WO2022172913A1 - 感光性樹脂組成物 - Google Patents
感光性樹脂組成物 Download PDFInfo
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- WO2022172913A1 WO2022172913A1 PCT/JP2022/004906 JP2022004906W WO2022172913A1 WO 2022172913 A1 WO2022172913 A1 WO 2022172913A1 JP 2022004906 W JP2022004906 W JP 2022004906W WO 2022172913 A1 WO2022172913 A1 WO 2022172913A1
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- WIPO (PCT)
- Prior art keywords
- resin composition
- photosensitive resin
- group
- alkali
- organic solvent
- Prior art date
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- 239000011342 resin composition Substances 0.000 title claims abstract description 76
- 239000011347 resin Substances 0.000 claims abstract description 91
- 229920005989 resin Polymers 0.000 claims abstract description 91
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000003960 organic solvent Substances 0.000 claims abstract description 47
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 39
- 150000002391 heterocyclic compounds Chemical class 0.000 claims abstract description 39
- 239000002243 precursor Substances 0.000 claims abstract description 12
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- 229920001721 polyimide Polymers 0.000 claims abstract description 7
- 239000009719 polyimide resin Substances 0.000 claims abstract description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 14
- 125000000962 organic group Chemical group 0.000 claims description 14
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical group O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 13
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 12
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 claims description 11
- -1 pyruvic acid N,N-dimethylacetamide Chemical compound 0.000 claims description 11
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- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 9
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 claims description 6
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims description 6
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 claims description 5
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- RRQYJINTUHWNHW-UHFFFAOYSA-N 1-ethoxy-2-(2-ethoxyethoxy)ethane Chemical compound CCOCCOCCOCC RRQYJINTUHWNHW-UHFFFAOYSA-N 0.000 claims description 3
- CRWNQZTZTZWPOF-UHFFFAOYSA-N 2-methyl-4-phenylpyridine Chemical compound C1=NC(C)=CC(C=2C=CC=CC=2)=C1 CRWNQZTZTZWPOF-UHFFFAOYSA-N 0.000 claims description 3
- XWKFPIODWVPXLX-UHFFFAOYSA-N 2-methyl-5-methylpyridine Natural products CC1=CC=C(C)N=C1 XWKFPIODWVPXLX-UHFFFAOYSA-N 0.000 claims description 3
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- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 claims description 3
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 claims description 3
- XXRCUYVCPSWGCC-UHFFFAOYSA-N Ethyl pyruvate Chemical compound CCOC(=O)C(C)=O XXRCUYVCPSWGCC-UHFFFAOYSA-N 0.000 claims description 3
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims description 3
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- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 claims description 3
- 229940116333 ethyl lactate Drugs 0.000 claims description 3
- 229940117360 ethyl pyruvate Drugs 0.000 claims description 3
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 claims description 3
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Images
Classifications
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- G—PHYSICS
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- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
- C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
- C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/22—Polybenzoxazoles
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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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- 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
- G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
-
- 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
-
- 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
-
- 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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/22—Exposing sequentially with the same light pattern different positions of the same surface
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
- Y10S430/1055—Radiation sensitive composition or product or process of making
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/156—Precursor compound
Definitions
- polyamide resins which have excellent heat resistance, electrical properties, and mechanical properties, have been used as surface protective films and interlayer insulating films for semiconductor devices. Since such a polyamide resin is subjected to a pattern forming process for use as a protective film for semiconductor elements and an interlayer insulating film, it is dissolved in an organic solvent, mixed with a photosensitive agent, and formed into a varnish-like photosensitive resin composition. provided as
- Patent Document 1 in relation to this, the technology disclosed in Patent Document 1 is known.
- Patent Document 1 in a photosensitive resin composition containing a polyimide precursor or a polybenzoxazole precursor and a polar solvent having a specific structure, the content of N-methyl-2-pyrrolidone in the photosensitive resin composition is reduced to 0.
- a technique is disclosed for obtaining a resin composition that does not gel over time and has improved sensitivity and mechanical properties by adjusting the concentration to 1% by mass or less.
- Patent Document 1 an appropriate solvent or the like is selected in order to reduce the content of N-methyl-2-pyrrolidone in the resin composition from the viewpoint of reducing the burden on the environment.
- this N-methyl-2-pyrrolidone is used as a so-called synthetic solvent, and N-methyl-2-pyrrolidone is reduced after the reaction.
- An operation is performed to wash the organic layer in order to Such an operation complicates the process, and there is concern that N-methyl-2-pyrrolidone may remain when scaled up.
- an object of the present invention is to provide a photosensitive resin composition in which the content of N-methyl-2-pyrrolidone, which has a high environmental load, is reduced.
- alkali-soluble resin photoacid generator, a first organic solvent; and a second organic solvent different from the first organic solvent;
- a photosensitive resin composition comprising The alkali-soluble resin contains at least one selected from polyamide resins, polyimide resins, and precursors thereof,
- the second organic solvent contains a heterocyclic compound having a carbonyl group (excluding N-methyl-2-pyrrolidone),
- a photosensitive resin composition is provided in which the second organic solvent is in an amount of 0.001% by mass or more and 4.0% by mass or less with respect to the entire photosensitive resin composition.
- a photosensitive resin composition in which the content of N-methyl-2-pyrrolidone (NMP), which has a large environmental impact, is reduced.
- NMP N-methyl-2-pyrrolidone
- the photosensitive resin composition according to this embodiment contains an alkali-soluble resin, a photoacid generator, a first organic solvent, and a second organic solvent different from the first organic solvent.
- the alkali-soluble resin contains at least one selected from polyamide resins, polyimide resins, and precursors thereof.
- the second organic solvent includes a heterocyclic compound having a carbonyl group (excluding N-methyl-2-pyrrolidone), and the second organic solvent is an amount of 0.001% by mass or more and 4.0% by mass or less with respect to the whole photosensitive resin composition.
- the first organic solvent dissolves or disperses each component of the photosensitive resin composition to provide the photosensitive resin composition as a varnish having a desired viscosity.
- the second organic solvent is a synthetic solvent used in the production and / or purification of the alkali-soluble resin to be blended in the photosensitive resin composition, and used It is a solvent that inevitably remains in the alkali-soluble resin.
- the amount of the second organic solvent is 0.001% by mass or more and 4.0% by mass or less with respect to the entire photosensitive resin composition.
