WO2023182136A1 - ポジ型感光性樹脂組成物、硬化膜、および半導体装置 - Google Patents

ポジ型感光性樹脂組成物、硬化膜、および半導体装置 Download PDF

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WO2023182136A1
WO2023182136A1 PCT/JP2023/010281 JP2023010281W WO2023182136A1 WO 2023182136 A1 WO2023182136 A1 WO 2023182136A1 JP 2023010281 W JP2023010281 W JP 2023010281W WO 2023182136 A1 WO2023182136 A1 WO 2023182136A1
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Prior art keywords
resin composition
photosensitive resin
positive photosensitive
mass
positive
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PCT/JP2023/010281
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English (en)
French (fr)
Japanese (ja)
Inventor
豊誠 高橋
咲子 鈴木
渉 高田
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Sumitomo Bakelite Co Ltd
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Sumitomo Bakelite Co Ltd
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Priority to KR1020247034614A priority Critical patent/KR20240165403A/ko
Priority to CN202380029949.1A priority patent/CN118922781A/zh
Priority to JP2024510085A priority patent/JPWO2023182136A1/ja
Publication of WO2023182136A1 publication Critical patent/WO2023182136A1/ja
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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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
    • G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
    • G03F7/0395—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having a backbone with alicyclic moieties
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W20/00—Interconnections in chips, wafers or substrates
    • H10W20/01—Manufacture or treatment
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W20/00—Interconnections in chips, wafers or substrates
    • H10W20/40—Interconnections external to wafers or substrates, e.g. back-end-of-line [BEOL] metallisations or vias connecting to gate electrodes
    • H10W20/45—Interconnections external to wafers or substrates, e.g. back-end-of-line [BEOL] metallisations or vias connecting to gate electrodes characterised by their insulating parts
    • H10W20/48—Insulating materials thereof

Definitions

  • the present invention relates to a positive photosensitive resin composition, a cured film thereof, and a semiconductor device including the cured film as an insulating layer.
  • thermosetting resins are sometimes used to form cured films such as insulating layers. Therefore, photosensitive resin compositions containing thermosetting resins have been studied so far. It is known to form an insulating film in a rewiring layer or an insulating film in a portion other than the rewiring layer using a photosensitive resin composition containing a thermosetting resin.
  • Patent Document 1 describes a photosensitive resin composition containing an alkaline aqueous solution soluble resin, a crosslinking agent, a photopolymerization initiator, and an epoxy resin (thermosetting resin) represented by a specific general formula. .
  • Patent Document 1 describes that this photosensitive resin composition has good photosensitivity. Further, Patent Document 1 states that a film formed from this photosensitive resin composition has excellent flexibility, adhesion, pencil hardness, solvent resistance, acid resistance, heat resistance, gold plating resistance, etc. There is.
  • the present invention was made in view of the above-mentioned problems, and by using a specific phenol resin, a crosslinking agent, and a photosensitizer in combination in a positive photosensitive resin composition, it can be cured at low temperature while being They discovered that a cured product has excellent mechanical properties and, as a result, a resin film with excellent adhesion to a substrate can be obtained, and the present invention has been completed.
  • a positive photosensitive resin composition used for a rewiring layer of a semiconductor device comprising:
  • the photosensitive resin composition is (A) Phenol resin having a biphenol structure, (B) a crosslinking agent, and (C) a photosensitizer,
  • a positive photosensitive resin composition is provided in which the cured product obtained by curing the positive photosensitive resin composition at 180° C. has a tensile strength at break of 100 MPa or more.
  • a cured film obtained by curing the above-mentioned positive photosensitive resin composition is provided.
  • a semiconductor element A rewiring layer provided on the surface of the semiconductor element, the semiconductor device comprising: A semiconductor device is provided in which the insulating layer in the rewiring layer is composed of the cured film.
  • a positive photosensitive resin composition having low temperature curability and a cured film with excellent mechanical strength obtained by curing the same are provided.
