formalin, paraformaldehyde, acetaldehyde, benzaldehyde, hydroxybenzaldehyde, chloroacetaldehyde, salicylaldehyde and the like. Of these, formalin is particularly preferred. Two or more of these aldehydes may be used in combination.
- the amount of the aldehyde used is preferably 0.6 mol or more, more preferably 0.7 mol or more, and preferably 3.0 mol or less, with respect to 1.0 mol of phenols, from the viewpoint of pattern processability. More preferable is 5 mol or less.
- an acidic catalyst is usually used.
- the acidic catalyst include hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, p-toluenesulfonic acid, and the like.
- the amount of these acidic catalysts used is usually 1 ⁇ 10 ⁇ 5 to 5 ⁇ 10 ⁇ 1 mol per 1 mol of phenols.
- water is usually used as a reaction medium. However, when a heterogeneous system is formed from the beginning of the reaction, a hydrophilic solvent or a lipophilic solvent is used as the reaction medium.
- hydrophilic solvent examples include alcohols such as methanol, ethanol, propanol, butanol and propylene glycol monomethyl ether; and cyclic ethers such as tetrahydrofuran and dioxane.
- lipophilic solvent examples include ketones such as methyl ethyl ketone, methyl isobutyl ketone, and 2-heptanone. The amount of these reaction media used is usually 20 to 1,000 parts by mass per 100 parts by mass of the reaction raw material.
- the reaction temperature of the polycondensation can be appropriately adjusted according to the reactivity of the raw material, but is usually 10 to 200 ° C.
- phenols, aldehydes, acidic catalysts, etc. are charged all at once and reacted, or phenols, aldehydes, etc. are added as the reaction proceeds in the presence of acidic catalysts, etc. Can be adopted as appropriate.
- the reaction temperature is generally increased to 130 to 230 ° C., and volatile components are reduced under reduced pressure. The resin having a phenolic hydroxyl group is removed.
- the polystyrene-reduced weight average molecular weight (Mw) of the phenol resin is preferably 2,000 or more and 15,000 or less, more preferably 3,000 or more and 10,000 or less. Within this range, pattern size variations after curing can be reduced while maintaining high sensitivity and high resolution.
- (A-1) an alkali-soluble resin containing at least one selected from a resin having a structure represented by the general formula (1) as a main component, (a-2) a polyimide, and a copolymer thereof; b)
- examples of the (b) phenol resin include a resol resin and a novolak resin, and a novolak resin is preferable from the viewpoint of high sensitivity and storage stability.
- the photosensitive resin composition of this invention contains the compound which has as a main component the structure represented by (c) following General formula (2).
- a nitrogen-containing compound is contained as an impurity in the photosensitive resin precursor composition.
- adhesion to copper and pattern processability are improved by containing a compound having a structure represented by the general formula (2) as a main component.
- R 5 , R 6 and R 7 may be the same or different and each is a hydrogen atom or a monovalent organic group having 1 or more carbon atoms, R 5 , R 6 and R 7 At least one of 7 represents a monovalent organic group having 1 or more carbon atoms.
- R 5 , R 6 and R 7 may be the same or different, and are a hydrogen atom or a monovalent organic group having 1 or more carbon atoms, and R 5 , R 6 and R 7 At least one of 7 is a monovalent organic group having 1 or more carbon atoms.
- a heterocyclic compound containing a nitrogen atom generally deactivates the photosensitizer and reduces pattern processability, but at least one of R 5 , R 6 and R 7 is a monovalent organic group having 1 or more carbon atoms. As a result, a decrease in sensitivity can be suppressed.
- Specific examples of the compound represented by the general formula (2) include methylpyridine, ethylpyridine, propylpyridine, butylpyridine, 4- (1-butylpentyl) pyridine, dimethylpyridine, trimethylpyridine, triethylpyridine, phenylpyridine, 2-methyl-4-phenyl-pyridine, 2-methyl-6-phenyl-pyridine, 4-tert-butylpyridine, diphenylpyridine, benzylpyridine, methoxypyridine, butoxypyridine, dimethoxypyridine, 1-methyl-2-pyridone, Examples thereof include, but are not limited to, 4-pyrrolidinopyridine, 1-methyl-4-phenylpyridine, 2- (1-ethylpropyl) pyridine, aminopyridine, dimethylaminopyridine and the like.
- the content of the compound whose main component is the structure represented by the general formula (2) is (a-1) a resin whose main component is the structure represented by the general formula (1), ) 0.01 parts by mass or more is preferable from the viewpoint of further improving the adhesiveness to copper with respect to 100 parts by mass of the alkali-soluble resin containing at least one selected from polyimide and copolymers thereof. .05 parts by mass or more is more preferable. Moreover, 5 mass parts or less are preferable at the point of pattern workability, and 3 mass parts or less are more preferable. Furthermore, 0.42 parts by mass or more and 0.68 parts by mass or less are more preferable in order to achieve both adhesion with copper and pattern workability.
- a quinonediazide compound can be contained for the purpose of imparting photosensitivity.
- the quinonediazide compound both 5-naphthoquinonediazidosulfonyl group and 4-naphthoquinonediazidesulfonyl group are preferably used.
- the 4-naphthoquinonediazide sulfonyl ester compound has absorption in the i-line region of a mercury lamp and is suitable for i-line exposure.
- the 5-naphthoquinonediazide sulfonyl ester compound has an absorption extending to the g-line region of a mercury lamp and is suitable for g-line exposure.
- a naphthoquinone diazide sulfonyl ester compound can be obtained by using a 4-naphthoquinone diazide sulfonyl group and a 5-naphthoquinone diazide sulfonyl group in the same molecule, or a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound. Can also be used in combination.
- the molecular weight of the quinonediazide compound is 1500 or less, the quinonediazide compound is sufficiently thermally decomposed in the subsequent heat treatment, and the heat resistance, mechanical properties, and adhesiveness of the resulting film can be maintained.
