CN106796399B - Positive photosensitive resin composition, method for producing patterned cured film, cured product, interlayer insulating film, covercoat, surface protective film, and electronic component - Google Patents
Positive photosensitive resin composition, method for producing patterned cured film, cured product, interlayer insulating film, covercoat, surface protective film, and electronic component Download PDFInfo
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- CN106796399B CN106796399B CN201580053869.5A CN201580053869A CN106796399B CN 106796399 B CN106796399 B CN 106796399B CN 201580053869 A CN201580053869 A CN 201580053869A CN 106796399 B CN106796399 B CN 106796399B
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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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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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
- G03F7/20—Exposure; Apparatus therefor
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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
Abstract
A positive photosensitive resin composition comprising (a) an alkali-soluble resin and (b) an acid generated by i-line exposure
A positive photosensitive resin composition comprising a salt, a solvent (c), and a crosslinking agent (d), wherein the total amount of the components (a), (b), and (d) is 88% by mass or more based on the total mass of the positive photosensitive resin composition excluding the solvent (c).
Description
Technical Field
The present invention relates to a positive photosensitive resin composition, a method for producing a patterned cured film using the same, a cured product, an interlayer insulating film, a covercoat, a surface protective film, and an electronic component.
Background
In the past, in the surface protection film and the interlayer insulation film of the semiconductor element, the methodUsing polyimide, polybenzene having excellent heat resistance, electrical properties, mechanical properties and the like
And (3) azole. In recent years, a photosensitive polyimide having photosensitive characteristics imparted to the polyimide itself has been used, and if this photosensitive polyimide is used, the process for producing a pattern cured film can be simplified, and a complicated production process can be shortened.
In the production of a pattern cured film, an organic solvent such as N-methylpyrrolidone is used for development, but from the viewpoint of environmental considerations, a resin composition that can be developed using an aqueous alkali solution by a method of mixing a polyimide or a polyimide precursor with a naphthoquinone diazide compound as a photosensitizer has been proposed (for example, see patent document 1 or 2).
As a resin composition developable with an aqueous alkali solution, a resin composition containing polybenzene is proposed
Azoles, polybenzes
An azole precursor or a novolac resin (see, for example, patent document 3).
On the other hand, with the recent progress of high integration and miniaturization of semiconductor elements, there is a demand for a package substrate with a thinner film, a smaller size, and a lower cost. Therefore, a package structure is proposed that does not use an Under Bump Metal (UBM) layer used for improving the reliability of a semiconductor element (see non-patent document 1 or 2).
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open No. 64-60630
Patent document 2: specification of U.S. Pat. No. 4395482
Patent document 3: japanese laid-open patent publication No. 2009-265520
Non-patent document
Non-patent document 1: "progress of WLCSP technology to meet GROWING market demand" (ADVANCES IN WLCSP TECHNOLOGIES FOR GROWING MARKET NEEDS), Abstract of sixth International Wafer Level Packaging Conference (Abstract of 6th Annual International Wafer Level Packaging Conference), [2009-10-27/10-30]
Non-patent document 2: "technical SOLUTIONS of the dynamic and diverse WLCSP market" (TECHNOLOGY SOLUTIONS FOR A DYNAMIC AND DIVERSE WLCSP MARKET), the seventh International Wafer Level Packaging Conference abstract (Abstracts of 7th International Wafer Level Packaging Conference), 2010-11-14, Santa Clara, USA
Non-patent document 3: hiroshi Ito et al, as novel dissolution inhibitors for novolak resins
Evaluation of Salt Cationic Photoinitiators (Evaluation of Onium Salt Cationic Photoinitiators as Novel Disolution Inhibitor for Novolac Resin), J.Electrochem.Soc.2322-2327(1988)
Disclosure of Invention
In the package structure in which the Under Bump Metal (UBM) layer is removed, it is preferable that the thickness of the patterned cured film formed using the positive photosensitive resin composition is thicker than the conventional film thickness (10 μm or less) because the design is such that the reliability is ensured by reinforcing the bump by the patterned cured film provided on the outermost layer.
However, if a thick film is formed using a conventional positive photosensitive resin composition using a naphthoquinone diazide compound, there is a problem that transmittance at a photosensitive wavelength is reduced, sensitivity is deteriorated, and a development time is prolonged. On the other hand, the resin composition having high sensitivity has a problem that although the development time is short, the unexposed portion is also developed.
As an alkali positive photosensitive resin composition not using a naphthoquinone diazide compound, a dissolution-suppressed positive photosensitive resin composition has been proposed (see non-patent document 3). However, the dissolution-suppressing positive photosensitive resin composition is technically difficult to be applied to a thick film.
The invention aims to provide a positive photosensitive resin composition which has good dissolution contrast between an exposed part and an unexposed part to a practical degree when a thick pattern cured film is formed, a method for manufacturing the pattern cured film using the positive photosensitive resin composition, an interlayer insulating film, a cover coat, a surface protective film and an electronic component.
The present inventors have attempted to form a thick film using a positive photosensitive resin composition in which an alkali-soluble resin and a naphthoquinone diazide compound are combined. However, the transmittance of the coating film at the photosensitive wavelength is reduced, and a sufficient alkali dissolution rate cannot be obtained in the exposed portion, and the opening portion is not obtained in the development time within the practical range. It is also known that: as the developing time becomes longer, the developer penetrates into the unexposed portion, and the resolution is lowered.
In view of the above problems, the present inventors have further studied and found that: by using alkali-soluble resins with acid generation by i-line exposure
Salt (hereinafter, also referred to as having i-line sensitivity)
Salt) can exhibit a practical dissolution contrast even when a thick pattern cured film is formed.
The present invention provides the following positive photosensitive resin composition.
< 1 > A positive photosensitive resin composition comprising (a) an alkali-soluble resin and (b) an acid generated by i-line exposure
A positive photosensitive resin composition comprising a salt, a solvent (c) and a crosslinking agent (d), wherein the total amount of the components (a), (b) and (d) is 88% by mass or more based on the total mass of the positive photosensitive resin composition excluding the solvent (c).
< 2 > a positive photosensitive resin composition comprising (a) an alkali-soluble resin and (b) an acid generated by i-line exposure
The positive photosensitive resin composition comprises a salt and (c) a solvent, and contains 0 to 100ppm of a naphthoquinone diazide compound or a compound containing an acid-reactive protecting group relative to 100 parts by mass of the component (a).
< 3 > the positive photosensitive resin composition according to claim 2, further comprising (d) a crosslinking agent.
< 4 > the positive photosensitive resin composition according to any one of claims 1 to 3, wherein the component (a) contains a polyimide, a polyimide precursor, and a polybenzo
Azoles, polybenzes
Azole precursors, novolac resins, or polyhydroxystyrene.
< 5 > the positive photosensitive resin composition according to any one of claims 1 to 4, wherein the component (b) is a compound which prevents the component (a) from dissolving in an aqueous alkali solution before i-line exposure and does not prevent the component (a) from dissolving in an aqueous alkali solution after i-line exposure.
< 6 > the positive photosensitive resin composition according to any one of claims 1 to 5, wherein the component (b) is a compound represented by the following general formula (b-1).
[ solution 1]
(wherein X represents a counter anion, and may have a substituent on the aromatic ring.)
< 7 > the positive photosensitive resin composition according to any one of claims 1 to 6, wherein the component (b) is a compound represented by the following formula (b-2).
