WO2011037182A1 - Photosensitive resin composition for resist material, and photosensitive resin laminate - Google Patents
Photosensitive resin composition for resist material, and photosensitive resin laminate Download PDFInfo
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- WO2011037182A1 WO2011037182A1 PCT/JP2010/066546 JP2010066546W WO2011037182A1 WO 2011037182 A1 WO2011037182 A1 WO 2011037182A1 JP 2010066546 W JP2010066546 W JP 2010066546W WO 2011037182 A1 WO2011037182 A1 WO 2011037182A1
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- photosensitive resin
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- resin composition
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
Definitions
- the present invention relates to a photosensitive resin composition and a photosensitive resin laminate, and more particularly to a photosensitive resin composition and a photosensitive resin laminate that are suitable as resists used for forming LSI chip or CSP (Chip Size Package) bumps.
- “Bump” refers to a protrusion of a small hump-like conductor provided to facilitate connection when connecting a component terminal and a wiring board.
- the case where the LSI chip and the substrate to be mounted are directly joined is called bare chip mounting.
- bumps are formed on the LSI chip terminals.
- a package in which an LSI chip is once sealed with an organic resin or the like is connected to a substrate to be mounted, bumps are formed on the package terminals.
- CSP is a component in which an LSI chip is packaged, and is generally a package that is equal to or slightly larger than the LSI chip size, and is rapidly spreading with the recent miniaturization of electronic devices.
- BGA All Grid Array
- LGA Land Grid Array
- SON Small Outline Non-leaded
- the plating method is excellent in that the bump pitch can be reduced according to the resolution of the resist. Further, by using a thick film resist such as a dry film, it is possible to deposit a high amount of plating, and it is possible to make a highly reliable bump having a sufficient height (refer to Patent Document 1 below).
- a thick film resist such as a dry film
- the resist must be peeled after bumps are formed by plating. In this peeling process, the resist must be completely peeled off so that there is no residual residue.
- the resist swells greatly, stress is applied to the bumps, so that the bumps may be lost.
- the problem to be solved by the present invention is a photosensitive resin composition for a resist material which has excellent developability, has a high resolution corresponding to a narrow pitch, and can dissolve a cured resist film in a stripping solution in a short time. It is providing a thing and a photosensitive resin laminated body.
- the present inventor has found that by using a specific photosensitive resin composition, the cured resist film dissolves in a stripping solution in a short time while having excellent developability and high resolution. It came to be completed.
- the present invention is the following [1] to [9]: [1] (A) Alkali-soluble polymer 30 to 70% by mass, (B) Compound having ethylenically unsaturated double bond 20 to 60% by mass, and (C) Photopolymerization initiator 0.1 to 20% by mass And (B) a compound having an ethylenically unsaturated double bond as a compound having at least a hydroxyl group, a phenyl group and two or more ethylenically unsaturated double bonds in the molecule. And the compound (B-2) having an ethylene oxide group and a (meth) acryloyl group in the molecule.
- a compound (B-1) having at least a hydroxyl group, a phenyl group, and two or more ethylenically unsaturated double bonds in the molecule is represented by the following formula (I): ⁇ Wherein R 1 is a —H or —CH 3 group, and n is an integer of 1 to 3. ⁇
- the photosensitive resin composition for resist materials as described in said [1] which is a compound represented by these.
- the compound (B-2) is represented by the following formulas (II) to (IV): ⁇ Wherein R 2 is a —C 2 H 4 — group, R 3 is a —C 3 H 6 — group, and — (O—R 2 ) — and — (O—R 3 ) — The repetition may be random or block, any of which may be on the acryloyl group side, m 1 + m 2 + m 3 is an integer from 1 to 15, and l 1 + l 2 + l 3 is from 0 to It is an integer of 15.
- R 2 is a —C 2 H 4 — group
- R 3 is a —C 3 H 6 — group
- the repetition may be random or block, any of which may be on the acryloyl group side
- k 1 + k 2 + k 3 is an integer from 1 to 15
- j 1 + j 2 + j 3 is from 0 to It is an integer of 15.
- a photosensitive resin laminate in which a layer containing the photosensitive resin composition for a resist material according to any one of [1] to [5] is laminated on a support film.
- a method for forming a resist pattern comprising a step of developing a body.
- a method of forming a semiconductor bump comprising: a step of developing the laminate, and a step of copper plating or solder plating on the sputtered copper thin film after the development.
- the resist film after curing can be dissolved in a stripping solution in a short time while having excellent developability and high resolution. As a result, it is possible to suppress defects such as missing bumps and residual resist peeling due to defective plating, and to produce semiconductor bumps with a narrow pitch with a high yield.
- the present invention includes (A) an alkali-soluble polymer of 30 to 70% by mass, (B) a compound having an ethylenically unsaturated double bond of 20 to 60% by mass, and (C) a photopolymerization initiator of 0.1 to 20% by mass. % Of the photosensitive resin composition for resist materials, wherein (B) the compound having an ethylenically unsaturated double bond has at least a hydroxyl group, a phenyl group and two or more ethylenically unsaturated double bonds in the molecule. And a compound (B-1) having a bond and a compound (B-2) having an ethylene oxide group and a (meth) acryloyl group in the molecule.
- resist material means a material that is used in the process of manufacturing parts and circuits and is not included in a finished product.
- the resist material is formed as a resist pattern on the substrate to be processed, and after the substrate to be processed is processed by a processing method such as etching, plating, or sand blast described later, the resist material is stripped, for example, with an alkaline stripping solution.
- the compound having an ethylenically unsaturated double bond includes a compound (B-1) having at least a hydroxyl group, a phenyl group, and two or more ethylenically unsaturated double bonds in the molecule.
- the compound (B-1) having at least a hydroxyl group, a phenyl group, and two or more ethylenically unsaturated double bonds in the molecule is represented by the formula (I): It is preferable that it is at least 1 type of compound chosen from the group which consists of a compound represented by these.
- R 1 is —H or CH 3 group, and —H group is more preferable from the viewpoint of peeling piece solubility.
- Compound (B-1) can be obtained by reacting diglycidyl ether of bisphenol A with (meth) acrylic acid. Commercially available diglycidyl ether of bisphenol A is often a mixture of bisphenol A diglycidyl ether and a multimeric epoxy resin produced in the process of synthesizing it.
- Compound (B-1) can also be obtained by reacting such a mixture of epoxy resins with (meth) acrylic acid, and in this case, it is obtained as a mixture of compounds having different values of n in general formula (I). It is done.
- Examples of the compound (B-1) include R-130 manufactured by Nippon Kayaku Co., Ltd. (in the above formula (I), R 1 is a —H group and n is 1, 2, 3).
- a mixture Ebecryl 600, Ebecryl 3700, Ebecryl 3704 manufactured by Daicel Cytec Co., Ltd., NK Oligo EA-1020 manufactured by Shin-Nakamura Chemical Co., Ltd., and the like.
- the compounding amount of the compound (B-1) is preferably 2% by mass to 35% by mass when the solid content of the entire photosensitive resin composition is 100% by mass. From the viewpoint of peeling piece solubility, it is preferably 2% by mass or more, from the viewpoint of developability, preferably 35% by mass or less, more preferably 5 to 30% by mass, and further preferably 10 to 25% by mass.
- the compound having an ethylenically unsaturated double bond includes a compound (B-2) having an ethylene oxide group and a (meth) acryloyl group in the molecule.
- a compound (B-2) having an ethylene oxide group and a (meth) acryloyl group in the molecule By including the compound (B-2), sufficient developability can be secured, and higher resolution and peelable piece solubility can be achieved. From the viewpoint of peeling piece solubility, it is preferable that all of the compound (B-2) has an acryloyl group.
- the compounding amount of the compound (B-2) is preferably 5% by mass to 40% by mass when the total solid content of the photosensitive resin composition is 100% by mass. 5 mass% or more is preferable from the viewpoint of peelable piece solubility and minimum development time, 40 mass% or less is preferable from the viewpoint of edge fuse property, more preferably 10 to 30 mass%, still more preferably 15 to 25 mass%. It is.
- Compound (B-2) may be monofunctional.
- a compound obtained by adding (meth) acrylic acid to one end of polyethylene oxide or a compound obtained by adding (meth) acrylic acid to one end and alkylating or allylating the other end. it can.
- examples of such a compound include phenoxyhexaethylene glycol mono (meth) acrylate, which is a (meth) acrylate of a compound obtained by adding polyethylene glycol to a phenyl group, polypropylene glycol added with an average of 2 mol of propylene oxide, and an average of 7 mol.
- Examples also include 4-normal nonylphenoxyoctaethylene glycol (meth) acrylate (M-114, manufactured by Toagosei Co., Ltd.), which is an acrylate of a compound obtained by adding polyethylene glycol with an average of 8 moles of ethylene oxide added to nonylphenol.
- M-114 4-normal nonylphenoxyoctaethylene glycol (meth) acrylate
- M-114 4-normal nonylphenoxyoctaethylene glycol (meth) acrylate
- M-114 4-normal nonylphenoxyoctaethylene glycol (meth) acrylate
- the compound (B-2) may be bifunctional.
- a compound having a (meth) acryloyl group at both ends of an ethylene oxide chain or a compound having a (meth) acryloyl group at both ends of an alkylene oxide chain in which an ethylene oxide chain and a propylene oxide chain are bonded randomly or in blocks Can do.
- examples of such compounds include tetraethylene glycol di (meth) acrylate, pentaethylene glycol di (meth) acrylate, hexaethylene glycol di (meth) acrylate, heptaethylene glycol di (meth) acrylate, and octaethylene glycol di (meth).
- it may be a compound having bisphenol A modified with ethylene oxide and having (meth) acryloyl groups at both ends.
- Examples of such a compound include 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane (NK ester BPE-200 manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meth) acrylic) Loxypentaethoxy) phenyl) propane (NK Nakamura Chemical Co., Ltd.
- NK ester BPE-500 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl) propane, 2,2-bis ( 4-((meth) acryloxyheptaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, , 2-bis (4-((meth) acryloxy nonaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydecaethoxy) phenyl) propane, 2,2-bis (4- ( (Meth) acryloxyundecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxidedodecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytrideca) Ethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetradecaethoxy) phenyl) propane
- di (meth) acrylate of polyalkylene glycol obtained by adding an average of 2 mol of propylene oxide and an average of 6 mol of ethylene oxide to both ends of bisphenol A, and an average of 2 mol of propylene oxide and an average of 15 respectively at both ends of bisphenol A.
- examples include poly (alkylene glycol) di (meth) acrylate added with a mole of ethylene oxide.