- molecular weight is 300 or more, decomposition
- the molecular weight of the preferred quinonediazide compound is 300 to 1500. More preferably, the thickness is 350 to 1200. Within this range, a film excellent in heat resistance, mechanical properties, and adhesiveness can be formed.
- the content of (d) the quinonediazide compound is (a-1) a resin whose main component is a structure represented by the general formula (1), (a-2) polyimide And 100 parts by mass of an alkali-soluble resin containing at least one selected from these copolymers, preferably 1 part by mass or more in terms of maintaining the film thickness of the unexposed part after development.
- a-1 a resin whose main component is a structure represented by the general formula (1)
- a-2 polyimide polyimide
- 100 parts by mass of an alkali-soluble resin containing at least one selected from these copolymers preferably 1 part by mass or more in terms of maintaining the film thickness of the unexposed part after development.
- 50 mass parts or less are preferable at the point of pattern workability, and 40 mass parts or less are more preferable.
- the quinonediazide compound used in the present invention is synthesized from a specific phenol compound by the following method. For example, there is a method of reacting 5-naphthoquinonediazidesulfonyl chloride with a phenol compound in the presence of triethylamine. As a method for synthesizing a phenol compound, there is a method in which an ⁇ - (hydroxyphenyl) styrene derivative is reacted with a polyhydric phenol compound under an acid catalyst.
- the positive photosensitive resin composition of the present invention may contain (e) a solvent.
- Solvents include polar aprotic solvents such as ⁇ -butyrolactone, ethers such as tetrahydrofuran, dioxane, and propylene glycol monomethyl ether, dialkylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, diethylene glycol dimethyl ether, and diethylene glycol ethyl methyl ether.
- Ketones such as acetone, methyl ethyl ketone, diisobutyl ketone, diacetone alcohol, N, N-dimethylformamide, N, N-dimethylacetamide, acetates such as 3-methoxybutyl acetate, ethylene glycol monoethyl ether acetate, ethyl acetate , Esters such as propylene glycol monomethyl ether acetate and ethyl lactate, toluene,
- the solvents such as aromatic hydrocarbons such as Ren alone or in combination may be used.
- the content of (e) the solvent is (a-1) in that a resin film having a film thickness capable of functioning the pattern processability of the positive photosensitive resin film can be obtained.
- an alkali-soluble resin containing at least one selected from a resin having a structure represented by the general formula (1) as a main component, (a-2) polyimide, and a copolymer thereof 50 parts by mass or more is preferable, and 100 parts by mass or more is more preferable.
- 2000 mass parts or less are preferable at the point from which the resin film used as the film thickness which functions as a protective film is obtained, and 1500 mass parts or less are more preferable.
- the positive photosensitive resin composition of the present invention may contain (f) a compound containing an alkoxymethyl group.
- the compound containing an alkoxymethyl group is preferably a compound represented by the following general formula (6). Although the compound represented by the general formula (6) has an alkoxymethyl group, the alkoxymethyl group undergoes a crosslinking reaction in a temperature range of 150 ° C. or higher. Therefore, by containing the compound, the polyimide precursor or the polybenzoxazole precursor can be crosslinked by heat and cured by heat treatment to obtain a better pattern shape.
- a compound having two or more alkoxymethyl groups is preferable for increasing the crosslinking density, and a compound having four or more alkoxymethyl groups is more preferable from the viewpoint of increasing the crosslinking density and further improving chemical resistance. Further, from the viewpoint of reducing variation in pattern dimensions after curing, it is preferable to have at least one compound having 6 or more alkoxymethyl groups.
- R 10 represents a 1 to 10 valent organic group.
- R 11 may be the same or different and represents an alkyl group having 1 to 4 carbon atoms. R is an integer of 1 to 10) Is shown.
- the compound (f) include the following compounds, but are not limited thereto. Moreover, you may contain 2 or more types of these.
- the content of the compound (f) is (a-1) a resin mainly composed of the structure represented by the general formula (1) from the viewpoint of increasing the crosslink density and further improving chemical resistance and mechanical properties.
- a-2) 1 part by mass or more is preferable with respect to 100 parts by mass of the alkali-soluble resin containing at least one selected from polyimides and copolymers thereof. Moreover, 20 mass parts or less are preferable from a viewpoint that the crack after heat processing can be suppressed.
- the positive photosensitive resin composition of the present invention can contain (g) a silane compound, and can improve the adhesion to the base substrate.
- a silane compound include N-phenylaminoethyltrimethoxysilane, N-phenylaminoethyltriethoxysilane, N-phenylaminopropyltrimethoxysilane, N-phenylaminopropyltriethoxysilane, and N-phenyl.
- silane compound is not limited thereto. Two or more of these may be contained.
- the content of the silane compound is such that (a-1) a resin having a structure represented by the general formula (1) as a main component, (a-2) polyimide, 0.01 parts by mass or more is preferable with respect to 100 parts by mass of the alkali-soluble resin including at least one selected from the group consisting of these and copolymers thereof. Moreover, 15 mass parts or less are preferable from a viewpoint of maintaining the heat resistance of positive photosensitive resin composition.
- the positive photosensitive resin composition of the present invention can contain (h) a compound having a phenolic hydroxyl group.
- a compound having a phenolic hydroxyl group By containing a compound having a phenolic hydroxyl group, the obtained positive photosensitive resin composition hardly dissolves in an alkali developer before exposure, and easily dissolves in an alkali developer upon exposure. Less film loss and easy development in a short time.
- (H) Bis-Z, TekP-4HBPA, TrisP-HAP, TrisP-PA, BisRS-2P, BisRS-3P are particularly preferred as compounds having a phenolic hydroxyl group.
- BIR-PC, BIR-PTBP, BIR-BIPC-F (trade name, available from Asahi Organic Materials Co., Ltd.), and the like.