[ solution 2]
(wherein Me is methyl.)
< 8 > the positive photosensitive resin composition according to any one of claims 1 to 7, which is used for forming an interlayer insulating film, a cover coat layer or a surface protective film.
< 9 > the positive photosensitive resin composition according to any one of 1 to 7, which is used for forming an interlayer insulating film, a cover coat layer or a surface protective film of a semiconductor device having a UBM-free structure.
< 10 > a method for producing a pattern cured film, comprising the steps of:
a step of forming a photosensitive resin film by coating the positive photosensitive resin composition of any one of 1 to 9 on a substrate and drying the coating,
A step of exposing the obtained photosensitive resin film in a predetermined pattern,
A step of developing the exposed resin film with an aqueous alkali solution to obtain a patterned resin film, and
and a step of heat-treating the patterned resin film.
< 11 > the method for producing a pattern cured film according to claim 10, wherein the temperature of the heat treatment is 250 ℃ or lower.
< 12 > a cured product of the positive photosensitive resin composition described in any one of 1 to 9.
< 13 > an interlayer insulating film, a cover coat or a surface protective film using the cured product of 12.
< 14 > an electronic part having the interlayer insulating film, the cover coat or the surface protective film described in 13.
The present invention can provide a positive photosensitive resin composition that can realize a practical dissolution contrast even when a thick pattern cured film is formed, a method for producing a pattern cured film using the same, a cured product, an interlayer insulating film, a covercoat layer, a surface protective film, and an electronic component.
Drawings
Fig. 1 is a schematic cross-sectional view showing a method for manufacturing a package structure without providing a UBM layer.
Fig. 2 is a schematic cross-sectional view of a semiconductor device having a rewiring structure as one embodiment of an electronic component of the present invention.
Detailed Description
The following will describe in detail embodiments of the 1 st and 2 nd positive photosensitive resin compositions, the method for producing a pattern cured film using the same, and the electronic component of the present invention. The present invention is not limited to the following embodiments.
In the present specification, "a or" B "may include either one of a and B, or both of a and B. In addition, as for the materials exemplified below, one kind may be used alone or two or more kinds may be used in combination unless otherwise specified. Further, in the present specification, the content of each component in the composition refers to the total amount of a plurality of substances present in the composition unless otherwise specified, when a plurality of substances corresponding to each component are present in the composition.
The 1 st and 2 nd positive photosensitive resin compositions may be collectively referred to as "positive photosensitive resin composition (resin composition) of the present invention".
[1 st Positive photosensitive resin composition ]
The 1 st embodiment of the 1 st positive photosensitive resin composition of the present invention is a positive photosensitive resin composition containing (a) an alkali-soluble resin and (b) an acid generated by i-line exposure
A positive photosensitive resin composition comprising a salt, a solvent (c) and a crosslinking agent (d), wherein the total amount of the components (a), (b) and (d) is 88% by mass or more based on the total mass of the positive photosensitive resin composition excluding the solvent (c). The total amount of the above-mentioned components (a), (b) and (d) is preferably not less than 90% by mass, more preferably not less than 95% by mass, still more preferably not less than 98% by mass, and may beIs 100% by mass.
The 1 st positive photosensitive resin composition of the present invention, according to the 2 nd embodiment, contains (a) an alkali-soluble resin and (b) an acid generated by i-line exposure
A salt, (c) a solvent, and (d) a crosslinking agent, and the naphthoquinone diazide compound is 0 or more and less than 100ppm with respect to 100 parts by mass of the component (a). In the 2 nd embodiment, the total amount of the components (a), (b) and (d) is preferably 88% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, still more preferably 98% by mass or more, and may be 100% by mass, based on the total mass of the positive photosensitive resin composition excluding the solvent (c).
They may be referred to as only component (a), component (b), component (c) and component (d), respectively. The 1 st and 2 nd forms are collectively referred to as the 1 st positive photosensitive resin composition of the present invention. Next, each component will be explained.
((a) component: alkali-soluble resin)
The alkali-soluble resin is not particularly limited, but is preferably a resin having high electrical insulation properties. Examples thereof include polyimide, polyimide precursor, and polybenzene
Azoles, polybenzes
Azole precursors, polyamides, polyamideimides, polyhydroxystyrenes, novolac resins, norbornene resins, epoxy resins, and acrylic resins.
Particularly, from the viewpoint of compatibility between insulation properties and mechanical properties, it is preferable to use polyimide, a polyimide precursor, and polybenzene
Azoles, polybenzes
Azole precursors, novolac resins, or polyhydroxystyrene.
Alkali-soluble resins are typically developed using aqueous alkali. Therefore, it is preferable to be soluble in an aqueous alkali solution.
Examples of the aqueous alkaline solution include an aqueous organic ammonium solution such as an aqueous tetramethylammonium hydroxide (TMAH) solution, an aqueous metal hydroxide solution, and an aqueous organic amine solution. In general, an aqueous solution of TMAH with a concentration of 2.38% by weight is preferably used. Therefore, the component (a) is preferably soluble in an aqueous TMAH solution.
In addition, one criterion for the solubility of the component (a) in an aqueous alkali solution is described below. The component (a) is dissolved in an arbitrary solvent to prepare a solution, and then spin-coated on a substrate such as a silicon wafer to form a resin film having a thickness of about 5 μm. Immersing the substrate in one of aqueous solutions of tetramethylammonium hydroxide, metal hydroxide and organic amine at 20-25 deg.C. As a result, it was judged that: when the component (a) is dissolved to form a solution, the component (a) used is soluble in an aqueous alkali solution.
The polyimide precursor preferably has a structure represented by formula (1).
[ solution 3]
In formula (1), A is any one of the 4-valent organic groups represented by formulas (2a) to (2e) below, and B is the 2-valent organic group represented by formula (3) below. R1And R2Each independently is a hydrogen atom or a 1-valent organic group.
[ solution 4]
In the above formula (2d), X and Y each independently represent a 2-valent group or a single bond which is not conjugated with the benzene ring to which each is bonded. In formula (2e), Z represents an oxygen atom or a sulfur atom.
[ solution 5]
In the formula (3), R3～R10Each independently represents a hydrogen atom, a fluorine atom or a 1-valent organic group, R3～R10At least one of (a) and (b) represents a fluorine atom, a methyl group or a trifluoromethyl group.
As R in the above formula (1)1And R2Examples of the 1-valent organic group include an alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a fluoroalkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and the like.
In X and Y in the above formula (2d), examples of the 2-valent group not conjugated to a benzene ring include an oxygen atom, dimethylmethylene, bis (trifluoromethyl) methylene, dimethylsilylene, methyltrifluoromethylmethylene and the like.
B in formula (1) is a structure derived from a diamine used as a raw material, and is a 2-valent organic group represented by formula (3).
As R3～R10Examples of the 1-valent organic group in (b) include a methyl group and a trifluoromethyl group. From the viewpoint of good i-line transmittance and low stress, two or more are preferably methyl groups or trifluoromethyl groups.
The polyimide may be a polyimide formed from the above polyimide precursor.
Polybenzene
The azole precursor is a precursor having a structural unit represented by the following formula (4).
[ solution 6]
(in the formula (4), U is a single bond or a 2-valent group, and W is a 2-valent group.)