  • FIG. 1 is a cross-sectional view showing a configuration example of a semiconductor device in an embodiment.
  • the numerical range "x to y" represents “x to y” and includes both the lower limit x and the upper limit y.
  • “1 to 5% by mass” means “1 to 5% by mass”.
  • similar components are denoted by common reference numerals, and description thereof will be omitted as appropriate.
  • the figure is a schematic diagram and does not correspond to the actual dimensional ratio.
  • alkyl group includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • the positive photosensitive resin composition of this embodiment is a resin material used to form a rewiring layer of a semiconductor device.
  • the positive photosensitive resin composition of this embodiment includes (A) a phenol resin, (B) a crosslinking agent, and (C) a photosensitizer,
  • the phenol resin (A) is a phenol resin having a biphenol structure, in other words, a biphenyl type phenol resin.
  • the positive photosensitive resin composition of this embodiment has a tensile strength at break of 100 MPa or more of a cured product obtained by curing the positive photosensitive resin composition at 180°C.
  • the present inventor conducted studies to improve the low-temperature curability of a positive photosensitive resin composition and to improve the mechanical strength of the resulting cured film.
  • the positive photosensitive resin composition to include a specific component, the tensile strength at break of the cured product obtained by curing the positive photosensitive resin composition at 180°C becomes 100 MPa or more. Therefore, it has been found that the above problem can be solved.
  • Each component used in the positive photosensitive resin composition of this embodiment will be explained below.
  • the positive photosensitive resin composition of this embodiment contains a biphenyl type phenol resin (a1) as a phenol resin.
  • a biphenyl-type phenolic resin (a1) from the viewpoint of improving curability at low temperatures and reliability of the cured film, a biphenyl-type phenolic resin having a structural unit having a biphenol skeleton represented by the following formula (2) is preferable. .
  • R 41 and R 42 are each independently a hydroxyl group, a halogen atom, a carboxyl group, a saturated or unsaturated alkyl group having 1 to 20 carbon atoms, or an alkyl ether having 1 to 20 carbon atoms.
  • a monovalent substituent selected from the group consisting of a saturated or unsaturated alicyclic group having 3 to 20 carbon atoms, or an organic group having an aromatic structure having 6 to 20 carbon atoms; may be bonded via an ether bond, an amide bond, or a carbonyl bond, r and s are each independently an integer of 0 to 3, and Y 4 and Z 4 are each independently , an aliphatic group having 1 to 10 carbon atoms which may have a single bond or an unsaturated bond, an alicyclic group having 3 to 20 carbon atoms, and an organic group having an aromatic structure having 6 to 20 carbon atoms.
  • Z 4 is selected from the group consisting of, and Z 4 is bonded to either one of the two benzene rings.
  • the weight average molecular weight of the biphenyl-type phenolic resin (a1) is 12,000 or more, preferably 15 ,000 or more, more preferably 18,000 or more, still more preferably 20,000 or more.
  • the weight average molecular weight of the biphenyl type phenol resin (a1) is 500,000 or less, preferably 400,000 or less, more preferably 300,000 or less, from the viewpoint of maintaining appropriate solvent solubility. or less, more preferably 200,000 or less.
  • the biphenyl-type phenolic resin (a1) having a structural unit represented by formula (2) can be obtained using the method described in JP 2018-155938A.
  • the content of the biphenyl phenolic resin (a1) in the positive photosensitive resin composition of this embodiment is determined based on the total solid content of the positive photosensitive resin composition from the viewpoint of improving curability during low temperature curing.
  • the content is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more.
  • the content of the biphenyl type phenol resin (a1) in the positive photosensitive resin composition is preferably 70% by mass based on the total solid content of the positive photosensitive resin composition from the viewpoint of deterioration of toughness. or less, more preferably 60% by mass or less, still more preferably 50% by mass or less.