- the content of the compound having a phenolic hydroxyl group is: (a-1) a resin mainly composed of a structure represented by the general formula (1), (a-2) a polyimide, and a copolymer thereof, 3 parts by mass or more and 40 parts by mass or less are preferable in terms of heat resistance and mechanical properties with respect to 100 parts by mass of the alkali-soluble resin containing at least one selected from
- esters such as ethyl lactate and propylene glycol monomethyl ether acetate, alcohols such as ethanol, cyclohexanone, methyl isobutyl
- ketones such as a ketone
- ethers such as tetrahydrofuran and a dioxane.
- inorganic particles such as silicon dioxide and titanium dioxide, polyimide powder, and the like can also be contained.
- the production method of the positive photosensitive resin composition of the present invention is exemplified.
- an alkali-soluble resin containing at least one selected from (a-1) a resin whose main component is a structure represented by the general formula (1), (a-2) a polyimide, and a copolymer thereof, (B) a phenol resin, (c) a compound having a structure represented by the general formula (2) as a main component, (d) a quinonediazide compound, (e) a solvent, and if necessary, other components made of a glass flask or stainless steel And a method of stirring and dissolving with a mechanical stirrer, a method of dissolving with ultrasonic waves, a method of stirring and dissolving with a planetary stirring deaerator, and the like.
- the viscosity of the composition is preferably 200 to 10,000 mPa ⁇ s. Further, in order to remove the foreign matter, it may be filtered through a filter having a pore size of
- a positive type photosensitive resin composition is applied on a substrate.
- a silicon wafer, ceramics, gallium arsenide, metal, glass, metal oxide insulating film, silicon nitride, indium tin oxide (ITO), or the like is used, but is not limited thereto.
- the coating method include spin coating, spray coating, roll coating, and slit die coating.
- a particularly advantageous effect can be obtained in coating by a spin coating method.
- the coating film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like, but is usually applied so that the film thickness after drying is 5 to 30 ⁇ m. It is preferably 2 ⁇ m or more from the viewpoint of chemical resistance in the flux treatment. Moreover, it is preferable that it is 15 um or less from the point of adhesiveness with the metal wiring after a flux process.
- the substrate coated with the positive photosensitive resin composition is dried to obtain a photosensitive resin film. Drying is preferably performed using an oven, a hot plate, infrared rays, or the like at 50 to 150 ° C. for 1 minute to several hours.
- the photosensitive resin film is exposed to actinic radiation through a mask having a desired pattern.
- actinic radiation used for exposure there are ultraviolet rays, visible rays, electron beams, X-rays and the like.
- the exposed portion may be removed using a developer after exposure.
- the developer is an aqueous solution of tetramethylammonium, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylamino
- An aqueous solution of a compound exhibiting alkalinity such as ethyl methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine and the like is preferable.
- these alkaline aqueous solutions may contain polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, ⁇ -butyrolactone, dimethylacrylamide, methanol, ethanol,
- polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, ⁇ -butyrolactone, dimethylacrylamide, methanol, ethanol,
- One or more alcohols such as isopropanol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone and methyl isobutyl ketone may be added.
- alcohols such as ethanol and isopropyl alcohol, and esters such as eth
- a cured pattern film having heat resistance After developing the pattern resin film, it is converted into a cured pattern film having heat resistance by applying a temperature of 200 to 500 ° C.
- This heat treatment is generally carried out for 5 minutes to 5 hours by selecting the temperature and raising the temperature stepwise, or selecting a certain temperature range and continuously raising the temperature. For example, heat treatment at 130 ° C., 200 ° C., 350 ° C. for 30 minutes each, method of linearly increasing the temperature from room temperature to 320 ° C. over 2 hours, charging at a high temperature of 200 ° C. over 2 hours The method of raising temperature linearly can be mentioned.
- the heat-cured pattern cured film formed by the positive photosensitive resin composition of the present invention includes a surface protective film layer of a semiconductor device, an insulating film used for forming a rewiring layer of a semiconductor device, a semiconductor passivation film, and a semiconductor It is suitably used for applications such as protective films for elements, interlayer insulating films for multilayer wiring for high-density mounting, and insulating layers for organic electroluminescent elements.
- FIG. 1 A preferred structure in the present invention is shown in FIG.
- a passivation film 2 is formed on the semiconductor element 1.
- the photosensitive resin composition according to the present invention is applied onto the passivation film 2 by spin coating, dried by heating using a hot plate or the like, and patterned through exposure and development. After the resin film pattern is formed, a high-temperature treatment process by curing is performed to form a resin film (pattern cured film) 3.
- a metal wiring 4 is formed on the resin film 3 by a technique such as sputtering, vapor deposition, electroless plating, or electrolytic plating. Further, in order to protect the metal wiring 4, the photosensitive resin composition according to the present invention is applied by spin coating, heated and dried using a hot plate or the like, and patterned through exposure and development.
- a high temperature treatment process by curing is performed to form a resin film (pattern cured film) 5.
- a semiconductor device having high adhesion between the resin films 3 and 5 and high adhesion between the resin films 3 and 5 and the metal wiring 4 can be provided. .
- a lambda ace STM-602 manufactured by Dainippon Screen Mfg. Co., Ltd. was used, and the film thickness after pre-baking and development was measured at a refractive index of 1.629 based on polyimide.
- the imidization ratio of polyimide was such that an N-methylpyrrolidone (NMP) solution having a polyimide resin solid content concentration of 50 mass% was applied onto a 6-inch silicon wafer by spin coating, and then 120 ° C. Baking was performed for 3 minutes with a hot plate (SKW-636 manufactured by Dainippon Screen Mfg. Co., Ltd.) to prepare a prebaked film having a thickness of 10 ⁇ m ⁇ 1 ⁇ m. This film was divided in half, and one side was placed in an inert oven (INH-21CD manufactured by Koyo Thermo Systems Co., Ltd.), raised to a curing temperature of 350 ° C.
- NMP N-methylpyrrolidone
- the obtained cured film (A) and the film before curing (B) were measured for infrared absorption spectra using a Fourier transform infrared spectrophotometer FT-720 (manufactured by Horiba, Ltd.). The peak intensity in the vicinity of 1377 cm ⁇ 1 due to CN stretching vibration of the imide ring was determined, and the ratio of “the peak intensity of the film (B) before curing / the peak intensity of the cured film (A)” was defined as the imidization ratio.