The 2-valent group of U in formula (4) is preferably a group having an aliphatic chain structure having 1 to 30 carbon atoms, and more preferably a group having a structure represented by formula (UV1) below.
[ solution 7]
(in the formula (UV1), R11And R12Each independently represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 6 carbon atoms or a fluoroalkyl group having 1 to 6 carbon atoms, and a is an integer of 1 to 30. )
R in the formula (UV1) is from the viewpoint of transparency of the polymer11And R12Preferably methyl or trifluoromethyl, more preferably trifluoromethyl.
a is preferably an integer of 1 to 5.
The 2-valent group of W is preferably a structure derived from a dicarboxylic acid, and examples of such a raw dicarboxylic acid include dodecanedioic acid, isophthalic acid, terephthalic acid, 2-bis (4-carboxyphenyl) -1,1,1,3,3, 3-hexafluoropropane, 4' -dicarboxybiphenyl, 4' -dicarboxydiphenyl ether, 4' -dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2-bis (p-carboxyphenyl) propane, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2, 6-naphthalenedicarboxylic acid, and the like.
As a polybenzo
Examples of the azole include polybenzoxazole as described above
Polybenzo formed from azole precursors
And (3) azole.
The novolac resin is preferably one obtained by polycondensation of at least one phenol selected from aromatic hydroxy compounds such as phenol, cresol, xylenol, resorcinol, and hydroquinone, and alkyl-substituted or halogen-substituted aromatic compounds thereof, and aldehyde compounds such as formaldehyde, acetaldehyde, and benzaldehyde, and examples thereof include phenol and formaldehyde resins, cresol and formaldehyde resins, and phenol, cresol, and formaldehyde copolycondensation resins.
The molecular weight of the polymer of component (a) is preferably 10000 to 100000, more preferably 15000 to 100000, and still more preferably 20000 to 85000 in terms of polystyrene. If the weight average molecular weight is less than 10000, the solubility in an alkali developing solution may become too high, and if it exceeds 100000, the solubility in a solvent may decrease, or the viscosity of the solution may increase to lower the workability.
The weight average molecular weight can be measured by gel permeation chromatography and can be determined by conversion using a standard polystyrene calibration curve.
(component (b): having i-line sensitivity
Salt)
(b) Composition as long as it has i-line sensitivity
The salt may be used without particular limitation, but preferably has iodine
A compound of structure or sulfonium structure. From the viewpoint of high contrast, iodine is more preferably contained
A compound of structure (la).
(b) The components are substances with the following functions: for example, when a resin film formed by applying a resin composition onto a substrate is irradiated with light, the resin composition reacts with the light to provide a difference in solubility between exposed portions and unexposed portions in a developer.
(b) Component (b) is preferably a substance having high compatibility with component (a).
(b) The component (b) is preferably a compound which inhibits the dissolution of the component (a) in an aqueous alkali solution before the i-line exposure and does not inhibit the dissolution of the component (a) in an aqueous alkali solution after the i-line exposure. By eliminating the dissolution inhibition of the exposed portion after the i-line exposure, when a thick pattern cured film is formed using the resin composition of the present invention, patterning can be performed with sensitivity and development time within a practical range.
As the component (b), for example, a compound represented by the following general formula (b-1) can be used.
[ solution 8]
(wherein X represents a counter anion, and may have a substituent on the aromatic ring.)
The substituent on the aromatic ring is not particularly limited as long as the effect of the present invention is not impaired. Specifically, there may be mentioned alkyl groups, alkenyl groups, alkoxy groups, trialkylsilyl groups, groups obtained by substituting a part or all of the hydrogen atoms of each of the above groups with fluorine atoms, chlorine atoms, bromine atoms, fluorine atoms, and the like. The aromatic ring may have a plurality of substituents.
As X-Examples thereof include p-toluenesulfonate ion, trifluoromethanesulfonate ion, hexafluoroboride ion, 9, 10-dimethoxyanthracene-2-sulfonate ion, 8-anilinonaphthalene-1-sulfonate ion, methylsulfonate ion, sulfate ion, nitrate ion, trichloroacetate ion and chloride ion.
As having iodine
Specific examples of the compound having a structure include diphenyliodine
-9, 10-dimethoxyanthracene-2-sulfonate, diphenyl iodide
-8-anilinonaphthalene-1-sulfonate, diphenyl iodide
Sulfonate and diphenyl iodide
Triflate and diphenyl iodide
Nonafluorobutane sulfonate and diphenyl iodide
Tosylate, diphenyl iodine chloride
Diphenyl iodine bromide
Diphenyl iodine iodide
Diphenyl iodide
Hexafluorophosphate, 4-methoxyphenyl iodide
Nitrate, 4-methoxyphenyl iodide
Triflate, 4' -di-tert-butyldiphenyliodide
Triflate, phenyl (5-trifluoromethylsulfonyl-4-octen-4-yl) iodide
Hexafluoroborate, and the like.
Among these compounds, the sensitivity and the dissolution contrast are improvedFrom the viewpoint of conversion, it is preferable to use diphenyliodine which is a compound represented by the following formula (b-2)
-9, 10-dimethoxyanthracene-2-sulfonate.
[ solution 9]
(wherein Me is methyl.)
Further, a compound represented by the following formula (b-3) is also preferable.
[ solution 10]
(b) The content of the component (a) is preferably 2 to 50 parts by mass, more preferably 3 to 40 parts by mass, and still more preferably 5 to 30 parts by mass, based on 100 parts by mass of the component (a).
When the component (b) is in the above range, dissolution inhibition of the component (a) is strongly caused in the unexposed portion, and the dissolution inhibiting effect disappears in the exposed portion, whereby the dissolution contrast between the unexposed portion and the exposed portion can be improved. Since the dissolution contrast is high, it can be suitably used also in forming a pattern cured film having a thick film. In addition, the developing time can be shortened.
(component (c): solvent)
Examples of the component (c) include γ -butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, N-butyl acetate, ethoxyethyl propionate, 3-methylmethoxypropionate, N-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoryl amide, tetramethylene sulfone, cyclohexanone, cyclopentanone, diethyl ketone, diisobutyl ketone, and methyl amyl ketone. In general, there is no particular limitation as long as other components in the photosensitive resin composition can be sufficiently dissolved.
Among these solvents, γ -butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, N-methyl-2-pyrrolidone, N-dimethylformamide, N-dimethylacetamide, and dimethylsulfoxide are preferably used from the viewpoint of excellent solubility of each component and coatability when forming a resin film.
(c) The content of the component (a) is not particularly limited, but is preferably 50 to 300 parts by mass, more preferably 100 to 200 parts by mass, per 100 parts by mass of the component (a).
(component (d): crosslinking agent)
In the step of subjecting the pattern resin film to a heat treatment after coating, exposure and development of the resin composition, the component (d) can react with the alkali-soluble resin (crosslinking reaction) or polymerize the crosslinking agent itself. Thus, even when the resin composition is cured at a relatively low temperature, for example, 250 ℃ or lower, good mechanical properties, chemical resistance and flux resistance can be imparted.
(d) The component (C) is not particularly limited as long as it is a compound which is crosslinked or polymerized in the step of heat treatment, but is preferably a compound having an alkoxyalkyl group such as a hydroxymethyl group or an alkoxymethyl group, an epoxy group, an oxetanyl group or a vinyl ether group.