- These bifunctional compounds having an ethylene oxide group and a (meth) acryloyl group in the molecule preferably have an acryloyl group.
- the compound (B-2) may be trifunctional or higher.
- a compound having a tri- or higher functional ethylene oxide group and a (meth) acryloyl group has at least 3 mol of a group capable of adding an ethylene oxide group and other alkylene oxide groups such as propylene oxide and butylene oxide in the molecule as a central skeleton.
- the alcohol obtained by adding an ethylene oxide group or the like to this is obtained as (meth) acrylate.
- Examples of the compound that becomes the central skeleton include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and isocyanurate rings.
- the trifunctional or higher functional compound (B-2) also preferably has an acryloyl group.
- Preferable examples of the compound having a trifunctional or higher functional ethylene oxide group and an acryloyl group include compounds represented by the following general formulas (II) to (IV).
- R 2 is a —C 2 H 4 — group
- R 3 is a —C 3 H 6 — group
- the repetition may be random or block.
- the repeating unit is preferably a block from the viewpoint of structural control in production. Either — (O—R 2 ) — or — (O—R 3 ) — may be on the acryloyl group side.
- m 1 + m 2 + m 3 is an integer of 1 to 15, and is 1 or more from the viewpoint of developability, 15 or less from the viewpoint of resolution, preferably 1 to 10, and more preferably 1 to 7.
- l 1 + l 2 + l 3 is an integer of 0 to 15, but is 15 or less, preferably 10 or less, more preferably 4 or less, and more preferably 0 from the viewpoint of peeling piece solubility.
- examples of such compounds include trimethylolpropane ethylene oxide (hereinafter also referred to as “EO”) 3 mol-modified triacrylate (A-TMPT-3EO manufactured by Shin-Nakamura Chemical Co., Ltd.), trimethylolpropane EO 6 mol-modified.
- EO trimethylolpropane ethylene oxide
- A-TMPT-3EO manufactured by Shin-Nakamura Chemical Co., Ltd.
- trimethylolpropane EO 6 mol-modified examples include triacrylate, trimethylolpropane EO 9 mol-modified triacrylate, trimethylolpropane EO 12 mol-modified triacrylate, and the like.
- R 2 is a —C 2 H 4 — group
- R 3 is a —C 3 H 6 — group
- the repetition may be random or block, and either may be on the acryloyl group side.
- the repeating unit is preferably a block from the viewpoint of structural control in production.
- k 1 + k 2 + k 3 is an integer of 1 to 15, and is 1 or more from the viewpoint of developability and 15 or less from the viewpoint of resolution, preferably 1 to 10, and more preferably 3 to 9.
- j 1 + j 2 + j 3 is an integer of 0 to 15, and is 15 or less, preferably 10 or less, and more preferably 0 from the viewpoint of peeling piece solubility.
- examples of such a compound include glycerin EO3 mol-modified triacrylate (A-GLY-3E manufactured by Shin-Nakamura Chemical Co., Ltd.) and glycerin EO 9 mol-modified triacrylate (A-GLY- manufactured by Shin-Nakamura Chemical Co., Ltd.). 9E), EO 6 mol PO6 mol modified triacrylate of glycerin (A-GLY-0606PE), EO 9 mol PO9 mol modified triacrylate of glycerin (A-GLY-0909PE).
- R 2 is a —C 2 H 4 — group
- R 3 is a —C 3 H 6 — group
- the repetition may be random or block, and either may be on the acryloyl group side.
- the repeating unit is preferably a block from the viewpoint of structural control in production.
- h 1 + h 2 + h 3 + h 4 is an integer of 1 to 40. From the viewpoint of developability, it is 1 or more, and from the viewpoint of resolution, it is 40 or less, preferably from 1 to 20, and more preferably from 3 to 15.
- i 1 + i 2 + i 3 + i 4 is an integer of 0 to 15, and is 15 or less, preferably 10 or less, and more preferably 0 from the viewpoint of peeling piece solubility.
- examples of such compounds include pentaerythritol 4EO-modified tetraacrylate (SR-494, manufactured by Sartomer Japan Co., Ltd.), pentaerythritol 35EO-modified tetraacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester ATM-35E). ).
- urethane compounds are also included.
- hexamethylene diisocyanate, tolylene diisocyanate or diisocyanate compounds such as 2,2,4-trimethylhexamethylene diisocyanate and compounds having a hydroxyl group and a (meth) acryl group in one molecule, such as 2-hydroxypropyl acrylate And urethane compounds with oligopropylene glycol monomethacrylate.
- hexamethylene diisocyanate and oligopropylene glycol monomethacrylate Nippon Yushi Co., Ltd., Blenmer PP1000.
- di (meth) acrylate or tri (meth) acrylate of isocyanuric acid ester modified with polypropylene glycol or polycaprolactone is also included.
- the compound represented by the formula (III) is a stripping piece solubility, development From the viewpoints of performance and resolution.
- the compounding amount of the compound having an ethylenically unsaturated double bond is 20 to 60% by mass when the total solid content of the photosensitive resin composition is 100% by mass, and the sensitivity, resolution, adhesion From the viewpoint of safety, it is 20% by mass or more, and from the viewpoint of resolution and adhesion, it is 60% by mass or less. From the viewpoint of film physical properties of the unexposed film when it is applied to a support film to form a dry film, the content is preferably 60% by mass or less, more preferably 30 to 45% by mass.
- the alkali-soluble polymer is a vinyl-based resin containing a carboxyl group, such as a copolymer such as (meth) acrylic acid, (meth) acrylic ester, (meth) acrylonitrile, (meth) acrylamide, and the like. is there.
- the alkali-soluble polymer preferably contains a carboxyl group and has an acid equivalent of 100 to 600.
- the acid equivalent means the mass of the alkali-soluble polymer having 1 equivalent of a carboxyl group therein.
- the acid equivalent is more preferably 250 or more and 450 or less.
- the acid equivalent is preferably 100 or more from the viewpoint of improving development resistance and improving resolution and adhesion, and is preferably 600 or less from the viewpoint of improving developability and peelability.
- the acid equivalent is measured by a potentiometric titration method using a Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd., using 0.1 mol / L sodium hydroxide.
- the weight average molecular weight of the alkali-soluble polymer is preferably 20,000 or more and 80,000 or less.
- the weight average molecular weight of the alkali-soluble polymer is preferably 80,000 or less from the viewpoint of improving the developability, and the properties of the development aggregate, the edge fuse property when the photosensitive resin laminate is used, the cut chip property, etc. From the viewpoint of the properties, it is preferably 20,000 or more.
- the edge fuse property is a phenomenon in which the photosensitive resin composition layer protrudes from the end surface of the roll when the photosensitive resin laminate is wound into a roll.
- the cut chip property is the phenomenon that the chip flies when the unexposed film is cut with a cutter.
- the weight average molecular weight of the alkali-soluble polymer is more preferably 20,000 or more and 60,000 or less, and more preferably 40,000 or more and 60,000 or less.
- the weight average molecular weight was determined by gel permeation chromatography (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 type, column: Shodex (registered trademark) manufactured by Showa Denko KK (KF-807, KF-806M).
- the alkali-soluble polymer is preferably a copolymer comprising at least one or more of the first monomers described below and at least one or more of the second monomers described below.
- the first monomer is a carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule. Examples include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester. Among these, (meth) acrylic acid is particularly preferable.
- (meth) acryl refers to acryl and / or methacryl. The same applies hereinafter.
- the second monomer is a non-acidic monomer having at least one polymerizable unsaturated group in the molecule.
- methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, and benzyl (meth) acrylate are preferable.
- Benzyl (meth) acrylate is preferred from the viewpoint of floating the bottom of the resist foot after development.
- the copolymerization ratio of the first monomer and the second monomer is preferably 10 to 60% by mass for the first monomer and 40 to 90% by mass for the second monomer. More preferably, the first monomer is 15 to 35% by mass, and the second monomer is 65 to 85% by mass.
- Preferred combinations of the first monomer and the second monomer include the following combinations, for example, butyl acrylate, methyl methacrylate, methacrylic acid copolymer, styrene, methyl methacrylate, methacrylic acid.
- Styrene benzyl methacrylate, methacrylic acid copolymer, benzyl methacrylate, methacrylic acid copolymer, benzyl methacrylate, 2-ethylhexyl acrylate, methacrylic acid copolymer, and the like. it can.
- the ratio of the alkali-soluble polymer to the total of the photosensitive resin composition is in the range of 30 to 70% by mass, preferably 40 to 60% by mass. From the viewpoint of development time, it is 70% by mass or less, and from the viewpoint of edge fuse property, it is 30% by mass or more.
- photopolymerization initiator (C) included in the present invention will be described.
- the photopolymerization initiator those generally known can be used.
- the content of the photopolymerization initiator is in the range of 0.1 to 20% by mass, and more preferably in the range of 0.5 to 10% by mass. From the viewpoint of obtaining sufficient sensitivity, it is preferably 0.1% by mass or more, and from the viewpoint of sufficiently transmitting light to the bottom surface of the resist and obtaining high resolution, it is preferably 20% by mass or less.
- (C) As the photopolymerization initiator, 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1, Quinones such as 4-naphthoquinone, 2,3-dimethylanthraquinone, 3-chloro-2-methylanthraquinone, aromatic ketones such as benzophenone, Michler's ketone [4,4'-bis (dimethylamin
- a combination of the above-mentioned lophine dimer and Michler's ketone [4,4′-bis (dimethylamino) benzophenone] or 4,4′-bis (diethylamino) benzophenone is a preferable combination from the viewpoints of sensitivity and resolution.
- the amount of the lophine dimer can be appropriately adjusted according to the sensitivity and the development aggregation property.
- 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer it is preferably 1% by mass or more from the viewpoint of sensitivity, and preferably 5% by mass or less from the viewpoint of aggregation. More preferably, it is 2 to 4% by mass.
- the amount of 4,4′-bis (diethylamino) benzophenone can be appropriately adjusted in consideration of sensitivity, rectangularity of the resist pattern, and light transmittance at the exposure wavelength.
- a photosensitive resin layer having a thickness of 70 ⁇ m or more it is preferably 0.05% by mass or less in consideration of pattern adhesion and rectangularity, and 0.01% by mass or more from the viewpoint of sensitivity. preferable.
- a light source such as a semiconductor laser
- the photosensitive resin composition used in the present invention may contain a leuco dye, a fluoran dye, a coloring substance, and the like. By including these dyes, the exposed portion is colored, which is preferable in terms of visibility. When an inspection machine or the like reads an alignment marker for exposure, it is advantageous that the contrast between the exposed part and the unexposed part is easier to recognize.