- a photosensitive resin film was obtained by pre-baking at 120 ° C. for 3 minutes using a coating and developing apparatus ACT8) manufactured by Electron Co., Ltd.
- ⁇ Exposure> The reticle from which the pattern was cut was set in an exposure machine (Ni-line i-line stepper NSR2005i9C), and the photosensitive resin film was exposed to i-line at an intensity of 365 nm for a predetermined time.
- Eth the minimum exposure amount at which the 50 ⁇ m pad pattern after development opened to 50 ⁇ m was determined. If Eth is 600 mJ / cm 2 or less, the pattern workability is good, 400 mJ / cm 2 or less is more preferable, and 300 mJ / cm 2 or less is more preferable.
- Tantalum (Ta) was sputtered on an 8-inch silicon wafer by 25 nm, copper was sputtered by 100 nm, and a copper substrate was prepared by laminating copper by 3 ⁇ m electrolytic plating. A patterned cured film was obtained on the copper substrate by the method described above. After applying flux WS9160 (produced by Arend Japan) to the pattern cured film on the copper substrate, the wafer with the pattern was subjected to a reflow treatment in a reflow furnace RN-SANUR820iN (produced by Panasonic Device Sunx Tatsuno Co., Ltd.).
- the reflow treatment conditions were such that the oxygen concentration was 1,000 ppm or less, the heater temperature and the conveyor speed were adjusted, and the wafer was heated at 270 ° C. for 60 seconds or more. After the treatment, it was washed with 50 ° C. water, air-dried, and dried for 1 hour or more in an atmosphere of 23 ° C. and 50% RH.
- a peel test was performed using the cured pattern film after the reflow treatment.
- a die share tester, Series 4000 manufactured by DAGE ARCTEK was used, and the conditions of die share were carried out at a share test speed of 100 ⁇ m / sec.
- the pattern cured film was peeled from the long sides of 120 ⁇ m in length and 30 ⁇ m in width, the maximum peel strength at 7 locations was measured, and the average value was defined as the adhesion strength.
- the adhesion strength is preferably 60 mN or more, more preferably 180 mN or more, and further preferably 420 mN or more.
- This precipitate was dissolved in 200 mL of GBL, 3 g of 5% palladium-carbon was added, and the mixture was vigorously stirred. A balloon filled with hydrogen gas was attached thereto, and stirring was continued until the balloon of hydrogen gas did not contract any more at room temperature, and further stirred for 2 hours with the balloon of hydrogen gas attached. After the completion of stirring, the palladium compound as a catalyst was removed by filtration, and the solution was concentrated to a half amount by a rotary evaporator. Ethanol was added thereto for recrystallization to obtain a hydroxyl group-containing diamine (c) crystal represented by the following formula.
- the temperature of the oil bath is raised over 3 hours, and then the pressure in the 1 L flask is reduced to 40 to 67 hPa to remove volatile components, and then cooled to room temperature to obtain a polymer solid of phenol resin A. It was. From GPC, the weight average molecular weight was 3,500.
- the temperature of the oil bath is raised over 3 hours, and then the pressure in the 1 L flask is reduced to 40 to 67 hPa to remove volatile components, and then cooled to room temperature to obtain a polymer solid of phenol resin B. It was. From GPC, the weight average molecular weight was 6,700.
- the solution was poured into 2 L of water, and a polymer solid precipitate was collected by filtration.
- the polymer solid was dried with a vacuum dryer at 80 ° C. for 72 hours to obtain a polyimide precursor polymer D.
- a varnish composed of 18 types of photosensitive resin compositions described in Tables 1 and 2 (Examples 1 to 32, Comparative Examples 1 to 6) was prepared to produce a photosensitive resin film, and pattern processability [minimum exposure Quantity (Eth)] was evaluated. Moreover, the copper adhesiveness [adhesion strength] of the pattern cured film after the reflow treatment was evaluated.
- the photosensitive resin composition (a-1) the polymers C to K and N obtained in Synthesis Examples 9 to 17 and 20 as resins whose main component is the structure represented by the general formula (1) Used, “C” to “K” and “N” are described in the column of “resin (a-1)” in Tables 1 and 2.
- the quinonediazide compounds (e) and (f) obtained in Synthesis Examples 5 and 6 were used, and “(e)” and “(f)” were listed in the “quinonediazide compound” column in Tables 1 and 2. It was described. In Tables 1 and 2, ⁇ -butyrolactone (GBL) was used as the type of solvent.
- Example 1 7.0 g of polymer C, 3.0 g of phenol resin A, 0.01 g of trimethylpyridine and 1.5 g of quinonediazide compound (f) were measured and dissolved in 15.0 g of GBL to obtain a varnish of a positive type photosensitive resin composition. Using the obtained varnish, the pattern workability [minimum exposure (Eth)] and the adhesion with copper [adhesion strength] were evaluated as described above.
- Examples 2 to 33, Comparative Examples 1 to 6 A varnish was prepared in the same manner as in Example 1 except that the polyimide / novolak resin ratio or other additives were changed as shown in Tables 1 and 2, and each evaluation test for pattern workability and copper adhesion was performed. .