Preferred are compounds in which these groups are bonded to a benzene ring, melamine resins or urea resins in which the N-position is substituted with a hydroxymethyl group or an alkoxymethyl group. Further, from the viewpoint that the dissolution rate of the exposed portion can be increased to improve the sensitivity when development is performed, compounds in which these groups are bonded to a benzene ring having a phenolic hydroxyl group are more preferable.
Among them, a compound having two or more hydroxymethyl groups or alkoxymethyl groups is preferable from the viewpoints of good sensitivity, varnish stability, and prevention of melting of the photosensitive resin film during curing of the photosensitive resin film after pattern formation.
When the resin composition is cured at a low temperature of 250 ℃ or lower as the component (d), a compound represented by the following formula (5) is preferred in order to obtain a cured film having excellent chemical resistance.
[ solution 11]
(in the formula (5), R1And R2Each independently is an alkyl group having 1 to 30 carbon atoms. )
Further, as the component (d), the following compounds are also preferably used.
[ solution 12]
(d) The content of the component (a) is preferably 1 to 50 parts by mass, more preferably 5 to 40 parts by mass, and still more preferably 10 to 30 parts by mass, based on 100 parts by mass of the component (a).
In the 1 st embodiment of the 1 st resin composition of the present invention, the naphthoquinone diazide compound is preferably 0 or more and less than 100ppm with respect to 100 parts by mass of the component (a). In the 1 st resin composition of the present invention, the content is more preferably 0 to 50ppm, still more preferably 0 to 10ppm, and particularly preferably no naphthoquinone diazide compound (0 ppm).
By making the naphthoquinone diazide compound in the above range, the 1 st resin composition of the present invention can maintain good photosensitive characteristics even in a thick film having a film thickness of 20 μm or more after coating.
Examples of the naphthoquinone diazide compound include a reaction product of a polyhydroxy compound and 1, 2-naphthoquinone diazide-4-sulfonyl chloride or 1, 2-naphthoquinone diazide-5-sulfonyl chloride.
Examples of the above-mentioned polyhydroxy compounds include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis (2-hydroxyphenyl) methane, bis (4-hydroxyphenyl) methane, 2-hydroxyphenyl-4 ' -hydroxyphenyl methane, 2-bis (4-hydroxyphenyl) hexafluoropropane, 2,3, 4-trihydroxybenzophenone, 2,3,4, 4' -tetrahydroxybenzophenone, 2 ', 4,4' -tetrahydroxybenzophenone, 2,3,4,2 ', 3 ' -pentahydroxybenzophenone, 2,3,4,3 ', 4', 5 ' -hexahydroxybenzophenone, bis (2,3, 4-trihydroxyphenyl) methane, bis (2,3, 4-trihydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2- [4- [1, 1-bis (4-hydroxyphenyl) ethyl ] phenyl ] propane, 4b,5,9b, 10-tetrahydro-1, 3,6, 8-tetrahydroxy-5, 10-dimethylindeno [2,1-a ] indene, tris (4-hydroxyphenyl) methane, 1,1, 1-tris (4-hydroxyphenyl) ethane and the like. In addition, the substance is not necessarily limited to those listed here.
In the 1 st resin composition of the present invention, the compound containing an acid-reactive protecting group is preferably 0 to 1000ppm with respect to 100 parts by mass of the component (a). In the 1 st resin composition of the present invention, more preferably 0 to 100ppm, further preferably 0 to 10ppm, and particularly preferably no compound (0ppm) containing an acid-reactive protecting group.
By setting the above range, a thick film pattern can be formed at low cost as compared with a chemically amplified positive photosensitive resin composition in which a PEB (Post Exposure Bake) step is essential.
Examples of the compound having an acid-reactive protecting group include compounds in which a hydrogen atom of a carboxylic acid is substituted with a 1-alkoxyalkyl group or the like. Examples of the carboxylic acid include phthalic acid, isophthalic acid, terephthalic acid, 4-carboxyphthalic acid, 5-t-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 1, 4-cyclohexanedicarboxylic acid, 4' -dicarboxydiphenyl ether, 2, 6-naphthalenedicarboxylic acid, 2-bis (4-carboxyphenyl) -1,1,1,3,3, 3-hexafluoropropane, 4' -dicarboxybiphenyl, 4' -dicarboxytetraphenylsilane, bis (4-carboxyphenyl) sulfone, 2-bis (p-carboxyphenyl) propane, cholic acid, deoxycholic acid and lithocholic acid. Examples of the 1-alkoxyalkyl group include a tertiary alkyl group such as a tert-butyl group or a tert-pentyl group, an isobornyl group, an ethoxymethyl group, a 1-ethoxyethyl group, a 1-butoxyethyl group, and a 1-isobutoxyethyl group.
The 1 st resin composition of the present invention may contain a coupling agent, a dissolution accelerator, a dissolution inhibitor, a surfactant, a leveling agent, and the like as required.
In the 1 st photosensitive resin composition of the present invention, the components (a) to (d) are preferably not less than 91% by mass, more preferably not less than 92% by mass, and still more preferably not less than 93% by mass, based on the entire composition.
[2 nd Positive photosensitive resin composition ]
The 2 nd positive photosensitive resin composition of the present invention contains (a) an alkali-soluble resin and (b) an acid generated by i-line exposure
The salt and the solvent (c) contain 0 to 100ppm of a naphthoquinone diazide compound or a compound containing an acid-reactive protecting group, based on 100 parts by mass of the component (a).
(a) The components (a) to (c) are the same as those of the 1 st positive photosensitive resin composition. The 2 nd positive photosensitive resin composition may or may not contain the crosslinking agent (d). (d) The composition was the same as that of the 1 st positive photosensitive resin composition.
The content of the naphthoquinone diazide compound in the 2 nd resin composition is 0 to 100ppm with respect to 100 parts by mass of the component (a). Further, the amount of the naphthoquinone diazide compound is preferably 0 to 50ppm, more preferably 0 to 10ppm, and further preferably not contained (0 ppm).
When the naphthoquinone diazide compound is contained in the above range, the 2 nd resin composition can maintain good photosensitive characteristics even when the film thickness after coating is 20 μm or more.
The content of the compound containing an acid-reactive protecting group in the 2 nd resin composition is 0 to 100ppm with respect to 100 parts by mass of the component (a). Further, it is preferably 0 to 50ppm, more preferably 0 to 10ppm, and further preferably a compound (0ppm) containing no acid-reactive protecting group.
By setting the above range, a thick pattern cured film can be formed at low cost as compared with a chemically amplified positive photosensitive resin composition in which a PEB (Post Exposure Bake) step is essential.
In the photosensitive resin composition 2, the components (a) to (c) are preferably not less than 91% by mass, more preferably not less than 92% by mass, still more preferably not less than 93% by mass, particularly preferably not less than 94% by mass, very preferably not less than 95% by mass, very particularly preferably not less than 96% by mass, particularly preferably not less than 97% by mass, and particularly preferably not less than 98% by mass, based on the entire composition.
The second positive photosensitive resin composition of the present invention is the same as the first positive photosensitive resin composition of the first embodiment except for the above-mentioned matters.
[ method for producing patterned cured film ]
In the production method of the present invention, the patterned cured film can be produced by a process including: the method for producing a photosensitive resin film includes a step of applying the resin composition onto a substrate and drying the resin composition to form a photosensitive resin film, a step of exposing the obtained photosensitive resin film in a predetermined pattern, a step of developing the exposed resin film with an alkaline aqueous solution to obtain a pattern resin film, and a step of heat-treating the pattern resin film.