  • the positive photosensitive resin composition of the present embodiment may further contain a phenol resin (a2) other than the above-mentioned biphenyl-type phenol resin (a1) from the viewpoint of improving curability at low temperatures and reliability of the cured film. good.
  • a phenol resin (a2) specifically, a novolac type phenolic resin such as a phenol novolac resin, a cresol novolac resin, a bisphenol novolac resin, a phenol-biphenyl novolak resin, an allylated novolac type phenolic resin, a xylylene novolac type phenolic resin;
  • Examples include reaction products of a phenol compound and an aldehyde compound, such as novolac type phenol resin, resol type phenol resin, and cresol novolak resin; and reaction products of a phenol compound, such as phenol aralkyl resin, and a dimethanol compound.
  • the phenol resin (a2) is preferably a resin having a structure represented by the following formula (1) from the viewpoint of obtaining a low-temperature curable resin composition.
  • n is preferably 6 or more, more preferably 10 or more, still more preferably 14 or more, from the viewpoint of improving curability at low temperatures. Further, from the viewpoint of solvent solubility, n is preferably 72 or less, more preferably 54 or less, and still more preferably 36 or less.
  • the weight average molecular weight of the biphenyl type phenol resin (a2) is, for example, 500 or more, preferably 2000 or more, more preferably 3000 or more, and even more preferably is 4000 or more.
  • the weight average molecular weight of the biphenyl type phenol resin (a2) is, from the viewpoint of solvent solubility, for example, 50,000 or less, preferably 20,000 or less, more preferably 15,000 or less, and even more preferably, 10,000 or less.
  • the content is preferably determined based on the total solid content of the positive type photosensitive resin composition from the viewpoint of improving toughness during low temperature curing. is 5% by mass or more, more preferably 10% by mass or more, still more preferably 15 parts by mass or more.
  • the content of the biphenyl phenolic resin (a2) in the positive photosensitive resin composition is determined based on the total solid content of the positive photosensitive resin composition, from the viewpoint of mechanical properties of the cured film obtained. Preferably it is 70 parts by mass or less, more preferably 60 parts by mass or less, still more preferably 50 parts by mass or less.
  • the positive photosensitive resin composition of this embodiment may contain thermosetting resins other than the above-mentioned phenolic resins (a1) and (a2).
  • thermosetting resins include phenol resins other than the above-mentioned biphenyl type phenol resins, hydroxystyrene resins, polyamide resins, polybenzoxazole resins, polyimide resins, and cyclic olefin resins.
  • the content of the phenolic resin (A) in the positive photosensitive resin composition is determined based on the total solid content of the photosensitive resin composition, from the viewpoint of improving curability at low temperatures and reliability of the cured film. , preferably 30% by mass or more, more preferably 45% by mass or more, even more preferably 50% by mass or more, still more preferably 55% by mass or more. Further, from the viewpoint of improving chemical resistance and photosensitivity, the content of component (A) in the photosensitive resin composition is preferably 95 parts by mass or less based on the total solid content of the photosensitive resin composition. It is more preferably 90% by mass or less, still more preferably 85% by mass or less.
  • the phenol resin (A) is the total amount of phenol resins used in the positive photosensitive resin composition of this embodiment, and the phenol resin (A) is the above-mentioned biphenyl type phenol resin (a1), and It consists of a phenolic resin (a2) used as necessary.
  • the positive photosensitive resin composition of this embodiment includes a crosslinking agent (B) having a reactive group capable of crosslinking with the phenol resin (A).
  • a crosslinking agent (B) a bifunctional or more functional urea resin crosslinking agent (b1) is preferably used.
  • Examples of the difunctional or more functional urea resin crosslinking agent (b1) include di- to tetrafunctional alkoxymethylated glycoluril compounds.
  • An alkoxymethylated glycoluril compound refers to a compound in which the hydrogen atom of the amino group of a glycoluril compound is substituted with an alkoxymethylol group.