Abstract
Description
(b)フェノール樹脂は、フェノール類とアルデヒド類とを公知の方法で重縮合することによって得られる。2種以上のフェノール樹脂を組み合わせて含有してもよい。
本発明のポジ型感光性樹脂組成物において、(e)溶剤の含有量は、ポジ型感光性樹脂膜のパターン加工性が機能する膜厚となる樹脂膜が得られる点で、(a-1)一般式(1)で表される構造を主成分とする樹脂、(a-2)ポリイミド、およびそれらの共重合体、から選ばれる少なくとも1種類を含むアルカリ可溶性樹脂100質量部に対して、50質量部以上が好ましく、100質量部以上がより好ましい。また、保護膜として機能する膜厚となる樹脂膜が得られる点で2000質量部以下が好ましく、1500質量部以下がより好ましい。
一般的には半導体素子1上にパッシベーション膜2が形成されている。パッシベーション膜2上に本発明による感光性樹脂組成物をスピンコートで塗布し、ホットプレートなどを用いて加熱乾燥し、露光・現像を通してパターン形成する。樹脂膜のパターン形成後に、キュアによる高温処理プロセスを行い、樹脂膜(パターン硬化膜)3を形成する。樹脂膜3上にスパッタ、蒸着、無電解めっき、電解めっきなどの手法で金属配線4を形成する。さらに、金属配線4を保護するために本発明による感光性樹脂組成物をスピンコートで塗布し、ホットプレートなどを用いて加熱乾燥し、露光・現像を通してパターン形成する。樹脂膜のパターン形成後に、キュアによる高温処理プロセスを行い、樹脂膜(パターン硬化膜)5を形成する。上記の手法にて樹脂膜3,5を形成することにより、樹脂膜3,5同士の高い密着性および樹脂膜3,5と金属配線4の高い密着性を有する半導体装置を提供することができる。
<膜厚の測定方法>
(a-2)ポリイミドのイミド化率は、6インチのシリコンウエハ上に、ポリイミド樹脂の固形分濃度50質量%のN-メチルピロリドン(NMP)溶液をスピンコート法で塗布し、次いで120℃のホットプレート(大日本スクリーン製造(株)製SKW-636)で3分間ベークし、厚さ10μm±1μmのプリベーク膜を作製した。この膜を半分に割り、片方をイナートオーブン(光洋サーモシステム製INH-21CD)に投入し、350℃の硬化温度まで30分間かけて上昇させ、350℃で60分間加熱処理を行った。その後、オーブン内が50℃以下になるまで徐冷し、硬化膜を得た。得られた硬化膜(A)と硬化前の膜(B)について、フーリエ変換赤外分光光度計FT-720(堀場製作所製)を用いて赤外吸収スペクトルを測定した。イミド環のC-N伸縮振動による1377cm-1付近のピーク強度を求め、「硬化前の膜(B)のピーク強度/硬化膜(A)のピーク強度」の比をイミド化率とした。
8インチシリコンウエハ上に感光性樹脂組成物のワニスをプリベーク後の膜厚T1(塗布後膜厚)=8.5~9.0μmとなるようにスピンコート法により塗布し、ついでホットプレート(東京エレクトロン(株)製の塗布現像装置ACT8)を用いて、120℃で3分間プリベークすることにより、感光性樹脂膜を得た。
露光機(Nicon社製i線ステッパーNSR2005i9C)に、パターンの切られたレチクルをセットし、365nmの強度で上記感光性樹脂膜を所定の時間、i線で露光した。
東京エレクトロン(株)製ACT8の現像装置を用い、50回転で水酸化テトラメチルアンモニウムの2.38質量%水溶液を10秒間、露光後の膜に噴霧した。この後、0回転で40秒間静置した。現像液を振り切り、再度水酸化テトラメチルアンモニウムを噴霧、20秒間静置した。この後、400回転で水にてリンス処理し、3,000回転で10秒振り切り乾燥した。
上記露光および現像において露光時間を変化させることを繰り返し、現像後の50μmパッドパターンが50μmに開口する最小露光量(Eth)を求めた。Ethが600mJ/cm2以下であればパターン加工性は良好であり、400mJ/cm2以下がより好ましく、300mJ/cm2以下がさらに好ましい。
上記パターン加工性の評価にて得られたパターン加工膜を縦型キュア炉 VF-1000B(光洋サーモシステム社製)にて窒素雰囲気下で酸素濃度20ppm以下の条件で、350℃で60分間の熱処理を実施し、パターン硬化膜を得た。
8インチのシリコンウエハ上にタンタル(Ta)を25nmスパッタリングし、銅を100nmスパッタリングし、さらに銅を3μm電解めっきにて積層した銅基板を作製した。銅基板上に上記記載の方法でパターン硬化膜を得た。銅基板上のパターン硬化膜にフラックスWS9160(アレントジャパン社製)を塗布後、当該パターン付きウエハを、リフロー炉RN-S ANUR820iN(パナソニックデバイスSUNX竜野社製)にて、リフロー処理した。リフロー処理条件は、酸素濃度1,000ppm以下で、ヒーター温度、コンベア速度を調整し、ウエハを270℃で60秒以上加熱する条件とした。処理後、50℃の水で洗浄し、風乾後、23℃、50%RH雰囲気下で1時間以上乾燥させた。
上記リフロー処理後のパターン硬化膜を用いて剥離試験を実施した。ダイシェアテスター、Series4000(DAGE ARCTEK製)を用いて、ダイシェアの条件はシェアテストスピード100μm/secの条件にて実施した。パターン硬化膜の縦120μm、横30μmの長辺より剥離させ、7箇所での剥離最大強度を測定し、平均値を密着強度とした。密着強度は60mN以上であれば良好であり、180mN以上であればより好ましく、420mN以上であればさらに好ましい。
乾燥窒素気流下、2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフルオロプロパン(BAHF)18.3g(0.05モル)とアリルグリシジルエーテル34.g(0.3モル)をγ-ブチロラクトン(GBL)100gに溶解させ、-15℃に冷却した。ここにGBL50gに溶解させた無水トリメリット酸クロリド22.1g(0.11モル)を反応液の温度が0℃を越えないように滴下した。滴下終了後、0℃で4時間反応させた。この溶液をロータリーエバポレーターで濃縮して、トルエン1Lに投入して、下記式で表されるヒドロキシル基含有酸無水物(a)を得た。