(resin film formation step)
Examples of the substrate include glass, semiconductor, and TiO2、SiO2Etc., silicon nitride, copper alloys, etc.
The coating is not particularly limited, and may be performed using a spin coater or the like.
Drying may be performed using a hot plate, an oven, or the like. The heating temperature is preferably 100-150 ℃. The heating time is preferably 30 seconds to 5 minutes. Thus, the resin composition can be formed into a film shape to obtain a resin film.
The film thickness of the resin film is preferably 5 to 100 μm, more preferably 8 to 50 μm, and further preferably 10 to 40 μm.
(Exposure Process)
In the exposure step, exposure may be performed in a predetermined pattern through a mask. The active light to be irradiated includes ultraviolet rays including i-rays, visible rays, radiation rays, and the like, and i-rays are preferable. As the exposure apparatus, a parallel exposure machine, a projection exposure machine, a stepper exposure machine, a scanner exposure machine, or the like can be used.
(developing step)
By performing the development treatment, a patterned resin film (pattern resin film) can be obtained. In general, when a positive photosensitive resin composition is used, a developer is used to remove exposed portions.
Examples of the aqueous alkaline solution used as the developer include sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide, etc., and tetramethylammonium hydroxide is preferred.
The concentration of the aqueous alkali solution is preferably 0.1 to 10 mass%.
The developing time varies depending on the type of the polymer used, but is preferably 10 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, and further preferably 30 seconds to 4 minutes from the viewpoint of productivity.
Alcohols or surfactants may be added to the developer. The amount of the additive is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the developer.
(Heat treatment Process)
By subjecting the pattern resin film to heat treatment, a crosslinked structure can be formed between functional groups of the component (a), between the component (a) and the component (d), or the like, and a pattern cured film can be obtained. The component (a) contains a polyimide precursor or a polybenzene
In the case of azole precursors, the respective precursors undergo a dehydration ring-closure reaction to form corresponding polymers.
The heating temperature is preferably 250 ℃ or lower, more preferably 120 to 250 ℃, and still more preferably 160 to 230 ℃.
By setting the range as described above, damage to the substrate and the device can be suppressed to a low level, the device can be produced with a high yield, and energy saving of the process can be achieved.
The heating time is preferably not more than 5 hours, more preferably 30 minutes to 3 hours.
When the amount is within the above range, the crosslinking reaction or the dehydration ring-closing reaction can be sufficiently performed.
The atmosphere for the heat treatment may be in the air or in an inert atmosphere such as nitrogen, but is preferably in a nitrogen atmosphere from the viewpoint of preventing the pattern resin film from being oxidized.
Examples of the apparatus used in the heat treatment step include a quartz tube furnace, a hot plate, a rapid annealing furnace, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, and a microwave curing furnace.
In addition, a microwave curing apparatus or an inverter microwave curing apparatus may be used for the heating treatment.
By using these apparatuses, only the pattern resin film can be efficiently heated while keeping the temperature of the substrate and the device at, for example, 220 ℃ or lower (see, for example, japanese patent No. 2587148). In the case of curing using microwaves, if microwaves are irradiated in a pulse shape while changing the frequency, standing waves can be prevented, and the substrate surface can be uniformly heated.
When a substrate includes metal wiring as in an electronic component, if microwave is irradiated in a pulse shape while changing the frequency, it is possible to prevent discharge from a metal and the like from occurring, and it is possible to protect the electronic component from damage.
When the microwave is irradiated in a pulse form, the heating temperature can be maintained at a predetermined temperature, and damage to the pattern resin film and the substrate can be prevented.
[ cured product ]
The cured product of the present invention is a cured product of the positive photosensitive resin composition of the present invention. The above-described heat treatment step can be employed as a method for obtaining a cured product.
The cured product of the present invention may be the above-described pattern cured film.
[ electronic component ]
The pattern cured film and the cured product produced by the above method can be used as an interlayer insulating film, a cover coat, or a surface protective film.
By using the above-mentioned interlayer insulating film, coverlay, surface protective film, etc., it is possible to manufacture electronic parts such as a semiconductor device, a multilayer wiring board, and various electronic devices with high reliability.
[ Process for manufacturing semiconductor device ]
Using the method of the present invention, a semiconductor device, particularly a device having an encapsulation structure without providing a UBM layer, can be manufactured.
The packaging structure without the UBM layer is as follows: the solder bump is directly mounted on the copper rewiring, and the outermost resin composition reinforces the bump in order to relax the stress applied to the bump and ensure reliability.
The manufacturing process is shown in fig. 1. The photosensitive resin composition is applied onto a substrate 10 having a rewiring layer 20 and dried to form a resin film (1-1), and the obtained resin film 30 is exposed to light in a predetermined pattern. The exposed resin film is developed with a developer (1-2), the patterned resin film obtained by the development is subjected to a heat treatment, and then conductive balls or conductive bumps 40(1-3) are mounted, thereby making it possible to manufacture a package without a UBM layer.
In the package intermediate, the bump is reinforced by the outermost patterned resin film to ensure reliability, and therefore, the thickness of the patterned cured film is preferably larger than the conventional film thickness (10 μm or less).
Fig. 2 is a schematic cross-sectional view of a semiconductor device having a rewiring structure without providing a UBM layer. In the semiconductor device 100 of fig. 2, a metal (aluminum or the like) wiring 120 is provided on a wafer 110, and an insulating layer 130 is laminated so as to cover both end portions of the wafer 110 and the metal wiring 120. An interlayer insulating film 140 is provided on the insulating layer 130 so as to cover the insulating layer 130 and a part of the metal wiring 120, and a rewiring layer 150 is laminated so as to cover the entire remaining exposed part of the metal wiring 120 and the interlayer insulating film 140. Conductive balls 170 are provided in contact with the rewiring layer 150, and a cover coat layer 160 is laminated on the rewiring layer 150 so as to fill the gaps formed between the rewiring layer 150 and the conductive balls 170.
By forming the thick overcoat layer 160 using the resin composition of the present invention, a semiconductor device can be manufactured without providing a UBM layer that is a complicated formation process.
The semiconductor device is one embodiment of the electronic component of the present invention, but is not limited to the above, and various configurations can be adopted.
Examples
The present invention will be described in more detail below based on examples and comparative examples. In addition, the present invention is not limited to the following examples.
[ polybenzo
Synthesis of oxazole precursors]
Synthesis example 1
60g of N-methylpyrrolidone was put into a 0.2 liter flask equipped with a stirrer and a thermometer, and 13.92g (38mmol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added and dissolved with stirring. Subsequently, while maintaining the temperature at 0 to 5 ℃, 10.69g (40mmol) of dodecanedioic dichloride was dropwise added over 10 minutes, and then the solution in the flask was stirred for 60 minutes. The solution was poured into 3 liters of water, and the precipitate was collected, washed 3 times with pure water, and then decompressed to obtain polyhydroxyamide (polybenzo)
Azole precursor) (hereinafter, referred to as polymer I). The weight average molecular weight of the polymer I was 33,100 and the degree of dispersion was 2.0, which was determined by Gel Permeation Chromatography (GPC) method in terms of standard polystyrene.