  • alkoxymethylated glycoluril examples include 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4 , 6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1,3,3-tetrakis(methoxymethyl) Examples include urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, and 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolinone.
  • the crosslinking agent (B) contains other crosslinking agents (b2) in addition to the above-mentioned urea resin crosslinking agent (b1) having 22 or more functional groups, as long as the low-temperature curability of the positive photosensitive resin composition is not impaired. But that's fine.
  • crosslinking agents (b2) include, for example, 1,2-benzenedimethanol, 1,3-benzenedimethanol, 1,4-benzenedimethanol (paraxylene glycol), 1,3,5-benzenedimethanol , 4,4-biphenyldimethanol, 2,6-pyridinedimethanol, 2,6-bis(hydroxymethyl)-p-cresol, 4,4'-methylenebis(2,6-dialkoxymethylphenol) and other methylols Compounds having groups; phenols such as phloroglucide; 1,4-bis(methoxymethyl)benzene, 1,3-bis(methoxymethyl)benzene, 4,4'-bis(methoxymethyl)biphenyl, 3,4'- Having an alkoxymethyl group such as bis(methoxymethyl)biphenyl, 3,3'-bis(methoxymethyl)biphenyl, methyl 2,6-naphthalene dicarboxylate, 4,4'-methylenebis(2,6-dimethoxymethylphenol)
  • the content of the bifunctional or higher urea resin crosslinking agent (b1) is determined based on the total solid content of the positive photosensitive resin composition, from the viewpoint of improving the toughness during low temperature curing of the positive photosensitive resin composition. Preferably it is 50% by mass or more, more preferably 55% by mass or more, and still more preferably 60% by mass or more.
  • the content of the bifunctional or more functional urea resin crosslinking agent (b1) in the positive photosensitive resin composition is determined from the viewpoint of maintaining thermomechanical properties during low temperature curing of the positive photosensitive resin composition. It is preferably 90% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less, based on the total solid content of the resin composition.
  • the content of the crosslinking agent (B) in the positive photosensitive resin composition of the present embodiment is preferably determined based on the total solid content of the positive photosensitive resin composition from the viewpoint of improving toughness during low temperature curing. is 50% by mass or more, more preferably 55% by mass or more, still more preferably 60% by mass or more.
  • the content of the crosslinking agent (B) in the positive photosensitive resin composition is preferably determined based on the total solid content of the positive photosensitive resin composition from the viewpoint of maintaining thermomechanical properties during low temperature curing. is 90% by mass or less, more preferably 85% by mass or less, still more preferably 80% by mass or less.
  • the crosslinking agent (B) consists of the above-mentioned bifunctional or more functional urea resin crosslinking agent (b1) and other crosslinking agents (b2) used as necessary.
  • the positive photosensitive resin composition of this embodiment contains a photosensitizer (C) from the viewpoint of stably forming a cured film.
  • the photosensitizer (C) is an acid generator that generates acid by absorbing thermal energy or light energy.
  • the photosensitizer (C) is a thermal acid generator (c1) that generates acid by thermal energy or a photoacid generator (c2) that generates acid by light energy. Contains either or both.
  • a sulfonium compound or a salt thereof is preferably used.
  • the sulfonium compound or its salt is a sulfonium salt having a sulfonium ion as a cation moiety.
  • the anion moiety of the sulfonium compound or its salt is specifically a sulfonate ion such as a boride ion, antimony ion, phosphorus ion, or trifluoromethanesulfonate ion, and from the viewpoint of improving the reaction rate at low temperature. , preferably a boride ion or an antimony ion, more preferably a boride ion. These anions may have a substituent.
  • the sulfonium compound or its salt preferably includes a sulfonium salt represented by the following formula (4).
  • R 2 is a monovalent organic group, and from the viewpoint of improving reactivity at low temperatures, it is preferably a chain or branched hydrocarbon group or a benzyl group that may have a substituent, and more preferably is a benzyl group which may be substituted with an alkyl group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or a benzyl group whose aromatic ring portion may be substituted with a methyl group. It is the basis.