- the leuco dye examples include tris (4-dimethylaminophenyl) methane [leucocrystal violet] and bis (4-dimethylaminophenyl) phenylmethane [leucomalachite green].
- leuco crystal violet is used as the leuco dye.
- the content is preferably 0.1 to 10% by mass in the photosensitive resin composition.
- the content is preferably 0.1% by mass or more from the viewpoint of the contrast between the exposed part and the unexposed part, and is preferably 10% by mass or less from the viewpoint of maintaining storage stability.
- it is a preferable embodiment of this invention from a viewpoint of adhesiveness and contrast to use in combination with a leuco dye and the following halogen compound in the photosensitive resin composition.
- the coloring substance examples include fuchsin, phthalocyanine green, auramin base, paramadienta, crystal violet, methyl orange, Nile Blue 2B, Victoria Blue, Malachite Green (Eizen (registered trademark) MALACHITE GREEN manufactured by Hodogaya Chemical Co., Ltd.), basic blue. 20, Diamond Green (Eizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.).
- the addition amount is preferably 0.001 to 1% by mass in the photosensitive resin composition. A content of 0.001% by mass or more is preferable from the viewpoint of improving handleability, and a content of 1% by mass or less is preferable from the viewpoint of maintaining storage stability.
- the photosensitive resin composition may contain an N-aryl- ⁇ -amino acid compound from the viewpoint of sensitivity.
- N-aryl- ⁇ -amino acid compound N-phenylglycine is preferable.
- the content is preferably 0.01% by mass or more and 1% by mass or less.
- the photosensitive resin composition may contain a halogen compound.
- the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2 , 3-dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, chlorinated triazine compounds, among others. Tribromomethylphenylsulfone is preferably used. When the halogen compound is contained, the content is 0.01 to 3% by mass in the photosensitive resin composition.
- the photosensitive resin composition is at least one selected from the group consisting of radical polymerization inhibitors, benzotriazoles, and carboxybenzotriazoles. You may further contain a compound more than a seed
- radical polymerization inhibitor examples include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2′-methylenebis. (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine and the like.
- benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis (N-2-ethylhexyl) aminomethylene-1,2,3-benzotriazole, Examples thereof include bis (N-2-ethylhexyl) aminomethylene-1,2,3-tolyltriazole, bis (N-2-hydroxyethyl) aminomethylene-1,2,3-benzotriazole.
- carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and N- (N, N-di-2-ethylhexyl) aminomethylene. Examples thereof include carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole and the like.
- the total content of the radical polymerization inhibitor, benzotriazoles, and carboxybenzotriazoles is preferably 0.01 to 3% by mass, more preferably 0.05 to 1%, based on the entire photosensitive resin composition. % By mass.
- the content is preferably 0.01% by mass or more from the viewpoint of imparting storage stability to the photosensitive resin composition, and more preferably 3% by mass or less from the viewpoint of maintaining sensitivity and suppressing decolorization of the dye. .
- the photosensitive resin composition may contain a plasticizer as necessary.
- plasticizers include polyethylene glycol, polypropylene glycol, polyoxypropylene polyoxyethylene ether, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene polyoxypropylene monomethyl ether, and polyoxyethylene monoethyl.
- Glycols and esters such as ether, polyoxypropylene monoethyl ether, polyoxyethylene polyoxypropylene monoethyl ether, phthalic acid esters such as diethyl phthalate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, citric acid Tributyl, triethyl citrate, acetyl triethyl citrate, tri-n-propyl acetyl citrate, tri-n-acetyl citrate Such as chill, and the like.
- the content of the plasticizer is preferably 5 to 50% by mass, more preferably 5 to 30% by mass in the photosensitive resin composition.
- the content is preferably 5% by mass or more from the viewpoint of suppressing development time delay and imparting flexibility to the cured film, and is preferably 50% by mass or less from the viewpoint of suppressing insufficient curing and cold flow.
- the photosensitive resin laminate includes a photosensitive resin layer made of a photosensitive resin composition and a support film. If necessary, you may have a protective layer on the surface on the opposite side to the support film side of the photosensitive resin layer.
- the support film used here is preferably a transparent film that transmits light emitted from the exposure light source. Examples of such support films include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, Examples include polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, and cellulose derivative film. These films can be stretched if necessary. The haze is preferably 5 or less. A thinner film is advantageous in terms of image forming property and economic efficiency, but a film having a thickness of 10 to 30 ⁇ m is preferably used in order to maintain the
- the protective layer used in the photosensitive resin laminate is that the protective layer is sufficiently smaller than the support film in terms of adhesion to the photosensitive resin layer and can be easily peeled off.
- a polyethylene film or a polypropylene film can be preferably used as the protective layer.
- a film having excellent releasability disclosed in JP-A-59-202457 can be used.
- the thickness of the protective layer is preferably 10 to 100 ⁇ m, more preferably 10 to 50 ⁇ m.
- the thickness of the photosensitive resin layer in the photosensitive resin laminate varies depending on the application, but is preferably 5 to 100 ⁇ m, more preferably 7 to 60 ⁇ m. The thinner the resolution, the higher the resolution, and the thicker the film strength. .
- a known method can be employed as a method for preparing a photosensitive resin laminate by sequentially laminating a support film, a photosensitive resin layer, and, if necessary, a protective layer.
- the photosensitive resin composition used for the photosensitive resin layer is mixed with a solvent that dissolves them to form a uniform solution, which is first applied onto the support film using a bar coater or a roll coater, and then dried to form the support film.
- a photosensitive resin layer made of a photosensitive resin composition can be laminated thereon.
- the thickness of the photosensitive resin layer after drying varies depending on the use, but is preferably 1 to 100 ⁇ m, more preferably 2 to 50 ⁇ m, and further preferably 3 to 15 ⁇ m.
- the thickness is preferably 3 ⁇ m or more from the viewpoint of tent properties, and is preferably 15 ⁇ m or less from the viewpoint of resolution.
- the thickness is preferably 70 to 150 ⁇ m, more preferably 70 to 120 ⁇ m.
- the thickness is preferably 150 ⁇ m or less from the viewpoint of securing the hole detachability for forming the semiconductor bump, and is preferably 70 ⁇ m or more from the viewpoint of securing the plating height necessary for bump connection.
- a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin layer.
- Examples of the solvent that dissolves the photosensitive resin composition include ketones typified by methyl ethyl ketone (MEK), alcohols typified by methanol, ethanol, and isopropanol.
- MEK methyl ethyl ketone
- the solvent is preferably added to the photosensitive resin composition so that the viscosity of the solution of the photosensitive resin composition applied on the support film is 500 to 4000 mPa ⁇ s at 25 ° C.
- the resist pattern using the photosensitive resin laminate can be formed by a process including a laminating process for laminating, an exposing process for exposing active light, and a developing process for removing unexposed portions.
- a copper-clad laminate is used for manufacturing a printed wiring board
- a glass substrate such as a plasma display panel substrate or a surface electrolytic display substrate is used for manufacturing an uneven substrate.
- a sealing cap substrate examples thereof include a silicon wafer having a through hole, and a ceramic substrate.
- a plasma display substrate is a substrate in which an electrode is formed on glass, a dielectric layer is applied, a partition wall glass paste is then applied, and a partition wall glass paste portion is subjected to sandblasting to form a partition wall. .
- Those obtained by subjecting these glass substrates to sand blasting are uneven substrates.
- a laminating process is performed using a laminator.
- the protective layer is peeled off, and then the photosensitive resin layer is laminated on the substrate surface by thermocompression bonding with the laminator.
- the photosensitive resin layer may be laminated only on one side of the substrate surface, or may be laminated on both sides.
- the heating temperature at this time is generally about 40 to 160 ° C.
- adhesion and chemical resistance are improved by performing the thermocompression bonding twice or more.
- a two-stage laminator provided with two rolls may be used, or it may be repeatedly crimped through a roll several times.
- an exposure process is performed using an exposure machine. If necessary, the support film is peeled off and exposed to active light through a photomask.
- the exposure amount is determined by the light source illuminance and the exposure time. The exposure amount may be measured using a light meter. Examples of the exposure machine include a scattered light exposure machine using an ultra-high pressure mercury lamp as a light source, a parallel light exposure machine with the same degree of parallelism, and a proximity exposure machine with a gap between the mask and the workpiece.
- a projection type exposure machine having a mask to image size ratio of 1: 1, a reduction projection exposure machine called a high illuminance stepper (registered trademark), and an exposure machine using a concave mirror called a mirror projection aligner (registered trademark). be able to.
- Direct drawing exposure is a method in which exposure is performed by directly drawing on a substrate without using a photomask.
- the light source for example, a semiconductor laser having a wavelength of 350 to 410 nm or an ultrahigh pressure mercury lamp is used.
- the drawing pattern is controlled by a computer, and the exposure amount in this case is determined by the light source illuminance and the moving speed of the substrate.
- a developing process is performed using a developing device. After the exposure, if there is a support film on the photosensitive resin layer, this is removed if necessary, and then the unexposed portion is developed and removed using a developer of an alkaline aqueous solution to obtain a resist image.
- an aqueous solution of Na 2 CO 3 or K 2 CO 3 is used as the alkaline aqueous solution.
- the alkaline aqueous solution is appropriately selected according to the characteristics of the photosensitive resin layer, but a Na 2 CO 3 aqueous solution having a concentration of about 0.2 to 2% by mass and about 20 to 40 ° C. is generally used.
- a surface active agent, an antifoaming agent, a small amount of an organic solvent for promoting development, and the like may be mixed in the alkaline aqueous solution.
- An amine-based alkaline aqueous solution such as a tetraammonium hydroxide (TMAH) aqueous solution can also be used in consideration of the influence on the substrate.
- TMAH tetraammonium hydroxide
- the density can be appropriately selected according to the developing speed.
- a heating step at about 100 to 300 ° C. may be further performed in some cases.
- chemical resistance can be further improved.
- a hot-air, infrared, or far-infrared heating furnace can be used.
- the printed wiring board can be obtained through the following steps following the above ⁇ resist pattern forming method> using a copper-clad laminate or a flexible substrate as a substrate.
- a conductor pattern is manufactured by using a known method such as an etching method or a plating method on a copper surface exposed by development.
- the resist pattern is peeled from the substrate with an aqueous solution having alkalinity stronger than that of the developer to obtain a desired printed wiring board.
- the alkaline aqueous solution for stripping (hereinafter also referred to as “stripping solution”) is not particularly limited, but an aqueous solution of NaOH or KOH having a concentration of about 2 to 5% by mass and a temperature of about 40 to 70 ° C. is generally used. A small amount of a water-soluble solvent can also be added to the stripping solution.