The conditions for measuring the weight average molecular weight by GPC are as follows. The measurement was performed using a solution of 0.5mg of the polymer in 1ml of a solvent [ Tetrahydrofuran (THF)/Dimethylformamide (DMF) ═ 1/1 (volume ratio) ].
A measuring device: l4000UV manufactured by Hitachi, Inc. of Detector
A pump: l6000 manufactured by Hitachi Kabushiki Kaisha
C-R4A Chromatopac, manufactured by Shimadzu corporation
The measurement conditions were as follows: chromatographic column Gelpack GL-S300 MDT-5X 2
Eluent: THF/DMF 1/1 (volumetric ratio)
LiBr(0.03mol/l)、H3PO4(0.06mol/l)
Flow rate: 1.0ml/min, detector: UV270nm
Synthesis example 2
60g of N-methylpyrrolidone was put into a 0.2 liter flask equipped with a stirrer and a thermometer, and 13.92g (38mmol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane was added and dissolved with stirring. Then, while maintaining the temperature at 0 to 5 ℃, 11.86g (40mmol) of 4,4' -diphenyletherdicarboxyl dichloride was added dropwise over 10 minutes, the temperature was returned to room temperature, and the solution in the flask was stirred for 3 hours. The solution was poured into 3 liters of water, and precipitates were collected, washed 3 times with pure water, and then decompressed to obtain polyhydroxyamide (hereinafter referred to as polymer II). The weight average molecular weight of the polymer II was 22,400 and the degree of dispersion was 3.2, which was determined in terms of polystyrene standard by GPC in the same manner as in synthesis example 1.
Synthesis example 3
Synthesis was carried out in the same manner as in Synthesis example 1 except that 10.69g (40mmol) of dodecanedioic acid dichloride used in Synthesis example 1 was replaced with 7.48g (28mmol) of dodecanedioic acid dichloride and 3.56g (12mmol) of 4,4' -diphenylether-dicarboxyl dichloride to obtain polyhydroxyamide (hereinafter referred to as polymer III). The weight average molecular weight of the polymer III was 41,800 and the degree of dispersion was 2.0, which was determined in terms of standard polystyrene in the same manner as in synthesis example 1.
[ Synthesis of polyimide precursor ]
Synthesis example 4
In a 0.2 liter flask equipped with a stirrer and a thermometer, 50g of N-methylpyrrolidone was charged, and 13.82g (18mmol) of 4,4 '-diamino-2, 2' -dimethylbiphenyl was added and dissolved with stirring. Subsequently, 6.20g (20mmol) of 4,4' -oxydiphthalic dianhydride was added dropwise over 10 minutes while maintaining the temperature at 0 to 5 ℃, and then the temperature was returned to room temperature, and the solution in the flask was stirred for 3 hours. The solution was poured into 3 liters of water, and precipitates were collected, washed 3 times with pure water, and then decompressed to obtain polyamic acid (hereinafter referred to as polymer IV). The weight average molecular weight of the polymer IV was 39,000 and the degree of dispersion was 4.5, which were determined in terms of polystyrene standard by GPC method in the same manner as in synthesis example 1.
[ (Synthesis of component b ]
Synthesis example 5
To have a stirring function150ml of ion-exchanged water was put into a 0.5 liter flask equipped with a stirrer and a thermometer, and diphenyliodonium chloride was added thereto
4.3g (14mmol) was dissolved by stirring while heating at 100 ℃. Further, 300ml of ion-exchanged water was separately put into a 1.0 liter flask equipped with a stirrer and a thermometer, and 4.7g (14mmol) of sodium 9, 10-dimethoxyanthracene sulfonate was added thereto and dissolved with stirring while heating at 100 ℃. Then, diphenyl iodine chloride
The aqueous solution was poured into an aqueous solution of 9, 10-dimethoxyanthracene sulfonic acid sodium salt, and stirred for 3 hours until it was returned to room temperature. The precipitate was recovered, washed 3 times with pure water, and then dried under reduced pressure to obtain diphenyliodine
-9, 10-dimethoxyanthracene-2-sulfonate (b 1).
Synthesis example 6
Into a 0.5 liter flask equipped with a stirrer and a thermometer was charged 300ml of ion-exchanged water, and diphenyliodonium chloride was added
10.0g (32mmol) was dissolved by stirring while heating at 100 ℃. Further, 300ml of ion-exchanged water was put into a 1.0 liter flask equipped with a stirrer and a thermometer, and 10.0g (32mmol) of ammonium 8-anilino-1-naphthalenesulfonate was added and dissolved with stirring while heating at 100 ℃. Then, diphenyl iodine chloride
The aqueous solution was poured into an aqueous solution of ammonium 8-anilino-1-naphthalenesulfonate, and stirred for 3 hours until the temperature was returned to room temperature. The precipitate was recovered, washed 3 times with pure water, and then dried under reduced pressure to obtain diphenyliodine
-8-anilinonaphthalene-1-sulfonate (b 2).
[ Synthesis of Compound having acid-reactive protecting group ]
Synthesis example 7
4.54g (17.6mmol) of 4,4' -dicarboxydiphenyl ether was charged into a 100ml three-necked flask and suspended in 30g of N-methylpyrrolidone. While cooling with ice, 3.74g (39.6mmol) of chloromethyl ether was added, followed by 3.55g (35.1mmol) of triethylamine. After stirring in an ice bath for 3 hours, the precipitated crystals were removed by filtration. To the mother liquor, a few drops of a saturated aqueous sodium bicarbonate solution were added to stop the reaction, and the organic layer extracted with ethyl acetate was washed with a saturated aqueous sodium bicarbonate solution, water, and saturated brine in this order, and dried over anhydrous sodium sulfate. After anhydrous sodium sulfate was filtered off, the solvent was distilled off under reduced pressure and dried to obtain compound (e1) containing an acid-reactive protecting group.
[ example of a Positive photosensitive resin composition 1]
Examples 1 to 19 and comparative examples 1 to 13
The photosensitive resin compositions of examples 1 to 19 and comparative examples 1 to 13 were prepared by using the components and blending amounts shown in tables 1 to 4. The amounts shown in tables 1 to 4 are parts by mass of the components (b) to (d), (b' -1) and (e1) per 100 parts by mass of each polymer as the component (a).
The components used are as follows.
(a) The components:
polymer I: polymer I obtained in Synthesis example 1
Polymer II: polymer II obtained in Synthesis example 2
Polymer III: polymer III obtained in Synthesis example 3
Polymer IV: synthesis of Polymer IV obtained in Synthesis example 4
Polymer V: cresol novolak EP4020G (manufactured by Asahi organic materials industries Co., Ltd.)
(b) The components:
(b1) the method comprises the following steps Diphenyl iodide obtained in Synthesis example 5
-9, 10-dimethoxyanthracene-2-sulfonate
(b2) The method comprises the following steps Diphenyl iodide obtained in Synthesis example 6
-8-anilinonaphthalene-1-sulfonic acid salt
[ solution 13]
(c) The components:
BLO: gamma-butyrolactone
NMP: n-methyl pyrrolidone
EL: lactic acid ethyl ester
(d) The components:
d1: 1,3,4, 6-tetrakis (methoxymethyl) glycoluril having the following structure (manufactured by Sanko chemical Co., Ltd., trade name "MX-270")
[ solution 14]
D2: "NIKALAC MX-280" (trade name, product of Sanhe chemical Co., Ltd.) having the following structure
[ solution 15]
The compounds used in the components other than (a) to (d) are as follows.