BAHF18.3g(0.05モル)をアセトン100mL、プロピレンオキシド17.4g(0.3モル)に溶解させ、-15℃に冷却した。ここに3-ニトロベンゾイルクロリド20.4g(0.11モル)をアセトン100mLに溶解させた溶液を滴下した。滴下終了後、-15℃で4時間反応させ、その後室温に戻した。析出した白色固体をろ別し、50℃で真空乾燥した。
2-アミノ-4-ニトロフェノール15.4g(0.1モル)をアセトン50mL、プロピレンオキシド30g(0.34モル)に溶解させ、-15℃に冷却した。ここにイソフタル酸クロリド11.2g(0.055モル)をアセトン60mLに溶解させた溶液を徐々に滴下した。滴下終了後、-15℃で4時間反応させた。その後、室温に戻して生成している沈殿をろ過で集めた。
2-アミノ-4-ニトロフェノール15.4g(0.1モル)をアセトン100mL、プロピレンオキシド17.4g(0.3モル)に溶解させ、-15℃に冷却した。ここに4-ニトロベンゾイルクロリド20.4g(0.11モル)をアセトン100mLに溶解させた溶液を徐々に滴下した。滴下終了後、-15℃で4時間反応させた。その後、室温に戻して生成している沈殿をろ過で集めた。この後、合成例2と同様にして、下記式で表されるヒドロキシル基含有ジアミン(d)の結晶を得た。
TrisP-PA(商品名、本州化学工業(株)製)21.23g(0.050モル)、5-ナフトキノンジアジドスルホニル酸クロリド(NAC5)、37.69g(0.140モル)を2Lフラスコに入れ、1,4-ジオキサン450gに溶解させ、室温にした。ここに、1,4-ジオキサン50gと混合したトリエチルアミン12.85gを系内が35℃以上にならないように滴下した。滴下後40℃で2時間撹拌した。トリエチルアミン塩を濾過し、濾液を水に投入した。その後、析出した沈殿を濾過で集めた。この沈殿を真空乾燥機で乾燥させ、下記式で表されるキノンジアジド化合物(e)を得た。
NAC5に代えて4-ナフトキノンジアジドスルホニル酸クロリド(NAC4)を入れる以外は合成例5と同じようにして下記式で表されるキノンジアジド化合物(f)を得た。
乾燥窒素気流下、m-クレゾール70.2g(0.65モル)、p-クレゾール37.8g(0.35モル)、37質量%ホルムアルデヒド水溶液75.5g(ホルムアルデヒド0.93モル)、シュウ酸二水和物0.63g(0.005モル)、メチルイソブチルケトン264gを1Lフラスコに仕込んだ後、1Lフラスコを油浴中に浸し、反応液を還流させながら、4時間重縮合反応を行った。その後、油浴の温度を3時間かけて昇温し、その後に、1Lフラスコ内の圧力を40~67hPaまで減圧して揮発分を除去し、室温まで冷却してフェノール樹脂Aのポリマー固体を得た。GPCから重量平均分子量は3,500であった。
乾燥窒素気流下、m-クレゾール70.2g(0.65モル)、p-クレゾール37.8g(0.35モル)、37質量%ホルムアルデヒド水溶液75.5g(ホルムアルデヒド0.93モル)、シュウ酸二水和物0.63g(0.005モル)、メチルイソブチルケトン264gを1Lフラスコに仕込んだ後、1Lフラスコを油浴中に浸し、反応液を還流させながら、6時間重縮合反応を行った。その後、油浴の温度を3時間かけて昇温し、その後に、1Lフラスコ内の圧力を40~67hPaまで減圧して揮発分を除去し、室温まで冷却してフェノール樹脂Bのポリマー固体を得た。GPCから重量平均分子量は6700であった。
乾燥窒素気流下、4,4’-ジアミノフェニルエーテル(DAE)4.60g(0.023モル)、1,3-ビス(3-アミノプロピル)テトラメチルジシロキサン(SiDA)1.24g(0.005モル)をN-メチル-2-ピロリドン(NMP)50gに溶解させた。ここに合成例1で得られたヒドロキシル基含有酸無水物(a)21.4g(0.030モル)をNMP14gとともに加えて、20℃で1時間撹拌し、次いで40℃で2時間撹拌した。その後、N,N-ジメチルホルムアミドジメチルアセタール7.14g(0.06モル)をNMP5gで希釈した溶液を10分かけて滴下した。滴下後、40℃で3時間撹拌した。反応終了後、溶液を水2Lに投入して、ポリマー固体の沈殿をろ過で集めた。ポリマー固体を50℃の真空乾燥機で72時間乾燥し、ポリイミド前駆体のポリマーCを得た。GPCにより得られたポリマーの重量平均分子量を測定し、n=10~100,000の範囲内にあることを確認した。
乾燥窒素気流下、合成例2で得られたヒドロキシル基含有ジアミン(b)13.90g(0.023モル)をNMP50gに溶解させた。ここに合成例1で得られたヒドロキシル基含有酸無水物(a)17.5g(0.025モル)をピリジン30gとともに加えて、40℃で2時間撹拌した。その後、N,N-ジメチルホルムアミドジエチルアセタール7.35g(0.05モル)をNMP5gで希釈した溶液を10分かけて滴下した。滴下後、40℃で2時間撹拌した。反応終了後、溶液を水2Lに投入して、ポリマー固体の沈殿をろ過で集めた。ポリマー固体を80℃の真空乾燥機で72時間乾燥しポリイミド前駆体のポリマーDを得た。GPCにより得られたポリマーの重量平均分子量を測定し、n=10~100,000の範囲内にあることを確認した。
乾燥窒素気流下、合成例3で得られたヒドロキシル基含有ジアミン化合物(c)15.13g(0.040モル)、SiDA1.24g(0.005モル)をNMP50gに溶解させた。ここに3,3’,4,4’-ジフェニルエーテルテトラカルボン酸無水物(ODPA)15.51g(0.05モル)をNMP21gとともに加えて、20℃で1時間撹拌し、次いで50℃で1時間撹拌した。その後、N,N-ジメチルホルムアミドジエチルアセタール13.2g(0.09モル)をNMP15gで希釈した溶液を10分かけて滴下した。滴下後、40℃で3時間撹拌した。反応終了後、溶液を水2Lに投入して、ポリマー固体の沈殿をろ過で集めた。ポリマー固体を80℃の真空乾燥機で72時間乾燥しポリイミド前駆体のポリマーEを得た。GPCにより得られたポリマーの重量平均分子量を測定し、n=10~100,000の範囲内にあることを確認した。