- the photosensitive resin composition of this embodiment does not contain N-methyl-2-pyrrolidone as the second organic solvent. This can be achieved by using an alkali-soluble resin that does not use N-methyl-2-pyrrolidone as a synthesis solvent. Furthermore, in this embodiment, the alkali-soluble resin contains a heterocyclic compound having a carbonyl group other than N-methyl-2-pyrrolidone as an unavoidable synthetic solvent. That is, the alkali-soluble resin used in this embodiment is produced using a heterocyclic compound having a carbonyl group other than N-methyl-2-pyrrolidone as its synthesis solvent. As a result, the photosensitive resin composition of the present embodiment does not contain N-methyl-2-pyrrolidone, thereby reducing the burden on the environment.
- Each component used in the photosensitive resin composition of the present embodiment will be described below.
- alkali-soluble resin used in the photosensitive resin composition of this embodiment is a polyamide resin, a polyimide resin, or a precursor thereof. More specifically, the alkali-soluble resin is a resin having a structure represented by general formula (1).
- X and Y are organic groups.
- R 1 is a hydroxyl group, —OR 3 , alkyl group, acyloxy group, or cycloalkyl group, and when there are more than one, they may be the same or different.
- R 2 is a hydroxyl group, a carboxyl group, —OR 3 , or —COO-R 3 , and when there are more than one, they may be the same or different.
- R 3 in R 1 and R 2 is an organic group having 1 to 15 carbon atoms. When there is no hydroxyl group as R 1 , at least one of R 2 is a carboxyl group. When there is no carboxyl group as R2 , at least one of R1 is a hydroxyl group.
- n is an integer of 0-8.
- organic groups having 1 to 15 carbon atoms as R 3 include formyl, methyl, ethyl, propyl, isopropyl, tert-butyl, tert-butoxycarbonyl, phenyl, benzyl and tetrahydrofuranyl. , tetrahydropyranyl group, and the like.
- the organic group as X in the general formula (1) is not particularly limited.
- * indicates bonding to the NH group in general formula (1).
- R5 represents one selected from an alkyl group, an alkyl ester group and a halogen atom, and may be the same or different.
- R6 represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group and a halogen atom.
- u is an integer from 0 to 4;
- Each of R 7 to R 10 is a monovalent or divalent organic group.
- the substituent R1 of X in the above general formula ( 1 ) is omitted.
- particularly preferred groups include those represented by the following formula (13) (some have R 1 in general formula (1)).
- * indicates bonding to the NH group in general formula (1).
- R 11 is one selected from an alkyl group, an alkoxy group, an acyloxy group and a cycloalkyl group, and when there are a plurality of R 11 , they may be the same or different.
- v is an integer of 0 or more and 3 or less.
- particularly preferred groups include those represented by the following formula (14) (some have R 1 in general formula (1)).
- alkylene group and substituted alkylene group as Z in the above formulas (12) and (13) and R 12 in the above formula (14) include -CH 2 -, -CH(CH 3 )-, -C(CH 3 ) 2 -, -CH(CH 2 CH 3 )-, -C(CH 3 )(CH 2 CH 3 )-, -C(CH 2 CH 3 )(CH 2 CH 3 )-, - CH(CH 2 CH 2 CH 3 )—, —C(CH 3 )(CH 2 CH 2 CH 3 )—, —CH(CH(CH 3 ) 2 )—, —C(CH 3 )(CH(CH 3 ) 2 )-, -CH(CH 2 CH 2 CH 2 CH 3 )-, -C(CH 3 )(CH 2 CH 2 CH 3 )-, -CH(CH 2 CH(CH 3 ) 2 )-, -CH(CH 2 CH(CH 3 ) 2 )-, -CH(CH 2 CH
- —CH 2 —, —CH(CH 3 )—, and —C(CH 3 ) 2 — are well-balanced resins with sufficient solubility not only in alkaline aqueous solutions but also in solvents. It is preferable because a film can be obtained.
- Y in the above general formula (1) is an organic group, and examples of such an organic group include those similar to X above. Examples thereof include aromatic groups having structures such as benzene ring, naphthalene ring and bisphenol structures; heterocyclic organic groups having structures such as pyrrole ring, pyridine ring and furan ring; and siloxane groups. Preferred examples are those represented by the following formula (15). These may be used singly or in combination of two or more.
- R 13 represents one selected from an alkyl group, an alkyl ester group, an alkyl ether group, a benzyl ether group and a halogen atom, and may be the same or different.
- R14 represents one selected from a hydrogen atom, an alkyl group, an alkyl ester group and a halogen atom.
- w is an integer of 0 or more and 2 or less.
- Each of R 15 to R 18 is a monovalent or divalent organic group.
- the substituent R2 of Y in the above general formula (1) is omitted.
- Particularly preferred among these groups represented by formula (15) are those represented by the following formula (16) (some have R 2 in general formula (1)).
- the structure may include both meta-position and para-position.
- R 19 represents one selected from an alkyl group, an alkyl ester group, an alkyl ether group, a benzyl ether group and a halogen atom, and may be the same or different.
- R 20 represents one selected from a hydrogen atom or an organic group having 1 to 15 carbon atoms, and may be partially substituted.
- x is an integer of 0 or more and 2 or less.
- the alkali-soluble resin is obtained by reacting a dicarboxylic acid compound represented by general formula (2) with a diamine compound represented by general formula (3). More specifically, the alkali-soluble resin is produced by the following steps 1 and 2 (step 1) a step of activating a carboxylic acid compound represented by the following general formula (2) to obtain an activated carboxylic acid product. (Step 2) A step of reacting the carboxylic acid activated product obtained in (Step 1) with an amine compound represented by the following general formula (3) to obtain a resin represented by the formula (1).
- at least one of (Step 1) and (Step 2) is carried out in a solvent containing a heterocyclic compound having a carbonyl group other than N-methyl-2-pyrrolidone.
- Y, R 2 and n in general formula (2) are synonymous with those shown in general formula (1).
- Step 1 or Step 2 By performing Step 1 or Step 2 above in a solvent other than N-methyl-2-pyrrolidone, the residual amount of N-methyl-2-pyrrolidone contained in the alkali-soluble resin is reduced. As a result, the environmental load of the photosensitive resin composition containing this alkali-soluble resin is reduced. In addition, especially by performing step 2 in a solvent other than N-methyl-2-pyrrolidone, it is possible to further reduce the environmental load and promote the increase in the molecular weight of the resin represented by formula (1). can do.
- At least one of steps 1 and 2 is carried out in a solvent containing a heterocyclic compound having a carbonyl group other than N-methyl-2-pyrrolidone.
- steps 1 and 2 the same solvent or different solvents may be used, but from the viewpoint of improving productivity and reaction efficiency, the same solvent is preferred.
- the reactivity between the monomer molecules of the photosensitive resin is similarly appropriately controlled, and it is believed that the molecular weight can be easily increased.