- the lead frame can be obtained through the following steps following the above-described ⁇ resist pattern forming method> using a metal plate, for example, copper, a copper alloy, or an iron-based alloy as a substrate. First, a conductive pattern is formed by etching the substrate exposed by development. Thereafter, the resist pattern is peeled by the same method as in the above-described ⁇ Printed wiring board manufacturing method> to obtain a desired lead frame.
- the semiconductor package can be obtained by performing the following steps following the above-described ⁇ resist pattern forming method> using a wafer in which circuit formation as an LSI has been completed as a substrate. First, the opening exposed by development is subjected to columnar plating with copper or solder to form a conductor pattern. Thereafter, the resist pattern is peeled off in the same manner as in the above-mentioned ⁇ Method for manufacturing printed wiring board>, and the thin metal layer other than the columnar plating is removed by etching to obtain a desired semiconductor package.
- ⁇ Manufacturing method of substrate having concave / convex pattern> Substrates that can be sandblasted, such as glass substrates, glass substrates coated with glass rib paste, ceramic substrates, metal substrates such as stainless steel, silicon wafers, ores such as sapphire, organic substrates such as synthetic resin layers
- a photosensitive resin laminate is laminated on the material in the same manner as in the above ⁇ resist pattern forming method>, and exposure and development are performed. After that, by passing through a sandblasting process in which a blast material is sprayed from the formed resist pattern to cut to a desired depth, and a resin part remaining on the substrate is removed from the substrate with an alkaline stripping solution or the like A fine pattern is formed on the substrate.
- blasting material used in the above sandblasting process known materials can be used. For example, fine particles of about 2 to 100 ⁇ m such as SiC, SiO 2 , Al 2 O 3 , CaCO 3 , ZrO 2 , glass, stainless steel, etc. are used. It is done.
- the semiconductor bump can be created by the following method.
- An insulating layer is provided on the silicon wafer substrate, and electrodes for connecting to the silicon wafer are formed on necessary portions.
- a conductive film such as copper is formed by a method such as sputtering.
- the liquid resist is spin-coated on the substrate thus obtained.
- the solvent is removed by pre-baking and dried to obtain a resist coating film.
- a pattern is formed by exposure and development. In the case of using a dry film, the pattern is formed by the same method as the above ⁇ Resist pattern formation method>.
- plating is performed in the pattern, but pretreatment includes a method of immersing in water or a plating solution itself.
- a nickel film called an under bump metal is formed by plating in order to ensure adhesion to the bump, and solder is plated thereon by a plating method to form a bump.
- copper plating is performed in the pattern, and then a solder bump is formed.
- the plating bath used for plating include the following.
- the nickel plating bath include a watt bath and a sulfamic acid bath.
- solder plating bath a bath of high lead, eutectic, lead-free or the like is selected according to the properties of the solder.
- an electrolytic copper plating bath such as copper sulfate is generally used.
- the stripping solution consists of an alkali component such as ethanolamine, an alkali component such as tetramethylammonium hydroxide (TMAH) or a combination of two or more organic alkalis, a highly polar water-soluble organic solvent such as glycol or dimethyl sulfoxide, water An organic stripping solution in combination of the above can be used.
- TMAH tetramethylammonium hydroxide
- Copper plating is generally a plating bath such as copper sulfate.
- the conductive film is removed by etching.
- etching a known method using copper chloride or the like can be used.
- the solder portion is heated by a heating process called reflow to produce a solder ball, which becomes a semiconductor bump.
- Examples 1 to 20 and Comparative Examples 1 and 2 First, a method for producing samples for evaluation of Examples and Comparative Examples will be described, and then an evaluation method and evaluation results for the obtained samples will be shown.
- Evaluation samples in Examples and Comparative Examples were produced as follows. ⁇ Preparation of photosensitive resin laminate> The photosensitive resin composition and the solvent having the composition shown in Table 1 below (however, the numbers of each component indicate the blending amount (parts by mass) as a solid content) are thoroughly stirred and mixed to obtain a photosensitive resin composition preparation liquid. Then, a 16 ⁇ m thick polyethylene terephthalate film as a support was uniformly coated on the surface using a bar coater, and dried in a dryer at 95 ° C. for 12 minutes to form a photosensitive resin layer. The thickness of the photosensitive resin layer was 120 ⁇ m.
- ⁇ Development> After the polyethylene terephthalate film was peeled off, a 1% by mass Na 2 CO 3 aqueous solution at 30 ° C. was sprayed and developed to dissolve and remove the unexposed portion of the photosensitive resin layer.
- the minimum time required for complete dissolution of the unexposed portion of the photosensitive resin layer was measured as the “minimum development time” and ranked as follows: A: Minimum development time is 140 seconds or less; ⁇ : The value of the minimum development time exceeds 140 seconds and is 200 seconds or less; X: The value of the minimum development time is over 200 seconds.
- the minimum mask line width in which the cured resist lines are normally formed is ranked as a “resolution” value as follows: A: The resolution value is 30 ⁇ m or less; ⁇ : Resolution value exceeds 30 ⁇ m and 50 ⁇ m or less; X: The value of resolution exceeds 50 ⁇ m.
- ⁇ Laminate> While peeling the polyethylene film of the photosensitive resin laminate, it was laminated on a silicon wafer preheated to 80 ° C. with a hot roll laminator (VA-400III, manufactured by Taisei Laminator Co., Ltd.) at a roll temperature of 80 ° C. The air pressure was 0.20 MPa, and the laminating speed was 1.0 m / min.
- ⁇ Exposure> Using a glass chrome mask, exposure was carried out with Prisma (trade name) ghi line manufactured by Ultratec Corporation. The illuminance measured on the substrate surface was 2500 mW / cm 2 .
- spin developing machine AD-1200 manufactured by Takizawa Sangyo Co., Ltd. spin developing machine AD-1200 manufactured by Takizawa Sangyo Co., Ltd.
- the evaluation substrate was subjected to an O 2 / CF 4 plasma treatment and immersed in pure water for 5 minutes.
- Copper sulfate conch (Meltex Co., Ltd.) was diluted 3.6 times with 19 wt% sulfuric acid, and 200 ppm of concentrated hydrochloric acid was added. Subsequently, capalacid HL and caparacid GS were added as brighteners at 0.4 ml / l and 20 ml / l, respectively.
- the plating resistance evaluation substrate (6 cm ⁇ 12.5 cm) after the pre-plating treatment was subjected to 4 ⁇ m / min with a Haring cell uniform plating apparatus (manufactured by Yamamoto Kakin Tester Co., Ltd.) using the prepared copper sulfate plating solution. The current value was adjusted so that copper was deposited at a height, and plating was performed. The thickness of the copper plating film at this time was 80 ⁇ m.
- solder plating was performed as described below, and peeling was performed as described later to prepare solder bumps (Example 22). Solder plating was performed for 3 hours in a solder plating solution (Plutin LA borofluoride solder bath manufactured by Meltex). The current density was adjusted to 1.5A / dm 2. The height of the solder plating was 90 ⁇ m.
- solder plating solution Plutin LA borofluoride solder bath manufactured by Meltex.
- the current density was adjusted to 1.5A / dm 2.
- the height of the solder plating was 90 ⁇ m.
- the evaluation substrate subjected to the plating treatment was peeled off by heating at 95 ° C. for 1 hour with a flip slip (trade name) manufactured by Dynaloy Co., Ltd.
- Examples 1 to 20 are all excellent in “peeling piece solubility”, “minimum development time”, and “resolution” by adopting the configuration of the present invention.
- Comparative Example 1 is an example lacking the component (B-1) contained in the present invention, but sufficient “peeling piece solubility” was not obtained.
- Comparative Example 2 is an example lacking the component (B-2) contained in the present invention, but the time required for development was extremely long, and sufficient “peeling piece solubility” was not obtained.
- the present invention relates to the manufacture of printed wiring boards, the manufacture of lead frames for IC chip mounting, the manufacture of metal foils such as the manufacture of metal masks, the manufacture of packages such as BGA or CSP, the manufacture of tape substrates such as COF and TAB, the production of semiconductor bumps It can be used for manufacturing, manufacturing of partition walls of flat panel displays such as ITO electrodes, address electrodes and electromagnetic wave shields, and a method of manufacturing a substrate having an uneven pattern by sandblasting.
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Abstract
Description
このように、高い解像度を有し、かつ、狭小ピッチにおいても剥離残が発生しないレジストが望まれていた。 The plating method is excellent in that the bump pitch can be reduced according to the resolution of the resist. Further, by using a thick film resist such as a dry film, it is possible to deposit a high amount of plating, and it is possible to make a highly reliable bump having a sufficient height (refer to Patent Document 1 below). When the film of the photosensitive resin layer is thick, it becomes more difficult to completely develop to the bottom. If there is a residue at the bottom, it may cause plating defects. In the plating method, the resist must be peeled after bumps are formed by plating. In this peeling process, the resist must be completely peeled off so that there is no residual residue. When the resist swells greatly, stress is applied to the bumps, so that the bumps may be lost. These problems become conspicuous as the bump pitch is narrowed.
Thus, there has been a demand for a resist that has a high resolution and that does not cause peeling residue even at a narrow pitch.
[1](A)アルカリ可溶性高分子30~70質量%、(B)エチレン性不飽和二重結合を有する化合物20~60質量%、及び(C)光重合開始剤0.1~20質量%を含むレジスト材料用感光性樹脂組成物であって、前記(B)エチレン性不飽和二重結合を有する化合物として、分子内に少なくともヒドロキシル基とフェニル基と2以上のエチレン性不飽和二重結合とを有する化合物(B-1)、及び分子内にエチレンオキシド基と(メタ)アクリロイル基を有する化合物(B-2)を含む前記組成物。 That is, the present invention is the following [1] to [9]:
[1] (A) Alkali-soluble polymer 30 to 70% by mass, (B) Compound having ethylenically unsaturated double bond 20 to 60% by mass, and (C) Photopolymerization initiator 0.1 to 20% by mass And (B) a compound having an ethylenically unsaturated double bond as a compound having at least a hydroxyl group, a phenyl group and two or more ethylenically unsaturated double bonds in the molecule. And the compound (B-2) having an ethylene oxide group and a (meth) acryloyl group in the molecule.