乾燥窒素気流下、合成例4で得られたヒドロキシル基含有ジアミン化合物(d)4.37g(0.018モル)とDAE4.51g(0.0225モル)とSiDA0.62g(0.0025モル)をNMP70gに溶解させた。ここに合成例1で得られたヒドロキシル基含有酸無水物(a)24.99g(0.035モル)、3,3’,4,4’-ビフェニルテトラカルボン酸二無水物(BPDA)4.41g(0.010モル)を室温でNMP25gとともに加え、そのまま室温で1時間、その後40℃で1時間撹拌した。その後、N,N-ジメチルホルムアミドジメチルアセタール13.09g(0.11モル)をNMP5gで希釈した溶液を10分かけて滴下した。滴下後、40℃で3時間撹拌した。反応終了後、溶液を水2Lに投入して、ポリマー固体の沈殿をろ過で集めた。ポリマー固体を80℃の真空乾燥機で72時間乾燥しポリイミド前駆体のポリマーFを得た。GPCにより得られたポリマーの重量平均分子量を測定し、n=10~100,000の範囲内にあることを確認した。
乾燥窒素気流下、DAE4.40g(0.022モル)、SiDA1.24g(0.005モル)をNMP50gに溶解させた。ここに合成例1で得られたヒドロキシル基含有酸無水物(a)21.4g(0.030モル)をNMP14gとともに加えて、20℃で1時間反応させ、次いで40℃で2時間撹拌した。その後、末端封止剤として、4-エチニルアニリン0.71g(0.006モル)を加え、さらに40℃で1時間反応させた。その後、N,N-ジメチルホルムアミドジメチルアセタール7.14g(0.06モル)をNMP5gで希釈した溶液を10分かけて滴下した。滴下後、40℃で3時間撹拌した。反応終了後、溶液を水2Lに投入して、ポリマー固体の沈殿をろ過で集めた。ポリマー固体を50℃の真空乾燥機で72時間乾燥しポリイミド前駆体のポリマーGを得た。GPCにより得られたポリマーの重量平均分子量を測定し、n=10~100,000の範囲内にあることを確認した。
乾燥窒素気流下、ジフェニルエーテル-4,4’-ジカルボン酸ジクロライド(DEDC)1モルと1-ヒドロキシベンゾトリアゾール2モルとを反応させて得られたジカルボン酸誘導体19.70g(0.040モル)とBAHF18.31g(0.050モル)をNMP200gに溶解させ、75℃で12時間撹拌し反応を終了した。反応終了後、溶液を水/メタノール=3/1(体積比)の溶液3Lに投入して、ポリマー固体の沈殿をろ過で集めた。ポリマー固体を80℃の真空乾燥機で20時間乾燥し、ポリベンゾオキサゾール前駆体のポリマーHを得た。GPCにより得られたポリマーの重量平均分子量を測定し、n=10~100,000の範囲内にあることを確認した。
乾燥窒素気流下、DAE48.1g(0.241モル)、SiDA25.6g(0.103モル)をNMP820gに溶解させ、ODPA105g(0.338モル)を加え、10℃以上30℃以下となるよう調節しながら8時間撹拌して、ポリイミド前駆体のポリマー溶液Iを得た。GPCにより得られたポリマーの重量平均分子量を測定し、n=10~100,000の範囲内にあした。
乾燥窒素気流下、SiDA198g(0.797モル)をNMP600gに溶解させ、ODPA123.6g(0.398モル)、無水マレイン酸78.2g(0.798モル)を加え、10℃以上30℃以下となるよう調節しながら8時間撹拌して、ポリイミド前駆体のポリマー溶液Jを得た。GPCにより得られたポリマーの重量平均分子量を測定し、n=10~100,000の範囲内にあることを確認した。
乾燥窒素気流下、セバシン酸ジクロライド1モルと1-ヒドロキシベンゾトリアゾール2モルとを反応させて得られたジカルボン酸誘導体17.47(0.040モル)とBAHF18.31g(0.050モル)をNMP200gに溶解させ、75℃で12時間撹拌し反応を終了した。反応終了後、溶液を水/メタノール=3/1(体積比)の溶液3Lに投入して、ポリマー固体の沈殿をろ過で集めた。ポリマー固体を80℃の真空乾燥機で20時間乾燥し、ポリベンゾオキサゾール前駆体のポリマーKを得た。GPCにより得られたポリマーの重量平均分子量を測定し、n=10~100,000の範囲内にあることを確認した。
乾燥窒素気流下、ODPA15.5g(0.2モル)をN-メチルピロリドン250gに溶解させた。ここにBAHF11.9g(0.13モル)、エチレングリコールとプロピレングリコール骨格のジアミンである、1-(2-(2-(2-アミノプロポキシ)エトキシ)プロポキシ)プロパン-2-アミン3.5g(0.06モル)、1,3-ビス(3-アミノプロピル)テトラメチルジシロキサン0.6g(0.01モル)をNMP250gとともに加えて、60℃で1時間反応させ、次いで200℃で6時間反応させた。反応終了後、溶液を室温まで冷却した後、溶液を水2.5Lに投入して白色沈殿を得た。この沈殿を濾過で集めて、水で3回洗浄した後、80℃の真空乾燥機で40時間乾燥し、目的の樹脂であるポリイミドの共重合体Lを得た。イミド化率は96%であった。
乾燥窒素気流下、ODPA15.5g(0.2モル)をNMP250gに溶解させた。ここにBAHF10.1g(0.11モル)、プロピレングリコール骨格のジアミンである、1-((1-((1-(2-アミノプロポキシ)プロパン-2-イル)オキシ)プロパン-2-イル)オキシ)プロパン-2-アミン3.9g(0.07モル)、をNMP50gとともに加え、次に末端封止剤として3-アミノフェノール1.1g(0.04モル)をNMP12.5gとともに加えて、60℃で1時間反応させ、次いで180℃で6時間反応させた。反応終了後、溶液を室温まで冷却した後、溶液を水2.5Lに投入して白色沈殿を得た。この沈殿を濾過で集めて、水で3回洗浄した後、80℃の真空乾燥機で40時間乾燥し、目的の樹脂であるポリイミドの共重合体Mを得た。イミド化率は91%であった。