- a 5-membered heterocyclic ring is selected as the heterocyclic compound having a carbonyl group, such effects are remarkably obtained.
- a heterocyclic compound having a carbonyl group has high solubility in a precursor having an amide bond and other resin components, and has an appropriate polarity.
- the reaction can proceed smoothly.
- the same solvent or different solvents may be used, but from the viewpoint of improving productivity and reaction efficiency, the same solvent is preferred.
- the heterocyclic compound having a carbonyl group includes a 4-membered ring, a 5-membered ring, a 6-membered ring, a 7-membered ring, etc. Among them, a 5-membered ring is preferred. These heterocyclic compounds having a carbonyl group may be partially substituted with a hydrocarbon group such as a methyl group, an ethyl group, or a propyl group. Examples of the heterocyclic compound having a carbonyl group include compounds further containing a nitrogen atom in addition to the heterocyclic ring (hereinafter referred to as "a carbonyl group-containing heterocyclic compound (i) having a nitrogen atom"). By using the carbonyl group-containing heterocyclic compound (i) having a nitrogen atom, the photosensitive resin composition of the present embodiment can obtain better reactivity and moderate solubility to remove residue at the opening. can be reduced.
- the heterocyclic ring in the five-membered heterocyclic ring having a carbonyl group is preferably one or more selected from furan, pyrrole, imidazole, oxazole, thiazole, and pyrazole. From the viewpoint of improving efficiency, it is more preferably one or more selected from pyrrole, imidazole, oxazole, thiazole, and pyrazole. Also, different types of heterocycles may be combined.
- examples of the furan having a carbonyl group include ⁇ -butyrolactone (GBL)
- examples of the pyrrole having a carbonyl group include N-ethyl-2-pyrrolidone (NEP)
- examples of the imidazole having a carbonyl group include 1,3-dimethyl-2-imidazolidinone (DMI)
- examples of the oxazole having a carbonyl group include 3-methyl-2-oxazolidone (MOZ). be done.
- N-ethyl-2-pyrrolidone, 3-methyl-2-oxazolidone and the like are given as examples of the carbonyl group-containing heterocyclic compound (i) having a nitrogen atom.
- At least one of ⁇ -butyrolactone and 3-methyl-2-oxazolidone is preferably selected from the viewpoint of increasing the molecular weight of the photosensitive resin and promoting the reactivity of the photosensitive resin with the end cap.
- solvents may be used together as the solvent of the present embodiment.
- heterocyclic compounds having different types of carbonyl groups may be used in combination
- different types of carbonyl group-containing heterocyclic compounds (i) having a nitrogen atom described above may be used in combination
- a heterocyclic ring having a carbonyl group A solvent other than the compound may be used.
- a compound that is commonly used as a solvent can be used in combination with the above-described heterocyclic compound having a carbonyl group.
- a known solvent can be used, but from the viewpoint of promoting reactivity and obtaining good solubility, a heterocyclic It is preferred to use ring compounds (ii) and compounds (iii) having a nitrogen atom and a carbonyl group.
- the above carbonyl group-containing heterocyclic compound (i) having a nitrogen atom and the above carbonyl group-free heterocyclic compound containing a nitrogen atom in addition to the heterocyclic ring may be used in combination, or the carbonyl group-containing heterocyclic compound (i) having a nitrogen atom and the compound (iii) having a nitrogen atom and a carbonyl group may be used in combination.
- the mixing ratio when the solvent is mixed is preferably 1 to 40 parts by weight of a compound other than the heterocyclic compound having a carbonyl group with respect to 100 parts by weight of the heterocyclic compound having a carbonyl group of the present embodiment, 1 to 30 parts by weight is more preferable.
- Such compounds include 2,6-lutidine, N,N-dimethylacetamide pyruvate, 3-methoxy-N,N-dimethylpropionamide, dimethylsulfoxide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and 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, pyruvin methyl acid, and ethyl pyruvate and methyl-3-methoxypropionate, and the like.
- step 1 or step 2 it is preferable to use the above-described heterocyclic compound having a carbonyl group as a solvent. be able to.
- the content of N-methyl-2-pyrrolidone is preferably 80% by mass or less, more preferably 60% by mass or less, even more preferably 40% by mass or less, based on the total solvent. It is particularly preferably not more than 5% by mass, and particularly preferably not more than 5% by mass.
- the solvent is substantially free of N-methyl-2-pyrrolidone.
- substantially free is used to exclude the intentional addition of N-methyl-2-pyrrolidone. A mode in which it is unavoidable to avoid contamination of is allowed.
- the photosensitive resin composition of this embodiment contains a photoacid generator.
- the photoacid generator is a compound that generates light upon exposure to actinic rays (e.g., ultraviolet rays, electron beams, X-rays). It is a compound that generates acid upon irradiation.
- Such photoacid generators include photosensitive diazoquinone compounds, photosensitive diazonaphthoquinone compounds, diaryliodonium salts, triarylsulfonium salts, onium salts such as sulfonium borate salts, 2-nitrobenzyl ester compounds, and N-iminosulfonates.
- the photoacid generator is used in an amount of 0.5% by mass or more and 10% by mass or less, preferably 1% by mass or more and 5% by mass or less based on the total solid content of the photosensitive resin composition.
- the first organic solvent used as the main solvent in the photosensitive resin composition of the present embodiment includes ⁇ -butyrolactone (GBL), ⁇ -valerolactone (GVL), 2,6-lutidine, N,N-pyruvate, Dimethylacetamide, 3-methoxy-N,N-dimethylpropionamide, dimethyl sulfoxide (DMSO), diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether (PGME), 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, and methyl-3-methoxypropionate is mentioned.
- a 1st organic solvent may
- the content of the first organic solvent in the photosensitive resin composition can be adjusted according to the desired viscosity suitable for the application of the photosensitive resin composition.
- the content of the first organic solvent is, for example, 10 to 80% by mass, preferably 20 to 70% by mass, relative to the entire photosensitive resin composition.
- the second organic solvent contained in the photosensitive resin composition of the present embodiment is a solvent contained in the alkali-soluble resin, specifically a synthetic solvent used in the production and/or purification of the alkali-soluble resin. It is a solvent that inevitably remains in the alkali-soluble resin.
- the synthetic solvent of the alkali-soluble resin can be removed by a known method such as extraction or distillation, but it is difficult to completely remove it, and when the synthetic solvent is reduced, the handleability of the alkali-soluble resin deteriorates. Sometimes. When almost no or no synthetic solvent remains in the alkali-soluble resin, the solubility of the alkali-soluble resin deteriorates, and the storage stability of the resin composition may deteriorate.