本発明は、(A)アルカリ可溶性高分子30~70質量%、(B)エチレン性不飽和二重結合を有する化合物20~60質量%、及び(C)光重合開始剤0.1~20質量%を含むレジスト材料用感光性樹脂組成物であって、前記(B)エチレン性不飽和二重結合を有する化合物として、分子内に少なくともヒドロキシル基とフェニル基と2以上のエチレン性不飽和二重結合とを有する化合物(B-1)、及び分子内にエチレンオキシド基と(メタ)アクリロイル基を有する化合物(B-2)を含む組成物である。 Hereinafter, the present invention will be described in detail.
The present invention includes (A) an alkali-soluble polymer of 30 to 70% by mass, (B) a compound having an ethylenically unsaturated double bond of 20 to 60% by mass, and (C) a photopolymerization initiator of 0.1 to 20% by mass. % Of the photosensitive resin composition for resist materials, wherein (B) the compound having an ethylenically unsaturated double bond has at least a hydroxyl group, a phenyl group and two or more ethylenically unsaturated double bonds in the molecule. And a compound (B-1) having a bond and a compound (B-2) having an ethylene oxide group and a (meth) acryloyl group in the molecule.
まず、本発明における(B)エチレン性不飽和二重結合を有する化合物について説明する。
(B)エチレン性不飽和二重結合を有する化合物は、分子内に少なくともヒドロキシル基とフェニル基と2以上のエチレン性不飽和二重結合とを有する化合物(B-1)を含む。上記分子内に少なくともヒドロキシル基とフェニル基と2以上のエチレン性不飽和二重結合とを有する化合物(B-1)は、上記式(I):
First, (B) the compound having an ethylenically unsaturated double bond in the present invention will be described.
(B) The compound having an ethylenically unsaturated double bond includes a compound (B-1) having at least a hydroxyl group, a phenyl group, and two or more ethylenically unsaturated double bonds in the molecule. The compound (B-1) having at least a hydroxyl group, a phenyl group, and two or more ethylenically unsaturated double bonds in the molecule is represented by the formula (I):
化合物(B-1)は、ビスフェノールAのジグリシジルエーテルなどと(メタ)アクリル酸とを反応させることにより得ることができる。市販のビスフェノールAのジグリシジルエーテルは、ビスフェノールAのジグリシジルエーテルとこれを合成する過程で生成する多量体のエポキシ樹脂との混合物であることが多い。化合物(B-1)はこのようなエポキシ樹脂の混合物に(メタ)アクリル酸を反応させることにより得ることもでき、この場合、一般式(I)中のnの値が異なる化合物の混合物として得られる。
化合物(B-1)の例としては、日本化薬(株)製R-130(上記式(I)において、R1が-H基であり、そしてnが1、2、3である化合物の混合物)、ダイセル・サイテック(株)製のEbecryl600、Ebecryl3700、Ebecryl3704、新中村化学工業(株)製NKオリゴ EA-1020などを挙げることができる。 In the formula (I), R 1 is —H or CH 3 group, and —H group is more preferable from the viewpoint of peeling piece solubility. n is an integer of 1 to 3, and n = 1 is preferable from the viewpoint of developability.
Compound (B-1) can be obtained by reacting diglycidyl ether of bisphenol A with (meth) acrylic acid. Commercially available diglycidyl ether of bisphenol A is often a mixture of bisphenol A diglycidyl ether and a multimeric epoxy resin produced in the process of synthesizing it. Compound (B-1) can also be obtained by reacting such a mixture of epoxy resins with (meth) acrylic acid, and in this case, it is obtained as a mixture of compounds having different values of n in general formula (I). It is done.
Examples of the compound (B-1) include R-130 manufactured by Nippon Kayaku Co., Ltd. (in the above formula (I), R 1 is a —H group and n is 1, 2, 3). A mixture), Ebecryl 600, Ebecryl 3700, Ebecryl 3704 manufactured by Daicel Cytec Co., Ltd., NK Oligo EA-1020 manufactured by Shin-Nakamura Chemical Co., Ltd., and the like.
このような化合物としては、ポリエチレングリコールをフェニル基に付加した化合物の(メタ)アクリレートであるフェノキシヘキサエチレングリコールモノ(メタ)アクリレートや、平均2モルのプロピレンオキサイドを付加したポリプロピレングリコールと平均7モルのエチレンオキサイドを付加したポリエチレングリコールをノニルフェノールに付加した化合物の(メタ)アクリレートである4-ノルマルノニルフェノキシヘプタエチレングリコールジプロピレングリコール(メタ)アクリレート、平均1モルのプロピレンオキサイドを付加したポリプロピレングリコールと平均5モルのエチレンオキサイドを付加したポリエチレングリコールをノニルフェノールに付加した化合物の(メタ)アクリレートである4-ノルマルノニルフェノキシペンタエチレングリコールモノプロピレングリコール(メタ)アクリレートが挙げられる。平均8モルのエチレンオキサイドを付加したポリエチレングリコールをノニルフェノールに付加した化合物のアクリレートである4-ノルマルノニルフェノキシオクタエチレングリコール(メタ)アクリレート(東亞合成(株)製、M-114)も挙げられる。これら分子内にエチレンオキシド基と(メタ)アクリロイル基を有する単官能の化合物はアクリロイル基を有ししていることが好ましい。 Compound (B-2) may be monofunctional. For example, a compound obtained by adding (meth) acrylic acid to one end of polyethylene oxide, or a compound obtained by adding (meth) acrylic acid to one end and alkylating or allylating the other end. it can.
Examples of such a compound include phenoxyhexaethylene glycol mono (meth) acrylate, which is a (meth) acrylate of a compound obtained by adding polyethylene glycol to a phenyl group, polypropylene glycol added with an average of 2 mol of propylene oxide, and an average of 7 mol. 4-Normal nonylphenoxyheptaethylene glycol dipropylene glycol (meth) acrylate, a (meth) acrylate of a compound obtained by adding polyethylene glycol to which ethylene oxide is added to nonylphenol, an average of 5 and a polypropylene glycol having an average of 1 mol of propylene oxide added 4-normal nonyl phthalate, which is a (meth) acrylate of a compound obtained by adding polyethylene glycol with a mole of ethylene oxide added to nonylphenol. Roh carboxymethyl pentaethylene glycol monopropylene glycol (meth) acrylate. Examples also include 4-normal nonylphenoxyoctaethylene glycol (meth) acrylate (M-114, manufactured by Toagosei Co., Ltd.), which is an acrylate of a compound obtained by adding polyethylene glycol with an average of 8 moles of ethylene oxide added to nonylphenol. These monofunctional compounds having an ethylene oxide group and a (meth) acryloyl group in the molecule preferably have an acryloyl group.
このような化合物としては、テトラエチレングリコールジ(メタ)アクリレート、ペンタエチレングリコールジ(メタ)アクリレート、ヘキサエチレングリコールジ(メタ)アクリレート、ヘプタエチレングリコールジ(メタ)アクリレート、オクタエチレングリコールジ(メタ)アクリレート、ノナエチレングリコールジ(メタ)アクリレート、デカエチレングリコールジ(メタ)アクリレート、12モルのエチレンオキシド鎖の両末端に(メタ)アクリロイル基を有する化合物、12モルのエチレンオキシド鎖の両末端に(メタ)アクリロイル基を有する化合物、平均12モルのプロピレンオキシドを付加したポリプロピレングリコールにエチレンオキシドをさらに両端にそれぞれ平均3モル付加したグリコールのジメタクリレート、平均18モルのプロピレンオキシドを付加したポリプロピレングリコールにエチレンオキシドをさらに両端にそれぞれ平均15モル付加したグリコールのジメタクリレートが挙げられる。また、ビスフェノールAにエチレンオキシド変性し両末端に(メタ)アクリロイル基を有する化合物でもよい。 In addition, the compound (B-2) may be bifunctional. For example, a compound having a (meth) acryloyl group at both ends of an ethylene oxide chain or a compound having a (meth) acryloyl group at both ends of an alkylene oxide chain in which an ethylene oxide chain and a propylene oxide chain are bonded randomly or in blocks Can do.
Examples of such compounds include tetraethylene glycol di (meth) acrylate, pentaethylene glycol di (meth) acrylate, hexaethylene glycol di (meth) acrylate, heptaethylene glycol di (meth) acrylate, and octaethylene glycol di (meth). Acrylate, nonaethylene glycol di (meth) acrylate, decaethylene glycol di (meth) acrylate, compound having (meth) acryloyl groups at both ends of 12 mol ethylene oxide chain, (meth) at both ends of 12 mol ethylene oxide chain A compound having an acryloyl group, a glycol dimethacrylate obtained by adding an average of 3 moles of ethylene oxide to both ends of polypropylene glycol added with an average of 12 moles of propylene oxide, 18 moles of polypropylene glycol obtained by adding propylene oxide dimethacrylate glycol averaged 15 mols each further ends of ethylene oxide and the like in. Further, it may be a compound having bisphenol A modified with ethylene oxide and having (meth) acryloyl groups at both ends.
次に本発明に含まれる(A)アルカリ可溶性高分子について説明する。
アルカリ可溶性高分子とは、カルボキシル基を含有したビニル系樹脂のことであり、例えば、(メタ)アクリル酸、(メタ)アクリル酸エステル、(メタ)アクリロニトリル、(メタ)アクリルアミド等の共重合体である。
(A)アルカリ可溶性高分子は、カルボキシル基を含有し、酸当量が100~600であることが好ましい。酸当量とは、その中に1当量のカルボキシル基を有するアルカリ可溶性高分子の質量をいう。酸当量は、より好ましくは250以上450以下である。酸当量は、現像耐性が向上し、解像度及び密着性が向上する点から、100以上が好ましく、現像性及び剥離性が向上する点から600以下が好ましい。酸当量の測定は、平沼産業(株)製平沼自動滴定装置(COM-555)を使用し、0.1mol/Lの水酸化ナトリウムを用いて電位差滴定法により行われる。 [(A) Alkali-soluble polymer]
Next, (A) the alkali-soluble polymer included in the present invention will be described.
The alkali-soluble polymer is a vinyl-based resin containing a carboxyl group, such as a copolymer such as (meth) acrylic acid, (meth) acrylic ester, (meth) acrylonitrile, (meth) acrylamide, and the like. is there.
(A) The alkali-soluble polymer preferably contains a carboxyl group and has an acid equivalent of 100 to 600. The acid equivalent means the mass of the alkali-soluble polymer having 1 equivalent of a carboxyl group therein. The acid equivalent is more preferably 250 or more and 450 or less. The acid equivalent is preferably 100 or more from the viewpoint of improving development resistance and improving resolution and adhesion, and is preferably 600 or less from the viewpoint of improving developability and peelability. The acid equivalent is measured by a potentiometric titration method using a Hiranuma automatic titrator (COM-555) manufactured by Hiranuma Sangyo Co., Ltd., using 0.1 mol / L sodium hydroxide.