(b' -1): a compound obtained by reacting 2- (4-hydroxyphenyl) -2- [4- [1, 1-bis (4-hydroxyphenyl) ethyl ] phenyl ] propane with naphthoquinone-1, 2-diazide-5-sulfonyl chloride in a molar ratio of 1:3
[ solution 16]
e 1: synthesis of the Compound having an acid-reactive protecting group obtained in Synthesis example 7
[ evaluation of dissolution Rate and dissolution contrast ]
The photosensitive resin compositions of examples 1 to 19 and comparative examples 1 to 13 were spin-coated on a silicon substrate, and dried at 120 ℃ for 3 minutes to form a resin film having a film thickness of 10 or 25 μm after drying. The obtained resin film was exposed to light via an interference filter using an ultrahigh pressure mercury lamp and a proximity exposure apparatus UX-1000SM-XJ01 (manufactured by USHIO Motor Co., Ltd.) to irradiate 400mJ/cm in a predetermined pattern2I-line of (1).
After exposure, development was performed at 23 ℃ (the development time required in each example was set to the respective development time) using an aqueous solution of 2.38 mass% TMAH until the silicon substrate of the exposed portion was exposed, and then rinsing was performed using water to obtain a pattern resin film.
The value obtained by dividing the film thickness after drying by the developing time was defined as the exposed portion dissolution rate.
Exposed portion dissolution rate (nm/s) — film thickness after drying/development time
The unexposed portion film thickness after development was measured, and the unexposed portion dissolution rate was determined by dividing the value obtained by subtracting the developed unexposed portion film thickness from the dried film thickness by the development time.
Unexposed portion dissolution rate (nm/s) (film thickness after drying-unexposed portion film thickness after development)/development time
The dissolution contrast was determined by dividing the dissolution rate of the exposed portion by the dissolution rate of the unexposed portion.
Dissolution contrast (dissolution rate of exposed portion/dissolution rate of unexposed portion)
The results are shown in tables 1 to 4.
[ Table 1]
[ Table 2]
[ Table 3]
[ Table 4]
The patterned resin films were each subjected to a heat treatment at 200 ℃ for 1 hour, resulting in a good patterned cured film.
Examples 20 to 28 and comparative examples 14 to 15
The photosensitive resin compositions of examples 20 to 28 and comparative examples 14 to 15 were prepared by using the components and the amounts shown in Table 5. The amounts in Table 5 are the same as in tables 1 to 4.
[ evaluation of Pattern formability ]
Except that the film thickness after drying is set to 10 to 30 μm, and the exposure is set to 800mJ/cm2A patterned resin film was formed in the same manner as in examples 1 to 19 and comparative examples 1 to 13, except that the developing time was 150 seconds.
The patterned resin film was observed with a line/pitch pattern having a line width of 20 μm using a microscope or a digital microscope VHX-100F (manufactured by KEYENCE K.K.) to confirm the presence or absence of scum. The case where patterning was performed without scum is referred to as a, and the case where patterning was performed with scum is referred to as B. The results are shown in table 5.
[ Table 5]
The patterned resin films were each subjected to a heat treatment at 200 ℃ for 1 hour, resulting in a good patterned cured film.
[ example of a Positive photosensitive resin composition ] of the invention
Examples 29 to 44 and comparative examples 16 to 28
The photosensitive resin compositions of examples 29 to 44 and comparative examples 16 to 28 were prepared by using the components and blending amounts shown in tables 6 to 8. The blending amounts in tables 6 to 8 are parts by mass of the components (b) to (d) and (b') per 100 parts by mass of each polymer as the component (a).
The component (b') is as follows.
(b' 1): synthesis of the Compound having an acid-reactive protecting group obtained in Synthesis example 7 (examples 1 to 28, comparative examples 1 to 15, (e1))
(b' 2): a compound represented by the following structural formula (TPPA 528 (trade name) manufactured by DAITO CHEMIX Co., Ltd., naphthoquinone diazide compound)
[ solution 17]
[ evaluation of dissolution Rate and dissolution contrast ]
The dissolution rate and dissolution contrast were evaluated in the same manner as in examples 1 to 19 and comparative examples 1 to 13. The following evaluation criteria were used in examples 29 to 44 and comparative examples 16 to 28.
A represents a case where the dissolution rate of the exposed portion is 150nm/s or more, B represents a case where the dissolution rate is 50nm/s or more and 150nm/s or more, and C represents a case where the dissolution rate is lower than 50 nm/s.
A represents a case where the dissolution rate of the unexposed portion is 30nm/s or less, B represents a case where the dissolution rate is 30nm/s or more and 100nm/s or more, and C represents a case where the dissolution rate is faster than 100 nm/s.
The dissolution contrast is a when it is 6 or more, B when it is 4 or more and less than 6, C when it is 2 or more and less than 4, and D when it is less than 2.
The results are shown in tables 6 and 7.
[ Table 6]
[ Table 7]
The patterned resin films were each subjected to a heat treatment at 200 ℃ for 1 hour, resulting in a good patterned cured film.
Examples 45 to 49 and comparative examples 29 and 30
The photosensitive resin compositions of examples 45 to 49 and comparative examples 29 and 30 were prepared using the components and amounts shown in Table 8.
[ evaluation of Pattern formability ]
The pattern formability was evaluated in the same manner as in examples 20 to 28 and comparative examples 14 and 15. The results are shown in Table 8.
[ Table 8]
The patterned resin films were each subjected to a heat treatment at 200 ℃ for 1 hour, resulting in a good patterned cured film.
Industrial applicability
The photosensitive resin composition of the present invention can be used for electronic components such as semiconductor devices, multilayer wiring boards, and various electronic devices.
While several embodiments and/or examples of the present invention have been described in detail above, those skilled in the art will readily appreciate that many modifications are possible in the illustrated embodiments and/or examples without materially departing from the novel teachings and advantages of this invention. Accordingly, many such variations are intended to be included within the scope of the present invention.
The contents of the documents described in this specification and the contents of the specification of the japanese application, which is the basis of the priority of the paris convention of the present application, are incorporated herein in their entirety.
Claims (13)
1. A positive photosensitive resin composition comprising (a) a polybenzene having a structural unit represented by the following formula (4)
Azole precursors, (b) acid generation by i-line exposure
A salt, (c) a solvent and (d) a crosslinking agent, wherein the total amount of the components (a), (b) and (d) is 88% by mass or more based on the total mass of the positive photosensitive resin composition excluding the solvent (c),
in the formula (4), U is a single bond or a 2-valent group, and W is a 2-valent group.
2. A positive photosensitive resin composition comprising (a) a polybenzene having a structural unit represented by the following formula (4)
Azole precursors, (b) acid generation by i-line exposure
A salt and (c) a solvent, wherein the positive photosensitive resin composition contains 0 to 100ppm of a naphthoquinone diazide compound or a compound containing an acid-reactive protecting group per 100 parts by mass of the component (a),
in the formula (4), U is a single bond or a 2-valent group, and W is a 2-valent group.
3. The positive photosensitive resin composition according to claim 2, further comprising (d) a crosslinking agent.
4. The positive photosensitive resin composition according to claim 1 or 2, wherein the component (b) is a compound that prevents the component (a) from dissolving in an aqueous alkali solution before i-line exposure and does not prevent the component (a) from dissolving in an aqueous alkali solution after i-line exposure.