- the amount of the second organic solvent is 0.001% by mass or more and 4.0% by mass or less with respect to the entire photosensitive resin composition.
- the first organic solvent and the second organic solvent can be used in a specific combination.
- the photosensitive resin composition can be prepared by appropriately selecting the first organic solvent according to the second organic solvent contained in the alkali-soluble resin to be used. This makes it possible to adjust the solubility of the alkali-soluble resin, thereby improving the storage stability and handleability of the resulting photosensitive resin composition.
- the first organic solvent is at least one selected from ⁇ -butyrolactone, dipropylene glycol monomethyl ether, and dimethyl sulfoxide
- the second organic solvent is at least one selected from N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and 3-methyl-2-oxazolidone.
- the photosensitive resin composition of the present embodiment is obtained by mixing the above-described alkali-soluble resin, photoacid generator, and optionally other components with a first organic solvent.
- the photosensitive resin composition of the present embodiment is provided in the form of a varnish or solution dissolved or dispersed in a first organic solvent from the viewpoint of handleability.
- a resin film can be produced by curing the photosensitive resin composition of the present embodiment.
- the resulting resin film can be used, for example, as a protective film, an interlayer film, or a permanent film such as a dam material. As a result, it is possible to improve the durability and the like of an electronic device having the resin film as a permanent film.
- Electronic device 100 shown in FIG. 1 is, for example, a semiconductor chip.
- a semiconductor package is obtained by mounting the electronic device 100 on the wiring substrate via the bumps 52 .
- the electronic device 100 includes a semiconductor substrate provided with semiconductor elements such as transistors, and a multilayer wiring layer provided on the semiconductor substrate (not shown).
- An interlayer insulating film 30 and a top layer wiring 34 provided on the interlayer insulating film 30 are provided in the uppermost layer of the multilayer wiring layers.
- the uppermost layer wiring 34 is made of Al, for example.
- a passivation film 32 is provided on the interlayer insulating film 30 and the uppermost layer wiring 34 . A portion of the passivation film 32 is provided with an opening through which the uppermost layer wiring 34 is exposed.
- a rewiring layer 40 is provided on the passivation film 32 .
- the rewiring layer 40 includes an insulating layer 42 provided on the passivation film 32, a rewiring 46 provided on the insulating layer 42, an insulating layer 44 provided on the insulating layer 42 and the rewiring 46, have An opening connected to the uppermost layer wiring 34 is formed in the insulating layer 42 .
- the rewiring 46 is formed on the insulating layer 42 and in openings provided in the insulating layer 42 and connected to the uppermost layer wiring 34 .
- the insulating layer 44 is provided with an opening connected to the rewiring 46 .
- one or more of the passivation film 32, the insulating layer 42, and the insulating layer 44 can be composed of a resin film formed by curing the photosensitive resin composition described above, for example.
- a coating film formed of a photosensitive resin material is exposed to ultraviolet light, developed, patterned, and then cured by heating to form the passivation film 32, the insulating layer 42, or the insulating layer 44. It is formed.
- a bump 52 is formed in the opening provided in the insulating layer 44 via a UBM (Under Bump Metallurgy) layer 50, for example.
- the electronic device 100 is connected to a wiring substrate or the like via bumps 52, for example.
- the obtained alkali-soluble resin 1 had the repeating unit (A-1) shown below.
- Synthesis Example 5 Alkali-soluble resin 5 was synthesized in the same manner as in Synthesis Example 1, except that the time for filtering the precipitate in Synthesis Example 1 and washing it with water was doubled.
- Synthesis Example 6 Alkali-soluble resin 6 was synthesized in the same manner as in Synthesis Example 1, except that the time for filtering and collecting the precipitate and washing with water in Synthesis Example 1 was changed to half.
- Alkali-soluble resin Alkali-soluble resin 1: Alkali-soluble resin 1 synthesized in Synthesis Example 1
- Alkali-soluble resin 2 Alkali-soluble resin 2 synthesized in Synthesis Example 2
- Alkali-soluble resin 3 Alkali-soluble resin 3 synthesized in Synthesis Example 3
- Alkali-soluble resin 4 Alkali-soluble resin 4 synthesized in Synthesis Example 4
- Alkali-soluble resin 5 Alkali-soluble resin 5 synthesized in Synthesis Example 5
- Alkali-soluble resin 6 Alkali-soluble resin 6 synthesized in Synthesis Example 6
- Alkali-soluble resin 7 Alkali-soluble resin 7 synthesized in Synthesis Example 7
- Alkali-soluble resin 8 Alkali-soluble resin 8 synthesized in Synthesis Example 8
- Alkali-soluble resin 9 Alkali-soluble resin 9 synthesized in Synthesis Example 9
- Alkali-soluble resin 10
- Photoacid generator 1 a compound represented by formula (B-2) synthesized by the following method (synthesis of compound represented by formula (B-2)) 11.04 g (0.026 mol) of phenol represented by the formula (B-1), 1, 18.81 g (0.070 mol) of 2-naphthoquinone-2-diazide-4-sulfonyl chloride and 170 g of acetone were added and dissolved by stirring. Then, a mixed solution of 7.78 g (0.077 mol) of triethylamine and 5.5 g of acetone was slowly added dropwise while cooling the flask with a water bath so that the temperature of the reaction solution did not exceed 35°C.
- Adhesion aid 1 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Silicone Co., Ltd.) (Solubilizer) ⁇ Solubilizer 1: 2,2'-dihydroxydiphenylmethane
- the film was rinsed with pure water for 10 seconds to obtain a photosensitive resin film.
- the bottom of the pattern of the 100 ⁇ m square via hole exposed with the energy of the minimum exposure dose + 100 mJ/cm 2 at which the pattern of the 100 ⁇ m square via hole is opened was observed from the top with a microscope, The degree of residue on the bottom of the pattern was evaluated according to the following criteria. The smaller the width of the residue, the better the patterning properties.
- the thickness of the coating film is measured with a non-contact film thickness meter at intervals of 1 cm from -14 cm to +14 cm on the x-axis and the y-axis, respectively, and the difference between the maximum film thickness and the minimum film thickness is the film thickness variation. and the average value of film thickness after development.
- the film thickness variation was evaluated according to the following criteria. The smaller the film thickness variation value, the more uniform the film thickness. Less than 0.1 ⁇ m: ⁇ Less than 0.3 ⁇ m: ⁇ Less than 0.6 ⁇ m: ⁇ 0.6 ⁇ m or more: ⁇
- the film thickness measurement described in the film thickness uniformity is performed on the heated wafer, the average value of the film thickness after heating is obtained, and the cured residual film rate is obtained by dividing the average film thickness after development by the average film thickness after heating. Obtained.