  • R3 is a monovalent organic group, and from the viewpoint of improving reactivity at low temperatures, it is preferably a chain or branched hydrocarbon group, more preferably an alkyl group having 1 to 4 carbon atoms. More preferably, it is a methyl group.
  • thermal acid generator (c1) include triphenylsulfonium salts such as triphenylsulfonium trifluoromethanesulfonate.
  • naphthoquinonediazide compounds As the photoacid generator (c2), naphthoquinonediazide compounds, diarylsulfonium salts, triarylsulfonium salts, dialkylphenacylsulfonium salts, diaryliodonium salts, aryldiazonium salts, aromatic tetracarboxylic acid esters, aromatic sulfonic acid esters, Examples include nitrobenzyl ester, aromatic N-oximide sulfonate, aromatic sulfamide, benzoquinone diazosulfonic acid ester, and the like. Among these, naphthoquinone diazide compounds are preferred.
  • the naphthoquinone diazide compound for example, a naphthoquinone diazide adduct of tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene, a naphthoquinone diazide adduct of tetrahydroxybenzophenone, etc. can be used.
  • the addition of naphthoquinonediazide can be produced, for example, by reacting o-quinonediazide sulfonyl chloride with a hydroxy compound or an amino compound.
  • the content of the photosensitizer (C) in the positive photosensitive resin composition is preferably 3 mass based on the total solid content of the positive photosensitive resin composition. % or more, more preferably 5% by mass or more, still more preferably 8% by mass or more. Further, the content of the photosensitizer (C) in the positive photosensitive resin composition is preferably 20% by mass or less based on the total solid content of the photosensitive resin composition, from the viewpoint of suppressing a decrease in reliability. It is more preferably 18 parts by mass or less, and still more preferably 16 parts by mass or less.
  • the photosensitizer (C) consists of a thermal acid generator (c1) and/or a photoacid generator (c2).
  • the positive photosensitive resin composition of the present embodiment preferably contains a combination of the above-mentioned thermal acid generator (c1) and photoacid generator (c2) as the photosensitizer (C). This improves the mechanical strength of the resulting cured product of the positive photosensitive resin composition.
  • the photosensitive resin composition contains a combination of a thermal acid generator (c1) and a photoacid generator (c2), the thermal acid generator (c1): photoacid expressed as a compounding ratio converted to their mass ratio
  • the amount of generator (c2) is, for example, 2:8 to 8:2, preferably 3:7 to 7:3, more preferably 4:6 to 6:4.
  • the positive photosensitive resin composition of this embodiment preferably contains a flexible epoxy resin (D). Thereby, the cured product of this photosensitive resin composition can have tensile strength at break within a desired range.
  • a flexible epoxy resin (D) an epoxy resin (d1) having an alkylene structure having an ether bond having 4 or more carbon atoms is preferably used.
  • the flexible epoxy resin (d1) is a compound in which part or all of the epoxy resin has a flexible structure selected from an alkylene structure having 2 to 20 carbon atoms and an alkylene structure having an ether bond having 2 to 20 carbon atoms. It is preferable that Examples of such flexible epoxy resins (d1) include EXA-4850-150, EXA-4816, and EXA-4822 (epoxy resins containing an alkylene structure having an ether bond); manufactured by ADEKA; EP-4000S, EP-4000SS, EP-4003S, EP-4010S, and EP-4011S (epoxy resins containing an alkylene structure with an ether bond); BEO-60E and BPO-20E (with an ether bond); (Epoxy resin containing an alkylene structure having an ether bond); Mitsubishi Chemical Corporation YX7105, YX7110, and YX7400 (epoxy resin containing an alkylene structure having an ether bond), and YX7180 (phenoxy resin containing an al
  • the content in the positive photosensitive resin composition is determined based on the total solid content of the positive photosensitive resin composition, from the viewpoint of improving toughness during low temperature curing.