第一の単量体は、分子中に重合性不飽和基を一個有するカルボン酸又は酸無水物である。例えば、(メタ)アクリル酸、フマル酸、ケイ皮酸、クロトン酸、イタコン酸、マレイン酸無水物、及びマレイン酸半エステルが挙げられる。中でも、特に(メタ)アクリル酸が好ましい。ここで、(メタ)アクリルとは、アクリル及び/又はメタクリルを示す。以下同様である。 The alkali-soluble polymer is preferably a copolymer comprising at least one or more of the first monomers described below and at least one or more of the second monomers described below.
The first monomer is a carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule. Examples include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester. Among these, (meth) acrylic acid is particularly preferable. Here, (meth) acryl refers to acryl and / or methacryl. The same applies hereinafter.
第一の単量体と第二の単量体の好ましい組み合わせとしては、以下の様な組み合わせ、例えば、アクリル酸ブチル、メタクリル酸メチル、メタクリル酸の共重合体、スチレン、メタクリル酸メチル、メタクリル酸の共重合体、スチレン、メタクリル酸ベンジル、メタクリル酸の共重合体、メタクリル酸ベンジル、メタクリル酸の共重合体、メタクリル酸ベンジル、アクリル酸2-エチルヘキシル、メタクリル酸の共重合体などを挙げることができる。 The copolymerization ratio of the first monomer and the second monomer is preferably 10 to 60% by mass for the first monomer and 40 to 90% by mass for the second monomer. More preferably, the first monomer is 15 to 35% by mass, and the second monomer is 65 to 85% by mass.
Preferred combinations of the first monomer and the second monomer include the following combinations, for example, butyl acrylate, methyl methacrylate, methacrylic acid copolymer, styrene, methyl methacrylate, methacrylic acid. Styrene, benzyl methacrylate, methacrylic acid copolymer, benzyl methacrylate, methacrylic acid copolymer, benzyl methacrylate, 2-ethylhexyl acrylate, methacrylic acid copolymer, and the like. it can.
次に本発明に含まれる(C)光重合開始剤について説明する。
(C)光重合開始剤としては、一般に知られているものが使用できる。(C)光重合開始剤の含有量は、0.1~20質量%の範囲であり、より好ましい範囲は0.5~10質量%である。十分な感度を得るという観点から、0.1質量%以上が好ましく、また、レジスト底面にまで光を充分に透過させ、高解像性を得るという観点から、20質量%以下が好ましい。 [(C) Photopolymerization initiator]
Next, the photopolymerization initiator (C) included in the present invention will be described.
(C) As the photopolymerization initiator, those generally known can be used. (C) The content of the photopolymerization initiator is in the range of 0.1 to 20% by mass, and more preferably in the range of 0.5 to 10% by mass. From the viewpoint of obtaining sufficient sensitivity, it is preferably 0.1% by mass or more, and from the viewpoint of sufficiently transmitting light to the bottom surface of the resist and obtaining high resolution, it is preferably 20% by mass or less.
また、半導体レーザーなどの光源で直接描画して露光する場合には、感度の観点から、光重合開始剤として、アクリジン化合物、及びピラゾリン化合物からなる群から選ばれる少なくとも一種の化合物を用いることが好ましい。 A combination of the above-mentioned lophine dimer and Michler's ketone [4,4′-bis (dimethylamino) benzophenone] or 4,4′-bis (diethylamino) benzophenone is a preferable combination from the viewpoints of sensitivity and resolution. In this case, the amount of the lophine dimer can be appropriately adjusted according to the sensitivity and the development aggregation property. When 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer is used, it is preferably 1% by mass or more from the viewpoint of sensitivity, and preferably 5% by mass or less from the viewpoint of aggregation. More preferably, it is 2 to 4% by mass. The amount of 4,4′-bis (diethylamino) benzophenone can be appropriately adjusted in consideration of sensitivity, rectangularity of the resist pattern, and light transmittance at the exposure wavelength. In the case of forming a photosensitive resin layer having a thickness of 70 μm or more, it is preferably 0.05% by mass or less in consideration of pattern adhesion and rectangularity, and 0.01% by mass or more from the viewpoint of sensitivity. preferable.
In the case of direct drawing and exposure with a light source such as a semiconductor laser, it is preferable to use at least one compound selected from the group consisting of an acridine compound and a pyrazoline compound as a photopolymerization initiator from the viewpoint of sensitivity. .
また、感光性樹脂組成物中に、ロイコ染料と下記ハロゲン化合物を組み合わせて用いることは、密着性及びコントラストの観点から、本発明の好ましい実施形態である。 Examples of the leuco dye include tris (4-dimethylaminophenyl) methane [leucocrystal violet] and bis (4-dimethylaminophenyl) phenylmethane [leucomalachite green]. Among these, from the viewpoint of improving the contrast, it is preferable to use leuco crystal violet as the leuco dye. When the leuco dye is contained, the content is preferably 0.1 to 10% by mass in the photosensitive resin composition. The content is preferably 0.1% by mass or more from the viewpoint of the contrast between the exposed part and the unexposed part, and is preferably 10% by mass or less from the viewpoint of maintaining storage stability.
Moreover, it is a preferable embodiment of this invention from a viewpoint of adhesiveness and contrast to use in combination with a leuco dye and the following halogen compound in the photosensitive resin composition.
尚、(A)アルカリ可溶性高分子、(B)エチレン性不飽和二重結合を有する化合物、化合物(B-1)、化合物(B-2)、及び(C)光重合開始剤は、それぞれ、複数ある場合には、感光性樹脂組成物中に複数含まれることができる。 The content of the plasticizer is preferably 5 to 50% by mass, more preferably 5 to 30% by mass in the photosensitive resin composition. The content is preferably 5% by mass or more from the viewpoint of suppressing development time delay and imparting flexibility to the cured film, and is preferably 50% by mass or less from the viewpoint of suppressing insufficient curing and cold flow.
The (A) alkali-soluble polymer, (B) the compound having an ethylenically unsaturated double bond, the compound (B-1), the compound (B-2), and the (C) photopolymerization initiator, When there are a plurality, they can be contained in the photosensitive resin composition.
次いで必要により、感光性樹脂層上に保護層をラミネートすることにより感光性樹脂積層体を作製することができる。 The thickness of the photosensitive resin layer after drying varies depending on the use, but is preferably 1 to 100 μm, more preferably 2 to 50 μm, and further preferably 3 to 15 μm. The thickness is preferably 3 μm or more from the viewpoint of tent properties, and is preferably 15 μm or less from the viewpoint of resolution. Particularly for semiconductor bump applications, the thickness is preferably 70 to 150 μm, more preferably 70 to 120 μm. The thickness is preferably 150 μm or less from the viewpoint of securing the hole detachability for forming the semiconductor bump, and is preferably 70 μm or more from the viewpoint of securing the plating height necessary for bump connection.
Next, if necessary, a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin layer.
感光性樹脂積層体を用いたレジストパターンは、ラミネートするラミネート工程、活性光を露光する露光工程、及び未露光部を除去する現像工程を含む工程によって形成することができる。 <Resist pattern formation method>
The resist pattern using the photosensitive resin laminate can be formed by a process including a laminating process for laminating, an exposing process for exposing active light, and a developing process for removing unexposed portions.
基板としては、プリント配線板製造のためには銅張積層板が、また凹凸基材の製造のためにはガラス基材、例えば、プラズマディスプレイパネル用基材や表面電解ディスプレイ基材が、有機EL封止キャップ用基材、貫通孔を形成したシリコンウエハ、セラミック基材などが挙げられる。プラズマディスプレイ用基材とは、ガラス上に電極を形成後、誘電体層を塗布し、次いで隔壁用ガラスペーストを塗布し、隔壁用ガラスペースト部分にサンドブラスト加工を施し隔壁を形成した基材である。これらのガラス基材にサンドブラスト加工を施したものが、凹凸基材となる。 Hereinafter, an example of a specific method will be shown.
As the substrate, a copper-clad laminate is used for manufacturing a printed wiring board, and a glass substrate such as a plasma display panel substrate or a surface electrolytic display substrate is used for manufacturing an uneven substrate. Examples thereof include a sealing cap substrate, a silicon wafer having a through hole, and a ceramic substrate. A plasma display substrate is a substrate in which an electrode is formed on glass, a dielectric layer is applied, a partition wall glass paste is then applied, and a partition wall glass paste portion is subjected to sandblasting to form a partition wall. . Those obtained by subjecting these glass substrates to sand blasting are uneven substrates.
プリント配線板は、基板として銅張積層板やフレキシブル基板を用いた上述の<レジストパターン形成方法>に続いて、以下の工程を経ることで得られうる。
まず、現像により露出した基板の銅面をエッチング法又はめっき法といった既知の方法を用いて導体パターンを製造する。
その後、レジストパターンを現像液よりも強いアルカリ性を有する水溶液により基板から剥離して所望のプリント配線板を得る。剥離用のアルカリ水溶液(以下、「剥離液」ともいう。)についても特に制限はないが、濃度約2~5質量%、温度約40~70℃のNaOH、KOHの水溶液が一般に用いられる。剥離液に、少量の水溶性溶媒を加えることもできる。 <Conductor Pattern Manufacturing Method and Printed Wiring Board Manufacturing Method>
The printed wiring board can be obtained through the following steps following the above <resist pattern forming method> using a copper-clad laminate or a flexible substrate as a substrate.
First, a conductor pattern is manufactured by using a known method such as an etching method or a plating method on a copper surface exposed by development.
Thereafter, the resist pattern is peeled from the substrate with an aqueous solution having alkalinity stronger than that of the developer to obtain a desired printed wiring board. The alkaline aqueous solution for stripping (hereinafter also referred to as “stripping solution”) is not particularly limited, but an aqueous solution of NaOH or KOH having a concentration of about 2 to 5% by mass and a temperature of about 40 to 70 ° C. is generally used. A small amount of a water-soluble solvent can also be added to the stripping solution.
リードフレームは、基板として金属板、例えば、銅、銅合金、鉄系合金を用いた上述の<レジストパターンの形成方法>に続いて、以下の工程を経ることで得られうる。
まず、現像により露出した基板をエッチングして導体パターンを形成する。その後、レジストパターンを上述の<プリント配線板の製造方法>と同様の方法で剥離して、所望のリードフレームを得る。 <Lead frame manufacturing method>
The lead frame can be obtained through the following steps following the above-described <resist pattern forming method> using a metal plate, for example, copper, a copper alloy, or an iron-based alloy as a substrate.