- the cured residual film rate was evaluated according to the following criteria. The higher the cured residual film ratio, the smaller the shrinkage after curing. Therefore, if the cured film thickness is the same, the higher the cured residual film ratio, the thinner the film thickness at the time of application. The thinner the film, the smaller the amount of exposure during patterning, so the throughput during exposure can be improved. 80% or more: ⁇ 75% or more and less than 80%: ⁇ Less than 75%: ⁇
- All of the photosensitive resin compositions of Examples did not contain a solvent with a high environmental load, and thus had a reduced environmental load. Moreover, all of the photosensitive resin compositions of Examples had excellent storage stability and good pattern formability.
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Abstract
Description
しかしながら、特許文献1の合成例1等として記載されている樹脂を作製する段階においては、このN-メチル-2-ピロリドンがいわゆる合成溶媒として用いられ、反応後にN-メチル-2-ピロリドンを低減するための有機層の洗浄を行う操作がなされている。このような操作はプロセスの煩雑化を招き、また、スケールアップを行った際ではN-メチル-2-ピロリドンが残存してしまうことが懸念される。
アルカリ可溶性樹脂、
光酸発生剤、
第一の有機溶剤、および
前記第一の有機溶剤とは異なる第二の有機溶剤、
を含む、感光性樹脂組成物であって、
前記アルカリ可溶性樹脂が、ポリアミド樹脂、ポリイミド樹脂、およびそれらの前駆体から選択される少なくとも1つを含み、
前記第二の有機溶剤が、カルボニル基を有する複素環化合物(ただし、N-メチル-2-ピロリドンを除く)を含み、
前記第二の有機溶剤が、当該感光性樹脂組成物全体に対して、0.001質量%以上4.0質量%以下の量である、感光性樹脂組成物が提供される。
本実施形態に係る感光性樹脂組成物は、アルカリ可溶性樹脂、光酸発生剤、第一の有機溶剤、および前記第一の有機溶剤とは異なる第二の有機溶剤を含む。本実施形態の感光性樹脂組成物において、前記アルカリ可溶性樹脂は、ポリアミド樹脂、ポリイミド樹脂、およびそれらの前駆体から選択される少なくとも1つを含む。また、本実施形態の感光性樹脂組成物において、前記第二の有機溶剤は、カルボニル基を有する複素環化合物(ただし、N-メチル-2-ピロリドンを除く)を含み、前記第二の有機溶剤が、当該感光性樹脂組成物全体に対して、0.001質量%以上4.0質量%以下の量である。
本実施形態の感光性樹脂組成物に用いられるアルカリ可溶性樹脂は、ポリアミド樹脂、もしくはポリイミド樹脂、またはそれらの前駆体である。より具体的には、アルカリ可溶性樹脂は、一般式(1)で表される構造を有する樹脂である。
なお、上記式(12)において、上記一般式(1)におけるXの置換基R1は省略している。
なお、上記式(15)において、上記一般式(1)におけるYの置換基R2は省略している。
下記式(16)中のテトラカルボン酸二無水物由来の構造については、一般式(1)におけるC=O基に結合する位置が両方メタ位であるもの、両方パラ位であるものを挙げているが、メタ位とパラ位をそれぞれ含む構造でもよい。
(工程1)下記一般式(2)で表されるカルボン酸化合物を活性化し、カルボン酸活性化物を得る工程。
(工程2)(工程1)で得られたカルボン酸活性化物に対して、下記一般式(3)で表されるアミン化合物を作用させ、式(1)で表される樹脂を得る工程。ここで、(工程1)、(工程2)の少なくとも一方は、N-メチル-2-ピロリドン以外の、カルボニル基を有する複素環化合物を含む溶媒中で行われる。
また、カルボニル基を有する複素環化合物としては、当該複素環以外にさらに窒素原子を含む化合物(以下、「窒素原子を有するカルボニル基含有複素環化合物(i)」とする。)が挙げられる。本実施形態の感光性樹脂組成物は、上記の窒素原子を有するカルボニル基含有複素環化合物(i)を用いることで、より良好な反応性が得られ、適度な溶解性により、開口部残渣を低減できる。
中でも、N-エチル-2-ピロリドン、3-メチル-2-オキサゾリドン等は、上記の窒素原子を有するカルボニル基含有複素環化合物(i)の一例として、挙げられる。
なお、感光性樹脂の分子量が増加する観点及び感光性樹脂のエンドキャップとの反応性が促進される観点から、γ-ブチロラクトンまたは3-メチル-2-オキサゾリドンの少なくとも一方を選択することが好ましい。
併用される溶媒としては、公知の溶媒を用いることができるが、反応性が促進され、良好な溶解性を得る観点から、カルボニル基を有さないが、当該複素環以外に窒素原子を含む複素環化合物(ii)、および、窒素原子およびカルボニル基を有する化合物(iii)を用いることが好適である。
また、良好な溶解性を保持する観点から、例えば、上記の窒素原子を有するカルボニル基含有複素環化合物(i)と、上記のカルボニル基を有さないが、当該複素環以外に窒素原子を含む複素環化合物(ii)とを併用すること、または、上記の窒素原子を有するカルボニル基含有複素環化合物(i)と、窒素原子およびカルボニル基を有する化合物(iii)とを併用してもよい。
このN-メチル-2-ピロリドンの含有量は溶媒全体に対して80質量%以下であることが好ましく、60質量%以下であることがより好ましく、40質量%以下であることがさらに好ましく、20質量%以下であることが殊更に好ましく、5質量%以下であることが特に好ましい。さらに、N-メチル-2-ピロリドンは溶媒に対して実質的に含まれていないことがとりわけ好ましい。