  • the content is preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more.
  • the content of the flexible epoxy resin (d1) in the positive photosensitive resin composition is preferably set relative to the total solid content of the photosensitive resin composition. is 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less.
  • the positive photosensitive resin composition of the present embodiment may contain an epoxy resin (d2) other than the above-mentioned epoxy resin (d1).
  • epoxy resins (d2) include bisphenol A phenoxy resin, bisphenol F phenoxy resin, bisphenol S phenoxy resin, bisphenolacetophenone phenoxy resin, novolak phenoxy resin, biphenyl phenoxy resin, fluorene phenoxy resin, Examples include cyclopentadiene type phenoxy resin, norbornene type phenoxy resin, naphthalene type phenoxy resin, anthracene type phenoxy resin, adamantane type phenoxy resin, terpene type phenoxy resin, and trimethylcyclohexane type phenoxy resin.
  • adhesion aid (E) The positive photosensitive resin composition of this embodiment preferably contains an adhesion aid (E). Thereby, for example, adhesion to the substrate can be further improved.
  • the adhesion aid (E) is not particularly limited.
  • an amino group-containing silane coupling agent an epoxy group-containing silane coupling agent, a (meth)acryloyl group-containing silane coupling agent, a mercapto group-containing silane coupling agent, a vinyl group-containing silane coupling agent, a ureido group-containing silane cup
  • a silane coupling agent such as a ring agent or a sulfide group-containing silane coupling agent can be used.
  • a silane coupling agent one type may be used alone, or two or more types may be used in combination.
  • amino group-containing silane coupling agents include bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropyltrimethoxysilane, and ⁇ -aminopropylmethyldiethoxy.
  • Silane ⁇ -aminopropylmethyldimethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropyltrimethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropyltriethoxysilane, N- ⁇ (aminoethyl) ⁇ -amino Examples include propylmethyldimethoxysilane, N- ⁇ (aminoethyl) ⁇ -aminopropylmethyldiethoxysilane, and N-phenyl- ⁇ -amino-propyltrimethoxysilane.
  • epoxy group-containing silane coupling agent examples include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropylmethyldiethoxysilane, ⁇ -(3,4-epoxycyclohexyl)ethyltrimethoxysilane, ⁇ -glycidyl Examples include propyltrimethoxysilane.
  • Examples of (meth)acryloyl group-containing silane coupling agents include ⁇ -((meth)acryloyloxypropyl)trimethoxysilane, ⁇ -((meth)acryloyloxypropyl)methyldimethoxysilane, ⁇ -((meth) Examples include acryloyloxypropyl)methyldiethoxysilane.
  • Examples of the mercapto group-containing silane coupling agent include 3-mercaptopropyltrimethoxysilane.
  • Examples of the vinyl group-containing silane coupling agent include vinyltris( ⁇ -methoxyethoxy)silane, vinyltriethoxysilane, and vinyltrimethoxysilane.
  • Examples of the ureido group-containing silane coupling agent include 3-ureidopropyltriethoxysilane.
  • Examples of the sulfide group-containing silane coupling agent include bis(3-(triethoxysilyl)propyl)disulfide, bis(3-(triethoxysilyl)propyl)tetrasulfide, and the like.
  • Examples of the acid anhydride-containing silane coupling agent include 3-trimethoxysilylpropylsuccinic anhydride, 3-triethoxysilylpropylsuccinic anhydride, 3-dimethylmethoxysilylpropylsuccinic anhydride, and the like.
  • adhesion aids include not only silane coupling agents, but also titanium coupling agents, zirconium coupling agents, and the like.
  • an adhesion aid When an adhesion aid is used, it may be used alone or two or more adhesion aids may be used in combination. When an adhesion aid is used, its content is preferably 0.3 to 15 parts by mass, more preferably 0.4 to 12 parts by mass, and even more preferably 0.5 parts by mass, per 100 parts by mass of the phenolic resin (A). ⁇ 10 parts by mass.