乾燥窒素気流下、2、2―ビス(4-カルボキシフェニル)ヘキサフルオロプロパンジクロライド1モルと1-ヒドロキシベンゾトリアゾール2モルとを反応させて得られたジカルボン酸誘導体23.58g(0.040モル)とBAHF18.31g(0.050モル)をNMP200gに溶解させ、75℃で12時間撹拌し反応を終了した。反応終了後、溶液を水/メタノール=3/1(体積比)の溶液3Lに投入して、ポリマー固体の沈殿をろ過で集めた。ポリマー固体を80℃の真空乾燥機で20時間乾燥し、ポリベンゾオキサゾール前駆体のポリマーNを得た。GPCにより得られたポリマーの重量平均分子量を測定し、n=10~100,000の範囲内にあることを確認した。
ポリマーC7.0g、フェノール樹脂A3.0g、トリメチルピリジン0.01g、キノンジアジド化合物(f)1.5g、を測りとり、GBL15.0gに溶解させてポジ型感光性樹脂組成物のワニスを得た。得られたワニスを用いて前記のようにパターン加工性[最小露光量(Eth)]、銅との密着性[密着強度]の評価を行った。
ポリイミド/ノボラックの樹脂比率またはその他添加剤を表1、表2のように変更する以外は実施例1と同様の方法でワニスを作製し、パターン加工性および銅密着性の各評価試験を行なった。
2 パッシベーション膜
3 樹脂膜
4 金属配線
5 樹脂膜
Claims (11)
- (a-1)下記一般式(1)で表される構造を主成分とする樹脂、(a-2)ポリイミド、およびそれらの共重合体、から選ばれる少なくとも1種類を含むアルカリ可溶性樹脂、および、(c)下記一般式(2)で表される構造を主成分とする化合物とを含有することを特徴とする感光性樹脂組成物。
- 前記(a-1)一般式(1)で表される構造を主成分とする樹脂、(a-2)ポリイミド、およびそれらの共重合体、から選ばれる少なくとも1種類を含むアルカリ可溶性樹脂100質量部に対し、前記(c)一般式(2)で表される構造を主成分とする化合物を0.42質量部以上0.68質量部以下含有することを特徴とする請求項1に記載の感光性樹脂組成物。
- さらに(b)フェノール樹脂を含有する、請求項1または2に記載の感光性樹脂組成物。
- 前記(a-1)一般式(1)で表される構造を主成分とする樹脂、(a-2)ポリイミド、およびそれらの共重合体、から選ばれる少なくとも1種類を含むアルカリ可溶性樹脂と(b)フェノール樹脂の含有量比が((a-1)+(a-2))/(b)=95/5~5/95(質量比)である請求項3に記載の感光性樹脂組成物。
- 前記(b)フェノール樹脂の重量平均分子量が2,000~15,000である請求項3または4に記載の感光性樹脂組成物。
- 前記(b)フェノール樹脂がノボラック樹脂である請求項3~5のいずれかに記載の感光性樹脂組成物。
- 請求項1~6のいずれかに記載の感光性樹脂組成物を硬化したパターン硬化膜。
- 請求項1~6のいずれかに記載の感光性樹脂組成物を基板上に塗布し乾燥して感光性樹脂膜を形成する感光性樹脂膜形成工程と、マスクを通して感光性樹脂膜を露光する露光工程と、露光後の感光性樹脂膜をアルカリ水溶液を用いて現像しパターン樹脂膜を形成する現像工程と、前記パターン樹脂膜を加熱処理して硬化膜を形成する加熱処理工程とを含むことを特徴とするパターン硬化膜の製造方法。
- 請求項7に記載のパターン硬化膜を表面保護膜層として有することを特徴とする半導体装置。
- 請求項7に記載のパターン硬化膜を再配線層の形成に用いられる絶縁膜として有することを特徴とする半導体装置。
- 請求項9または10に記載の半導体装置であって、請求項7に記載のパターン硬化膜を2~15μmの膜厚にて基板上に有し、その上に銅の配線を有し、銅配線間の絶縁膜としてさらに請求項7に記載のパターン硬化膜を2~15μmの膜厚にて有することを特徴とする半導体装置。
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CN115232017A (zh) * | 2021-03-15 | 2022-10-25 | 华为技术有限公司 | 一种化合物、一种树脂及其制备方法和应用 |
CN114380998B (zh) * | 2022-01-12 | 2023-08-11 | 武汉柔显科技股份有限公司 | 碱溶性树脂、正型感光树脂组合物、固化膜及显示装置 |
CN114316263B (zh) * | 2022-01-17 | 2023-02-03 | 深圳职业技术学院 | 交联型聚酰胺酸酯、其制备方法、包含其的聚酰亚胺组合物及聚酰亚胺树脂膜的制备方法 |
CN114561008B (zh) * | 2022-03-04 | 2023-08-11 | 武汉柔显科技股份有限公司 | 碱溶性树脂、正型感光树脂组合物、固化膜及显示装置 |
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Also Published As
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KR20170131372A (ko) | 2017-11-29 |
CN107407878A (zh) | 2017-11-28 |
TW201642027A (zh) | 2016-12-01 |
JPWO2016152656A1 (ja) | 2018-02-22 |
CN107407878B (zh) | 2020-11-17 |
US20180039174A1 (en) | 2018-02-08 |
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