なお、この「実質的に含まれていない」とは、N-メチル-2-ピロリドンを意図的に添加する態様を排除する趣旨で用いており、製造プロセス上、このN-メチル-2-ピロリドンの混入を避けることが不可避である態様は許容するものである。
本実施形態の感光性樹脂組成物は、光酸発生剤を含む。光酸発生剤は、活性光線(たとえば、紫外線、電子線、X線)の照射により光を発生する化合物であり、好ましくは、200~500nmの波長、特に好ましくは350~450nmの波長の放射線の照射により酸を発生する化合物である。このような光酸発生剤としては、感光性ジアゾキノン化合物、感光性ジアゾナフトキノン化合物、ジアリールヨードニウム塩、トリアリールスルホニウム塩もしくはスルホニウム・ボレート塩などのオニウム塩、2-ニトロベンジルエステル化合物、N-イミノスルホネート化合物、イミドスルホネート化合物、2,6-ビス(トリクロロメチル)-1,3,5-トリアジン化合物、ジヒドロピリジン化合物等が挙げられる。これらは1種を単独で使用しても、2種以上を組み合わせて使用してもよい。
光酸発生剤は、感光性樹脂組成物の固形分全体に対して、0.5質量%以上10質量%以下、好ましくは1質量%以上5質量%以下の量で使用される。
本実施形態の感光性樹脂組成物に主溶剤として用いられる第一の有機溶剤としては、γ-ブチロラクトン(GBL)、γ-バレロラクトン(GVL)、2,6-ルチジン、ピルビン酸N,N-ジメチルアセトアミド、3-メトキシ-N,N-ジメチルプロピオンアミド、ジメチルスルホキシド(DMSO)、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジブチルエーテル、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル(PGME)、プロピレングリコールモノメチルエーテルアセテート、乳酸メチル、乳酸エチル、乳酸ブチル、メチル-1,3-ブチレングリコールアセテート、1,3-ブチレングリコール-3-モノメチルエーテル、ピルビン酸メチル、ピルビン酸エチル、およびメチル-3-メトキシプロピオネートが挙げられる。第一の有機溶剤は、1種を単独で用いても、2種以上を組み合わせて用いてもよい。
本実施形態の感光性樹脂組成物に含まれる第二の有機溶剤は、アルカリ可溶性樹脂に含まれる溶剤、具体的には、アルカリ可溶性樹脂の製造および/またはその精製処理において用いられた合成溶媒であり、アルカリ可溶性樹脂に不可避的に残存する溶剤である。アルカリ可溶性樹脂の合成溶媒は、抽出や蒸留などの公知の方法により除去することができるが、完全に除去することは困難であり、また合成溶媒を低減すると、アルカリ可溶性樹脂の取扱い性が悪化する場合がある。アルカリ可溶性樹脂に残存する合成溶媒がほとんど無いもしくはまったく無い場合、アルカリ可溶性樹脂の溶解性が悪くなり、樹脂組成物の保存安定性が悪化する場合があった。アルカリ可溶性樹脂に合成溶媒を残存させることにより、上述の不利点を相殺することができ、経時的な高粘度化が抑制され、よって優れた保存安定性および取扱い性を有する感光性樹脂組成物を得ることができる。しかしながら、アルカリ可溶性樹脂に残存する合成溶媒が多すぎると感光性樹脂組成物の塗膜のアルカリ現像液に対する溶解性が高まり、露光部のみでなく未露光部の塗膜もアルカリ現像液により多く溶解し、結果として露光部に相当する開口部の底部に残渣が発生することになる。本実施形態の感光性樹脂組成物において、第二の有機溶剤は、感光性樹脂組成物全体に対して、0.001質量%以上4.0質量%以下の量である。これにより、樹脂組成物の取扱い性が損なわれることなく、ワニス状の感光性樹脂組成物を得ることができる。
本実施形態の感光性樹脂組成物は、上述したアルカリ可溶性樹脂、光酸発生剤、および必要に応じてその他の成分を、第一の有機溶剤と混合することにより得られる。本実施形態の感光性樹脂組成物は、取扱い性の観点から、第一の有機溶媒に溶解または分散されたワニスまたは溶液の形態で提供される。
本実施形態の感光性樹脂組成物を硬化することにより、樹脂膜を製造することができる。得られる樹脂膜は、たとえば保護膜、層間膜、またはダム材等の永久膜として使用することができる。これにより、当該樹脂膜を永久膜として備える電子装置について、耐久性等の向上を図ることができる。
図1に示す電子装置100は、たとえば半導体チップである。この場合、たとえば電子装置100を、バンプ52を介して配線基板上に搭載することにより半導体パッケージが得られる。電子装置100は、トランジスタ等の半導体素子が設けられた半導体基板と、半導体基板上に設けられた多層配線層と、を備えている(図示せず)。多層配線層のうち最上層には、層間絶縁膜30と、層間絶縁膜30上に設けられた最上層配線34が設けられている。最上層配線34は、たとえばAlにより構成される。また、層間絶縁膜30上および最上層配線34上には、パッシベーション膜32が設けられている。パッシベーション膜32の一部には、最上層配線34が露出する開口が設けられている。
以下に示す方法で、アルカリ可溶性樹脂を合成した。各合成例で使用した溶媒を以下に示す。
・溶媒1:N-エチル-2-ピロリドン(NEP)
・溶媒2:1,3-ジメチル-2-イミダゾリジノン(DMI)
・溶媒3:3-メチル-2-オキサゾリドン(MOZ)
・溶媒4:N-メチル-2-ピロリドン(NMP)
・溶媒5:γ-ブチロラクトン(GBL)
以下に示す手順で、溶媒1(NEP)を用いて、アミド結合を有する前駆体を得た。具体的には、以下の通りである。また、得られたアミド結合を有する前駆体の重量平均分子量(Mw)、数平均分子量(Mn)を測定し、結果を表1に示した。
ジフェニルエーテル-4,4'-ジカルボン酸258.2g(1モル)と1-ヒドロキシベンゾトリアゾール270.3g(2モル)とを溶媒1(1500g)に溶解した後、溶媒1(412g)に溶解したジシクロヘキシルカルボジイミド412.7g(2モル)を内温0~5℃に保ちながら2時間かけて滴下した。滴下終了後、内温を室温に戻し更に12時間撹拌して反応させた。反応終了後、析出したジシクロヘキシルカルボジウレアを濾過によって取り除き、得られた濾液に純水4000gを滴下し、結晶を析出させた。この結晶を濾過によって採取し、イソプロピルアルコール8000mlを用いて洗浄した後、真空乾燥し、ジカルボン酸誘導体467gを得た。