First, a conductive pattern is formed by etching the substrate exposed by development. Thereafter, the resist pattern is peeled by the same method as in the above-described <Printed wiring board manufacturing method> to obtain a desired lead frame.
半導体パッケージは、基板としてLSIとしての回路形成が終了したウェハを用いた上述の<レジストパターンの形成方法>に続いて、以下の工程を経ることで得られうる。
まず、現像により露出した開口部に、銅やはんだによる柱状のめっきを施して、導体パターンを形成する。その後、レジストパターンを上述の<プリント配線板の製造方法>と同様の方法で剥離し、更に、柱状めっき以外の部分の薄い金属層をエッチングにより除去することで所望の半導体パッケージを得る。 <Semiconductor package manufacturing method>
The semiconductor package can be obtained by performing the following steps following the above-described <resist pattern forming method> using a wafer in which circuit formation as an LSI has been completed as a substrate.
First, the opening exposed by development is subjected to columnar plating with copper or solder to form a conductor pattern. Thereafter, the resist pattern is peeled off in the same manner as in the above-mentioned <Method for manufacturing printed wiring board>, and the thin metal layer other than the columnar plating is removed by etching to obtain a desired semiconductor package.
サンドブラスト加工が可能な基材、例えば、ガラス基材、ガラスリブペーストを塗布したガラス基材、セラミック基材、ステンレスなどの金属基材、シリコンウエハ、サファイアなどの鉱石、合成樹脂層などの有機基材上に、前記した<レジストパターン形成方法>と同様な方法で、感光性樹脂積層体をラミネートし、露光、現像を施す。その後、形成されたレジストパターン上からブラスト材を吹き付けて目的の深さに切削するサンドブラスト加工工程、基材上に残存した樹脂部分をアルカリ剥離液等で基材から除去する剥離工程を経ることにより、基材上に微細なパターンが形成される。上前記サンドブラスト加工工程に用いるブラスト材は公知のものを用いることができ、例えば、SiC,SiO2、Al2O3、CaCO3、ZrO2、ガラス、ステンレス等の2~100μm程度の微粒子が用いられる。 <Manufacturing method of substrate having concave / convex pattern>
Substrates that can be sandblasted, such as glass substrates, glass substrates coated with glass rib paste, ceramic substrates, metal substrates such as stainless steel, silicon wafers, ores such as sapphire, organic substrates such as synthetic resin layers A photosensitive resin laminate is laminated on the material in the same manner as in the above <resist pattern forming method>, and exposure and development are performed. After that, by passing through a sandblasting process in which a blast material is sprayed from the formed resist pattern to cut to a desired depth, and a resin part remaining on the substrate is removed from the substrate with an alkaline stripping solution or the like A fine pattern is formed on the substrate. As the blasting material used in the above sandblasting process, known materials can be used. For example, fine particles of about 2 to 100 μm such as SiC, SiO 2 , Al 2 O 3 , CaCO 3 , ZrO 2 , glass, stainless steel, etc. are used. It is done.
半導体バンプは以下の方法で作成することができる。
シリコンウエハ基板に絶縁層を設け、必要部分にシリコンウエハと接続するための電極を形成する。次いで、銅などの導電膜をスパッタなど方法で形成する。
液状レジストを用いる場合は、こうして得られた基板上に液状レジストをスピンコートする。プリベークにより溶媒を除去、乾燥し、レジスト塗布膜を得る。ついで露光、現像によりパターンを形成する。ドライフィルムを用いる場合は、前記した<レジストパターンの形成方法>と同様な方法でパターンを形成する。 <Semiconductor bump manufacturing method>
The semiconductor bump can be created by the following method.
An insulating layer is provided on the silicon wafer substrate, and electrodes for connecting to the silicon wafer are formed on necessary portions. Next, a conductive film such as copper is formed by a method such as sputtering.
When a liquid resist is used, the liquid resist is spin-coated on the substrate thus obtained. The solvent is removed by pre-baking and dried to obtain a resist coating film. Next, a pattern is formed by exposure and development. In the case of using a dry film, the pattern is formed by the same method as the above <Resist pattern formation method>.
(実施例1~20、及び比較例1~2)
最初に実施例及び比較例の評価用サンプルの作製方法を説明し、次いで、得られたサンプルについての評価方法およびその評価結果を示す。 Hereinafter, examples of embodiments of the present invention will be specifically described.
(Examples 1 to 20 and Comparative Examples 1 and 2)
First, a method for producing samples for evaluation of Examples and Comparative Examples will be described, and then an evaluation method and evaluation results for the obtained samples will be shown.
実施例及び比較例における評価用サンプルは次の様にして作製した。
<感光性樹脂積層体の作製>
下記表1に示す組成(但し、各成分の数字は固形分としての配合量(質量部)を示す)の感光性樹脂組成物及び溶媒をよく攪拌、混合して感光性樹脂組成物調合液とし、支持体として16μm厚のポリエチレンテレフタレートフィルムの表面にバーコーターを用いて均一に塗布し、95℃の乾燥機中で12分間乾燥して感光性樹脂層を形成した。感光性樹脂層の厚みは120μmであった。
次いで、感光性樹脂層のポリエチレンテレフタレートフィルムを積層していない表面上に、保護層として21μm厚のポリエチレンフィルムを張り合わせて感光性樹脂積層体を得た。
以下の表1に、感光性樹脂組成物調合液中の配合量及び評価結果を、そして以下の表2に、表1に示す感光性樹脂組成物調合液中の材料成分の名称を、示す。 1. Production of Evaluation Samples Evaluation samples in Examples and Comparative Examples were produced as follows.
<Preparation of photosensitive resin laminate>
The photosensitive resin composition and the solvent having the composition shown in Table 1 below (however, the numbers of each component indicate the blending amount (parts by mass) as a solid content) are thoroughly stirred and mixed to obtain a photosensitive resin composition preparation liquid. Then, a 16 μm thick polyethylene terephthalate film as a support was uniformly coated on the surface using a bar coater, and dried in a dryer at 95 ° C. for 12 minutes to form a photosensitive resin layer. The thickness of the photosensitive resin layer was 120 μm.
Next, a 21 μm thick polyethylene film was laminated as a protective layer on the surface of the photosensitive resin layer on which the polyethylene terephthalate film was not laminated to obtain a photosensitive resin laminate.
Table 1 below shows the blending amounts and evaluation results in the photosensitive resin composition preparation liquid, and Table 2 below shows the names of the material components in the photosensitive resin composition preparation liquid shown in Table 1.
<基板>
8μm銅箔を積層した0.05mm厚のフレキシブル銅張積層板(住友金属鉱山(株)製、エスパーフレックス(登録商標))を用いた。
<ラミネート>
感光性樹脂積層体のポリエチレンフィルムを剥がしながら、ホットロールラミネーター(旭化成エレクトロニクス(株)製、AL-700)により、ロール温度105℃でラミネートした。エアー圧力は0.35MPaとし、ラミネート速度は1.5m/minとした。 2. Evaluation of minimum development time and resolution <Substrate>
A 0.05 mm thick flexible copper-clad laminate (manufactured by Sumitomo Metal Mining Co., Ltd., Esperflex (registered trademark)) with 8 μm copper foil laminated thereon was used.
<Laminate>
While peeling the polyethylene film of the photosensitive resin laminate, lamination was performed at a roll temperature of 105 ° C. using a hot roll laminator (AL-700, manufactured by Asahi Kasei Electronics Co., Ltd.). The air pressure was 0.35 MPa, and the laminating speed was 1.5 m / min.
クロムガラスフォトマスクを用いて、オーク株式会社製高精度露光機(EXM-1066-H-01、ghi線、23mW、真空密着方式)によりストゥーファー21段ステップタブレットを介して露光した場合に残膜する段数が7段となるような露光量で露光した。
なお、クロムガラスフォトマスクには、露光部と未露光部の幅が1:1の比率のラインパターンマスクを用いた。 <Exposure>
When exposed using a chrome glass photomask with a high precision exposure machine (EXM-1066-H-01, ghi line, 23 mW, vacuum contact method) manufactured by Oak Co., Ltd. The exposure was performed so that the number of steps to be filmed was seven.
Note that a line pattern mask having a ratio of 1: 1 between the exposed portion and the unexposed portion was used as the chromium glass photomask.
ポリエチレンテレフタレートフィルムを剥離した後、30℃の1質量%Na2CO3水溶液をスプレーして現像し、感光性樹脂層の未露光部分を溶解除去した。
未露光部分の感光性樹脂層が完全に溶解するのに要する最も少ない時間を「最小現像時間」として測定し、以下のようにランク分けした:
◎:最小現像時間の値が140秒以下;
○:最小現像時間の値が140秒超え、200秒以下;
×:最小現像時間の値が200秒超。 <Development>
After the polyethylene terephthalate film was peeled off, a 1% by mass Na 2 CO 3 aqueous solution at 30 ° C. was sprayed and developed to dissolve and remove the unexposed portion of the photosensitive resin layer.
The minimum time required for complete dissolution of the unexposed portion of the photosensitive resin layer was measured as the “minimum development time” and ranked as follows:
A: Minimum development time is 140 seconds or less;
○: The value of the minimum development time exceeds 140 seconds and is 200 seconds or less;
X: The value of the minimum development time is over 200 seconds.
◎:解像度の値が30μm以下;
○:解像度の値が30μm超え、50μm以下;
×:解像度の値が50μm超。 Further, a resist pattern was formed by developing under the same conditions for twice the minimum development time. The minimum mask line width in which the cured resist lines are normally formed is ranked as a “resolution” value as follows:
A: The resolution value is 30 μm or less;
○: Resolution value exceeds 30 μm and 50 μm or less;
X: The value of resolution exceeds 50 μm.
<露光>
感光性樹脂積層体を支持フィルム側から露光し硬化膜を作成した。露光には、オーク株式会社製HMW-801を用いた。露光量は、前記2.「最小現像時間」、及び「解像度」の評価において実施した露光量と同じとした。
<現像>
露光した感光性樹脂積層体から支持フィルムを剥離し、30℃の1質量%Na2CO3水溶液を「最小現像時間」の2倍の時間スプレーして現像した。その後、保護層を剥離して硬化膜を得た。 3. Release strip solubility evaluation <exposure>
The photosensitive resin laminate was exposed from the support film side to prepare a cured film. For the exposure, HMW-801 manufactured by Oak Co., Ltd. was used. The exposure amount is the same as in 2. The exposure amount was the same as that used in the evaluation of “minimum development time” and “resolution”.