5. The positive photosensitive resin composition according to claim 1 or 2, wherein the component (b) is a compound represented by the following general formula (b-1),
wherein X is a counter anion, and has a substituent on the aromatic ring or has no substituent on the aromatic ring.
6. The positive photosensitive resin composition according to claim 1 or 2, wherein the component (b) is a compound represented by the following formula (b-2),
in the formula, Me is methyl.
7. The positive photosensitive resin composition according to claim 1 or 2, which is used for forming an interlayer insulating film, a cover coat layer, or a surface protective film.
8. The positive photosensitive resin composition according to claim 1 or 2, which is used for forming an interlayer insulating film, a cover coat layer, or a surface protective film of a semiconductor device having an underbump metallurgy structure.
9. A method for manufacturing a pattern cured film, comprising the steps of:
a step of forming a photosensitive resin film by applying the positive photosensitive resin composition according to any one of claims 1 to 8 onto a substrate and drying the applied composition;
exposing the obtained photosensitive resin film in a predetermined pattern;
a step of obtaining a pattern resin film by developing the exposed resin film with an alkaline aqueous solution; and
and a step of heat-treating the pattern resin film.
10. The method for manufacturing a pattern cured film according to claim 9, wherein the temperature of the heat treatment is 250 ℃ or lower.
11. A cured product of the positive photosensitive resin composition according to any one of claims 1 to 8.
12. An interlayer insulating film, a covercoat layer or a surface protective film using the cured product according to claim 11.
13. An electronic part having the interlayer insulating film, the covercoat layer or the surface protective film of claim 12.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014204005 | 2014-10-02 | ||
| JP2014-204005 | 2014-10-02 | ||
| JPPCT/JP2015/052382 | 2015-01-28 | ||
| PCT/JP2015/052382 WO2016121035A1 (en) | 2015-01-28 | 2015-01-28 | Positive photosensitive resin composition, method for producing patterned cured film, interlayer insulating film, cover coat layer, surface protection film and electronic component |
| PCT/JP2015/005021 WO2016051809A1 (en) | 2014-10-02 | 2015-10-01 | Positive photosensitive resin composition, method for producing patterned cured film, cured product, interlayer insulating film, cover coat layer, surface protective film and electronic component |
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| CN106796399A CN106796399A (en) | 2017-05-31 |
| CN106796399B true CN106796399B (en) | 2021-01-22 |
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| JP (2) | JP6743701B2 (en) |
| KR (1) | KR102585279B1 (en) |
| CN (1) | CN106796399B (en) |
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| KR102337564B1 (en) * | 2018-09-28 | 2021-12-13 | 삼성에스디아이 주식회사 | Photosensitive resin composition, photosensitive resin layer and electronic device using the same |
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| JP2007240555A (en) * | 2006-03-03 | 2007-09-20 | Hitachi Chemical Dupont Microsystems Ltd | Positive photosensitive polyamideimide resin composition, method for producing pattern, and electronic component |
| TW201321899A (en) * | 2011-11-09 | 2013-06-01 | Jnc Corp | Positive photosensitive composition |
Family Cites Families (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2931297A1 (en) | 1979-08-01 | 1981-02-19 | Siemens Ag | HEAT-RESISTANT POSITIVE RESISTS AND METHOD FOR PRODUCING HEAT-RESISTANT RELIEF STRUCTURES |
| US4927736A (en) | 1987-07-21 | 1990-05-22 | Hoechst Celanese Corporation | Hydroxy polyimides and high temperature positive photoresists therefrom |
| JPH05181274A (en) * | 1991-12-26 | 1993-07-23 | Nippon Steel Chem Co Ltd | Polyimido-based photosensitive composition |
| TWI255393B (en) * | 2000-03-21 | 2006-05-21 | Hitachi Chemical Co Ltd | Photosensitive resin composition, photosensitive element using the same, process for producing resist pattern and process for producing printed wiring board |
| US6969576B2 (en) * | 2001-11-30 | 2005-11-29 | Sandia National Laboratories | Photosensitive dissolution inhibitors and resists based on onium salt carboxylates |
| JP3812654B2 (en) * | 2002-01-23 | 2006-08-23 | Ｊｓｒ株式会社 | Positive photosensitive insulating resin composition and cured product thereof |
| CN100457749C (en) * | 2003-01-22 | 2009-02-04 | Jsr株式会社 | Sulfonium salts, radiation-sensitive acid generators, and positive radiation-sensitive resin compositions |
| EP1744213B1 (en) * | 2004-05-07 | 2014-09-03 | Hitachi Chemical DuPont Microsystems Ltd. | Positive photosensitive resin composition, method for forming pattern, and electronic component |
| JP4777644B2 (en) * | 2004-12-24 | 2011-09-21 | Ｏｋｉセミコンダクタ株式会社 | Semiconductor device and manufacturing method thereof |
| US7803510B2 (en) * | 2005-08-17 | 2010-09-28 | Fujifilm Electronic Materials U.S.A., Inc. | Positive photosensitive polybenzoxazole precursor compositions |
| JP2008015184A (en) * | 2006-07-05 | 2008-01-24 | Sekisui Chem Co Ltd | Positive photosensitive composition, method for producing patterned film, and semiconductor device |
| US9519216B2 (en) * | 2008-02-04 | 2016-12-13 | Fujifilm Electronic Materials U.S.A., Inc. | Positive photosensitive resin compositions |
| JP5169446B2 (en) | 2008-04-28 | 2013-03-27 | 日立化成デュポンマイクロシステムズ株式会社 | Photosensitive resin composition, polybenzoxazole film using the resin composition, method for producing patterned cured film, and electronic component |
| JP2010139931A (en) * | 2008-12-15 | 2010-06-24 | Toyobo Co Ltd | Positive photosensitive resin composition and pattern forming method |
| TWI397546B (en) * | 2010-01-14 | 2013-06-01 | Chang Chun Plastics Co Ltd | Novel water soluble polyimide resin, its preparation and use |
| JP5806493B2 (en) * | 2011-03-31 | 2015-11-10 | 太陽インキ製造株式会社 | Positive photosensitive resin composition, dry film, cured product, and printed wiring board |
| JP2013256603A (en) * | 2012-06-13 | 2013-12-26 | Hitachi Chemical Dupont Microsystems Ltd | Resin composition, method of manufacturing pattern cured film using the resin composition, and electronic part |
| JP2015022228A (en) * | 2013-07-22 | 2015-02-02 | Jnc株式会社 | Positive-type photosensitive composition |
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| JP2007240555A (en) * | 2006-03-03 | 2007-09-20 | Hitachi Chemical Dupont Microsystems Ltd | Positive photosensitive polyamideimide resin composition, method for producing pattern, and electronic component |
| TW201321899A (en) * | 2011-11-09 | 2013-06-01 | Jnc Corp | Positive photosensitive composition |
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| TW201619699A (en) | 2016-06-01 |
| JPWO2016051809A1 (en) | 2017-08-10 |
| JP6743701B2 (en) | 2020-08-19 |
| JP2020126271A (en) | 2020-08-20 |
| JP6919746B2 (en) | 2021-08-18 |
| TWI708994B (en) | 2020-11-01 |
| WO2016051809A1 (en) | 2016-04-07 |
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