得られたジカルボン酸誘導体40.87g(0.083モル)と、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36.63g(0.1モル)とを温度計、攪拌機、原料投入口、乾燥窒素ガス導入管を備えた4つ口のセパラブルフラスコに入れ、溶媒1(180.8g)を加えて溶解させた。その後窒素を流しながら、オイルバスを用いて75℃まで昇温し、75℃にて12時間反応させた。次に、溶媒1(13.0g)に溶解させた3,6-エンドメチレン-1,2,3,6-テトラヒドロフタル酸無水物5.58g(0.034モル)を加え、さらに3時間攪拌した後、室温まで冷却し反応を終了した。
次に、反応混合物をろ過した後、反応混合物を水/イソプロピルアルコール=3/1の溶液に投入、沈殿物を濾集し水で充分洗浄した後、真空下で乾燥し、一般式(A-1)の繰り返し単位をもつアミド結合を有する前駆体(300~400℃で加熱すると脱水閉環し、ポリベンゾオキサゾールとなる樹脂、アルカリ可溶性樹脂1)を得た。
溶媒1を溶媒2(DMI)に変更した以外は、合成例1と同様の方法により、アルカリ可溶性樹脂2を合成した。
溶媒1を溶媒3(MOZ)に変更した以外は、合成例1と同様の方法により、アルカリ可溶性樹脂3を合成した。
溶媒1を溶媒4(NMP)に変更した以外は、合成例1と同様の方法により、アルカリ可溶性樹脂4を合成した。
合成例1における沈殿物を濾集し水で洗浄する時間を2倍に変更した以外は、合成例1と同様の方法により、アルカリ可溶性樹脂5を合成した。
合成例1における沈殿物を濾集し水で洗浄する時間を半分に変更した以外は、合成例1と同様の方法により、アルカリ可溶性樹脂6を合成した。
溶媒1を、溶媒1(NEP)と溶媒2(DMI)の1:1(質量比)混合溶液に変更した以外は、合成例1と同様の方法により、アルカリ可溶性樹脂7を合成した。
溶媒1を、溶媒1(NEP)と溶媒3(MOZ)の1:1(質量比)混合溶液に変更した以外は、合成例1と同様の方法により、アルカリ可溶性樹脂8を合成した。
3,3'-ジアミノ-4,4'-ジヒドロキシジフェニルスルホン44.9g(0.16モル)と2,2-ビス(3-アミノ-4-ヒドロキシフェニル)ヘキサフロロプロパン58.6g(0.16モル)と溶媒1(75.0g)とを温度計、攪拌機、原料投入口、乾燥窒素ガス導入管を備えた4つ口のセパラブルフラスコに入れ、溶媒5(230.5g)を加えて溶解させた。この混合溶液に4,4'-オキシジフタル酸無水物93.1g(0.30モル)をγ-ブチロラクトン120gと共に添加した後、室温で60分間撹拌した。その後、オイルバスを用いて125℃にて8時間撹拌して反応させた。この反応混合物の温度を60℃に冷却した後、5-エチニル-イソベンゾフラン-1,3-ジオン5.2g(0.030モル)をγ-ブチロラクトン40gと共に添加し、80℃にて3時間撹拌して反応を終了させて、ポリイミド前駆体であるアルカリ可溶性樹脂9を合成した。
溶媒1を使用しなかったこと以外は、合成例1と同様の方法により、アルカリ可溶性樹脂10を合成した。
溶媒1(NEP)の使用量を6倍量に変更した以外は、合成例1と同様の方法により、アルカリ可溶性樹脂11を合成した。
(実施例1~13、比較例1~3)
表1に記載の配合にしたがって、樹脂組成物を作製した。詳細には、上記の合成例で得られたアルカリ可溶性樹脂を、表1に記載の第一の有機溶剤に溶解し、光酸発生剤を加え、さらにその他の成分を加えて、感光性樹脂組成物を得た。得られた感光性樹脂組成物中に含まれる、アルカリ可溶性樹脂に含まれる溶媒(第二の有機溶剤)の量を、感光性樹脂組成物全体に対する割合(質量%)として表1に記載する。また表1に記載の各成分は以下のとおりである。
・アルカリ可溶性樹脂1:合成例1で合成したアルカリ可溶性樹脂1
・アルカリ可溶性樹脂2:合成例2で合成したアルカリ可溶性樹脂2
・アルカリ可溶性樹脂3:合成例3で合成したアルカリ可溶性樹脂3
・アルカリ可溶性樹脂4:合成例4で合成したアルカリ可溶性樹脂4
・アルカリ可溶性樹脂5:合成例5で合成したアルカリ可溶性樹脂5
・アルカリ可溶性樹脂6:合成例6で合成したアルカリ可溶性樹脂6
・アルカリ可溶性樹脂7:合成例7で合成したアルカリ可溶性樹脂7
・アルカリ可溶性樹脂8:合成例8で合成したアルカリ可溶性樹脂8
・アルカリ可溶性樹脂9:合成例9で合成したアルカリ可溶性樹脂9
・アルカリ可溶性樹脂10:合成例10で合成したアルカリ可溶性樹脂10
・アルカリ可溶性樹脂11:合成例11で合成したアルカリ可溶性樹脂11
・GBL:γ-ブチロラクトン
・GVL:γ-バレロラクトン
・PGME:ジプロピレングリコールモノメチルエーテル
・DMSO:ジメチルスルホキシド
・光酸発生剤1:以下の方法で合成した式(B-2)で表される化合物
(式(B―2)で表される化合物の合成)
温度計、攪拌機、原料投入口、乾燥窒素ガス導入管を備えた4つ口のセパラブルフラスコに、式(B-1)で表されるフェノール11.04g(0.026モル)と、1,2-ナフトキノン-2-ジアジド-4-スルホニルクロライド18.81g(0.070モル)と、アセトン170gと、を入れて撹拌し、溶解させた。次いで、反応溶液の温度が35℃以上にならないようにウォーターバスでフラスコを冷やしながら、トリエチルアミン7.78g(0.077モル)とアセトン5.5gの混合溶液をゆっくり滴下した。そのまま室温で3時間反応させた後、酢酸1.05g(0.017モル)を添加し、さらに30分反応させた。次いで、反応混合物をろ過した後、ろ液を水/酢酸(990ml/10ml)の混合溶液に投入した。次いで、沈殿物を濾集して水で充分洗浄した後、真空下で乾燥した。これにより、式(B-2)の構造で表される化合物を得た。
・密着助剤1:3-メタクリロキシプロピルトリメトキシシラン(信越シリコーン社製)
(溶解促進剤)
・溶解促進剤1:2,2'-ジヒドロキシジフェニルメタン
(実施例1~12、比較例1~3)
上述で得られた感光性樹脂組成物の各々について、下記の項目の性能を評価した。評価結果を表1に示す。
(粘度安定性)
上述で得られた感光性樹脂組成物を25℃での粘度をη0とし、23℃の条件下にて7日間保管した後における25℃での粘度をη1として、η1/η0の値を下記の基準により評価した。η1/η0の値が小さいほど、粘度の経時変化が小さく、粘度安定性が良好であることを表す。
η1/η0≦5% : ◎
5%<η1/η0≦10% : 〇
10%<η1/η0≦20% : △
20%<η1/η0 : ×