<Development>
The support film was peeled off from the exposed photosensitive resin laminate, and developed by spraying a 1% by mass Na 2 CO 3 aqueous solution at 30 ° C. for twice the “minimum development time”. Thereafter, the protective layer was peeled off to obtain a cured film.
得られた硬化膜約500mgを、60℃、3%NaOH水溶液100mlに3時間浸漬した。その後残存する硬化膜を濾過し、真空乾燥し、得られた濾過物の質量を最初に浸漬した硬化膜の質量で除することにより残膜率を求め、「剥離片溶解性」を評価した。以下のようにランク分けした:
◎:残膜率の値が1時間以内に0%になる;
○:残膜率の値が10%以下;
×:残膜率の値が10%を超える。 <Evaluation of stripping piece solubility>
About 500 mg of the obtained cured film was immersed in 100 ml of 3% NaOH aqueous solution at 60 ° C. for 3 hours. Thereafter, the remaining cured film was filtered, vacuum-dried, and the mass of the obtained filtrate was divided by the mass of the cured film that was first immersed to determine the remaining film ratio, and the “peeling piece solubility” was evaluated. The ranking was as follows:
A: The value of the remaining film rate becomes 0% within 1 hour;
○: The value of the remaining film rate is 10% or less;
X: The value of the remaining film ratio exceeds 10%.
1.半導体バンプの作成
<基板>
銅ポスト又ははんだバンプを作成する場合は、5インチのシリコンウエハ上にアネルバ製スパッタリング装置により2000オングストローム厚みのクロム層を形成し、さらに2000オングストロームの銅層を形成させた銅スパッタシリコンウエハを用いた。 (Examples 21 and 22)
1. Creating semiconductor bumps <Board>
When making copper posts or solder bumps, a copper sputtered silicon wafer in which a 2000 angstrom thick chromium layer was formed on a 5 inch silicon wafer by an Anelva sputtering apparatus and a 2000 angstrom copper layer was further formed was used. .
感光性樹脂積層体のポリエチレンフィルムを剥がしながら、80℃に予熱したシリコンウエハ上に、ホットロールラミネーター(大成ラミネーター(株)製、VA-400III)により、ロール温度80℃でラミネートした。エアー圧力は0.20MPaとし、ラミネート速度は1.0m/minとした。
<露光>
ガラスクロムマスクをもちいて、ウルトラテック(株)製プリズマ(商品名)ghi線により露光した。基板面で測定した照度は2500mW/cm2であった。 <Laminate>
While peeling the polyethylene film of the photosensitive resin laminate, it was laminated on a silicon wafer preheated to 80 ° C. with a hot roll laminator (VA-400III, manufactured by Taisei Laminator Co., Ltd.) at a roll temperature of 80 ° C. The air pressure was 0.20 MPa, and the laminating speed was 1.0 m / min.
<Exposure>
Using a glass chrome mask, exposure was carried out with Prisma (trade name) ghi line manufactured by Ultratec Corporation. The illuminance measured on the substrate surface was 2500 mW / cm 2 .
30℃、1wt%のK2CO3水溶液を用い、スピン現像機(滝沢産業(株)製スピン現像機AD-1200)を用いて現像した。
<デスカム及びめっき前処理>
評価基板を、O2/CF4プラズマ処理し、5分間純水に浸すことにより実施した。
<硫酸銅めっき>
以下のように銅めっきし後述の通り剥離して銅ポストを作製した(実施例21)。硫酸銅コンク(メルテックス(株)製)を19wt%硫酸で3.6倍に希釈し、濃塩酸を200ppm添加した。次いで光沢剤としてカパラシッドHLとカパラシッドGSをそれぞれ0.4ml/l、20ml/l添加した。めっき前処理後の耐めっき性評価基板(6cm×12.5cm)を、作製された硫酸銅めっき液を用いてハーリングセル均一めっき装置(株式会社 山本鍍金試験器社製)により、毎分4μmの高さで銅が析出するよう電流値を調節し、めっきした。このときの銅めっき被膜の厚みは80μm厚であった。 <Development>
Development was performed using a spin developing machine (spin developing machine AD-1200 manufactured by Takizawa Sangyo Co., Ltd.) using an aqueous solution of K 2 CO 3 at 30 ° C. and 1 wt%.
<Descam and plating pretreatment>
The evaluation substrate was subjected to an O 2 / CF 4 plasma treatment and immersed in pure water for 5 minutes.
<Copper sulfate plating>
A copper post was prepared as described below and peeled off as described below to produce a copper post (Example 21). Copper sulfate conch (Meltex Co., Ltd.) was diluted 3.6 times with 19 wt% sulfuric acid, and 200 ppm of concentrated hydrochloric acid was added. Subsequently, capalacid HL and caparacid GS were added as brighteners at 0.4 ml / l and 20 ml / l, respectively. The plating resistance evaluation substrate (6 cm × 12.5 cm) after the pre-plating treatment was subjected to 4 μm / min with a Haring cell uniform plating apparatus (manufactured by Yamamoto Kakin Tester Co., Ltd.) using the prepared copper sulfate plating solution. The current value was adjusted so that copper was deposited at a height, and plating was performed. The thickness of the copper plating film at this time was 80 μm.
以下のようにはんだめっきし後述の通り剥離してはんだバンプを作成した(実施例22)。はんだめっき液(メルテックス社製プルティンLAホウフッ化はんだ浴)中で3時間はんだめっきした。電流密度は1.5A/dm2になるように調整した。はんだめっきの高さは90μmであった。
<剥離>
めっき処理を施した評価基板を、ダイナロイ(株)社製のFlip srip(商品名)により95℃、1時間加熱することにより剥離した。 <Solder plating>
Solder plating was performed as described below, and peeling was performed as described later to prepare solder bumps (Example 22). Solder plating was performed for 3 hours in a solder plating solution (Plutin LA borofluoride solder bath manufactured by Meltex). The current density was adjusted to 1.5A / dm 2. The height of the solder plating was 90 μm.
<Peeling>
The evaluation substrate subjected to the plating treatment was peeled off by heating at 95 ° C. for 1 hour with a flip slip (trade name) manufactured by Dynaloy Co., Ltd.
これに反し、比較例1は、本願発明に含まれる(B-1)成分を欠く例であるが、十分な「剥離片溶解性」が得られなかった。また、比較例2は、本願発明に含まれる(B-2)成分を欠く例であるが、現像に要する時間が極めて長く、かつ、充分な「剥離片溶解性」が得られなかった。 From Table 1, it can be seen that Examples 1 to 20 are all excellent in “peeling piece solubility”, “minimum development time”, and “resolution” by adopting the configuration of the present invention.
On the contrary, Comparative Example 1 is an example lacking the component (B-1) contained in the present invention, but sufficient “peeling piece solubility” was not obtained. Comparative Example 2 is an example lacking the component (B-2) contained in the present invention, but the time required for development was extremely long, and sufficient “peeling piece solubility” was not obtained.
Claims (9)
- (A)アルカリ可溶性高分子30~70質量%、(B)エチレン性不飽和二重結合を有する化合物20~60質量%、及び(C)光重合開始剤0.1~20質量%を含むレジスト材料用感光性樹脂組成物であって、前記(B)エチレン性不飽和二重結合を有する化合物として、分子内に少なくともヒドロキシル基とフェニル基と2以上のエチレン性不飽和二重結合とを有する化合物(B-1)、及び分子内にエチレンオキシド基と(メタ)アクリロイル基を有する化合物(B-2)を含む前記組成物。 A resist containing (A) an alkali-soluble polymer 30 to 70% by mass, (B) a compound having an ethylenically unsaturated double bond 20 to 60% by mass, and (C) a photopolymerization initiator 0.1 to 20% by mass. A photosensitive resin composition for materials having (B) an ethylenically unsaturated double bond as a compound having at least a hydroxyl group, a phenyl group, and two or more ethylenically unsaturated double bonds in the molecule. The composition comprising the compound (B-1) and the compound (B-2) having an ethylene oxide group and a (meth) acryloyl group in the molecule.
- 前記分子内に少なくともヒドロキシル基とフェニル基と2以上のエチレン性不飽和二重結合とを有する化合物(B-1)が、下記式(I):
- 前記化合物(B-2)が、分子内にエチレンオキシド基とアクリロイル基とを有する化合物である、請求項1又は2に記載のレジスト材料用感光性樹脂組成物。 3. The photosensitive resin composition for a resist material according to claim 1, wherein the compound (B-2) is a compound having an ethylene oxide group and an acryloyl group in the molecule.
- 前記化合物(B-2)が、下記式(II)~(IV):
- 前記化合物(B-2)が、上記式(III)で表される化合物である、請求項4に記載のレジスト材料用感光性樹脂組成物。 The photosensitive resin composition for a resist material according to claim 4, wherein the compound (B-2) is a compound represented by the formula (III).
- 支持フィルム上に、請求項1又は2に記載のレジスト材料用感光性樹脂組成物を含む層が積層されている感光性樹脂積層体。 The photosensitive resin laminated body by which the layer containing the photosensitive resin composition for resist materials of Claim 1 or 2 is laminated | stacked on the support film.
- 前記レジスト材料用感光性樹脂組成物を含む層の膜厚が70~150μmである、請求項6に記載の感光性樹脂積層体。 The photosensitive resin laminate according to claim 6, wherein the layer containing the photosensitive resin composition for a resist material has a thickness of 70 to 150 μm.
- 請求項6に記載の感光性樹脂積層体を基材にラミネートする工程、該ラミネートされた感光性樹脂積層体に露光する工程、及び該露光された感光性樹脂積層体を現像する工程を含むことを特徴とするレジストパターンの形成方法。 7. A step of laminating the photosensitive resin laminate according to claim 6 on a substrate, a step of exposing the laminated photosensitive resin laminate, and a step of developing the exposed photosensitive resin laminate. A method of forming a resist pattern characterized by the above.
- 請求項6に記載の感光性樹脂積層体をスパッタ銅薄膜上にラミネートする工程、該ラミネートされた感光性樹脂積層体に露光する工程、該露光された感光性樹脂積層体を現像する工程、及び該現像後のスパッタ銅薄膜に銅めっき又ははんだめっきをする工程を含むことを特徴とする半導体バンプの形成方法。 A step of laminating the photosensitive resin laminate according to claim 6 on a sputtered copper thin film, a step of exposing the laminated photosensitive resin laminate, a step of developing the exposed photosensitive resin laminate, and A method of forming a semiconductor bump, comprising the step of copper plating or solder plating on the sputtered copper thin film after development.
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TWI413859B (en) | 2013-11-01 |
CN102549498B (en) | 2013-10-30 |
KR101548791B1 (en) | 2015-08-31 |
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