なお、感光性樹脂組成物の粘度は、東機産業株式会社製TVE-22Hデジタル粘度計を用いて測定した。
上述で得られた感光性樹脂組成物を、それぞれ、8インチシリコンウェハ上にスピンコーターを用いて塗布した後、ホットプレートにて120℃で4分間プリベークし、膜厚約8.0μmの塗膜を得た。この塗膜に1μmから100μmサイズの段階的なホールパターン及びラインパターンを有するテストマスクを通して、i線ステッパーを用いて、露光量を変化させて照射した。
次に、現像液として2.38%のテトラメチルアンモニウムヒドロキシド水溶液を用い、プリベーク後の膜厚と現像後の膜厚の差が1.0μmになるように現像時間を調節して2回パドル現像を行うことによって露光部を溶解除去した後、純水で10秒間リンスし、感光性樹脂膜を得た。得られた感光性樹脂膜において、100μmの正方形のビアホールのパターンが開口される最低露光量+100mJ/cm2のエネルギーで露光された100μmの正方形のビアホールのパターン底部を顕微鏡にて上面より観察し、パターン底部における残渣の程度を下記の基準で評価した。残渣の幅が小さいほど、パターニング性が良好であることを表す。
残渣がないもしくは幅0.5μm未満 : ◎
残渣が幅0.5μm以上1μm未満 : 〇
残渣が幅1μm以上5μm未満 : △
残渣が幅5μm以上 : ×
上述で得られた感光性樹脂組成物を、それぞれ、8インチシリコンウェハ上にスピンコーターを用いて塗布した後、ホットプレートにて120℃で4分間プリベークし、膜厚約8.0μmの塗膜を得た。8インチシリコンウェハ円周上にある切りかけ部(ノッチ)を手前にし、横方向の直径をx軸、縦方向の直径をy軸とし、8インチシリコンウェハの中心をx=0、y=0とした場合、x軸とy軸をそれぞれ-14cmから+14cmまで1cm間隔で塗膜の膜厚を非接触式膜厚計にて測定し、その最大膜厚と最小膜厚の差である膜厚ばらつきと現像後膜厚の平均値を得た。その膜厚ばらつきを下記の基準で評価した。膜厚ばらつきの値が小さいほど、膜厚が均一であることを表す。
0.1μm未満 : ◎
0.3μm未満 : 〇
0.6μm未満 : △
0.6μm以上 : ×
上述で得られた感光性樹脂組成物を、それぞれ、8インチシリコンウェハ上にスピンコーターを用いて塗布した後、ホットプレートにて120℃で4分間プリベークし、膜厚約8.0μmの塗膜を得た。次に、現像液として2.38%のテトラメチルアンモニウムヒドロキシド水溶液を用い、プリベーク後の膜厚と現像後の膜厚の差が1.0μmになるように現像時間を調節して2回パドル現像を行った後、純水で10秒間リンスした。そのウェハを加熱オーブンに投入し、窒素を流しながら5℃/分で室温から150℃まで昇温後、そのまま150℃で30分の加熱処理を行い、更に、5℃/分で300℃まで昇温後、そのまま300℃で30分の加熱処理を行い、室温まで冷却した。加熱済みウェハについて膜厚均一性で記載した膜厚測定を行い、加熱後膜厚の平均値を求め、現像後の平均膜厚を加熱後の平均膜厚で除した値として硬化残膜率を得た。その硬化残膜率を下記の基準で評価した。硬化残膜率が高いほど、硬化後の収縮が小さくなるため、硬化後膜厚が同じ場合、硬化残膜率が高いほど塗布時の膜厚を薄くすることができる。薄くなるほどパターニング時の露光量は少なくすることができるため、露光時のスループットを向上することができる。
80%以上 : ◎
75%以上、80%未満 : 〇
75%未満 : ×
30 層間絶縁膜
32 パッシベーション膜
34 最上層配線
40 再配線層
42 絶縁層
44 絶縁層
46 再配線
50 UBM層
52 バンプ
Claims (5)
- アルカリ可溶性樹脂、
光酸発生剤、
第一の有機溶剤、および
前記第一の有機溶剤とは異なる第二の有機溶剤、
を含む、感光性樹脂組成物であって、
前記アルカリ可溶性樹脂が、ポリアミド樹脂、ポリイミド樹脂、およびそれらの前駆体から選択される少なくとも1つを含み、
前記第二の有機溶剤が、カルボニル基を有する複素環化合物(ただし、N-メチル-2-ピロリドンを除く)を含み、
前記第二の有機溶剤が、当該感光性樹脂組成物全体に対して、0.001質量%以上4.0質量%以下の量である、
感光性樹脂組成物。 - 前記カルボニル基を有する複素環化合物が、ピロール、イミダゾール、オキサゾール、チアゾール、およびピラゾール、ならびにこれらの誘導体から選択される少なくとも1つを含む、請求項1に記載の感光性樹脂組成物。
- 前記カルボニル基を有する複素環化合物が、N-エチル-2-ピロリドン、1,3-ジメチル-2-イミダゾリジノン、3-メチル-2-オキサゾリドンから選択される少なくとも1つを含む、請求項1または2に記載の感光性樹脂組成物。
- 前記第一の有機溶剤が、γ-ブチロラクトン、γ-バレロラクトン、2,6-ルチジン、ピルビン酸N,N-ジメチルアセトアミド、3-メトキシ-N,N-ジメチルプロピオンアミド、ジメチルスルホキシド、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールジブチルエーテル、プロピレングリコールモノメチルエーテル、ジプロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、乳酸メチル、乳酸エチル、乳酸ブチル、メチル-1,3-ブチレングリコールアセテート、1,3-ブチレングリコール-3-モノメチルエーテル、ピルビン酸メチル、ピルビン酸エチル、およびメチル-3-メトキシプロピオネートから選択される少なくとも1つを含む、請求項1~3のいずれかに記載の感光性樹脂組成物。
- 前記アルカリ可溶性樹脂が、ポリアミド樹脂を含み、前記ポリアミド樹脂が、以下の式(1)で表される繰り返し単位を有する、請求項1~4のいずれかに記載の感光性樹脂組成物:
XおよびYは、有機基であり、
R1は、水酸基、-O-R3、アルキル基、アシルオキシ基、またはシクロアルキル基であり、複数有する場合にはそれぞれ同一であっても異なってもよく、
R2は、水酸基、カルボキシル基、-O-R3、または-COO-R3であり、複数有する場合にはそれぞれ同一であっても異なってもよく、
R1およびR2におけるR3は、炭素数1~15の有機基であり、
R1として水酸基がない場合、R2の少なくとも1つはカルボキシル基であり、
R2としてカルボキシル基がない場合、R1の少なくとも1つは水酸基であり、
mは0~8の整数であり、
nは0~8の整数である。
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