  • the positive photosensitive resin composition of this embodiment can contain a surfactant.
  • a surfactant By including a surfactant, wettability during coating can be improved and a uniform resin film and cured film can be obtained.
  • the surfactant include fluorine surfactants, silicone surfactants, alkyl surfactants, and acrylic surfactants.
  • the surfactant preferably contains a surfactant containing at least one of a fluorine atom and a silicon atom. This contributes to obtaining a uniform resin film (improving coating properties), improving developability, and improving adhesive strength.
  • a surfactant for example, a nonionic surfactant containing at least one of a fluorine atom and a silicon atom is preferable.
  • F-251, F-253, F-281, F-430, F-477, F-551 of the "Megafac" series manufactured by DIC Corporation F-552, F-553, F-554, F-555, F-556, F-557, F-558, F-559, F-560, F-561, F-562, F-563, F- 565, F-568, F-569, F-570, F-572, F-574, F-575, F-576, R-40, R-40-LM, R-41, R-94, etc.
  • Fluorine-containing oligomer structure surfactants fluorine-containing nonionic surfactants such as Ftergent 250 and Ftergent 251 manufactured by Neos Co., Ltd., SILFOAM (registered trademark) series manufactured by Wacker Chemie (for example, SD 100 TS) , SD 670, SD 850, SD 860, SD 882) and the like.
  • the photosensitive resin composition can contain one or more surfactants.
  • the amount thereof is, for example, 0.001 to 1 part by mass, preferably 0.005 to 0.5 part by mass, per 100 parts by mass of the phenolic resin (A). .
  • the positive photosensitive resin composition of this embodiment preferably contains a solvent. Thereby, a photosensitive resin film can be easily formed on the stepped substrate by a coating method.
  • the positive photosensitive resin composition of this embodiment contains a solvent
  • the positive photosensitive resin composition of this embodiment is, for example, varnish-like.
  • the solvent usually includes an organic solvent.
  • the organic solvent is not particularly limited as long as it can dissolve or disperse each of the above-mentioned components and does not substantially chemically react with each component.
  • organic solvents examples include acetone, methyl ethyl ketone, toluene, propylene glycol methyl ethyl ether, propylene glycol dimethyl ether, propylene glycol 1-monomethyl ether 2-acetate, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and benzyl.
  • examples include alcohol, propylene carbonate, ethylene glycol diacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, dipropylene glycol methyl-n-propyl ether, butyl acetate, and ⁇ -butyrolactone. These may be used alone or in combination.
  • the concentration of nonvolatile components in the positive photosensitive resin composition is preferably 30 to 75% by mass, more preferably 35 to 70% by mass. By setting it as this range, each component can be fully dissolved or dispersed. In addition, good coating properties can be ensured, which in turn leads to improved flatness during spin coating. Furthermore, by adjusting the content of nonvolatile components, the viscosity of the positive photosensitive resin composition can be appropriately controlled.
  • the positive photosensitive resin composition of the present embodiment may contain components other than the above-mentioned components, if necessary.
  • examples of such components include antioxidants, fillers such as silica, sensitizers, film-forming agents, and the like.
  • the positive photosensitive resin composition of this embodiment has a tensile strength at break of 100 MPa or more of a cured product obtained by curing the positive photosensitive resin composition at 180°C. I can do it.
  • the lower limit of the tensile breaking strength of the cured film of the positive photosensitive resin composition of this embodiment is 100 MPa or more, preferably 105 MPa or more, more preferably 110 MPa, from the viewpoint of suppressing tensile brittle fracture. % or more.
  • the upper limit of the tensile strength at break of the cured film is, for example, 200 MPa or less, preferably 180 MPa or less, and more preferably 150 MPa or less.
  • the positive photosensitive resin composition of the present embodiment has a tensile elongation rate of a cured film of the positive photosensitive resin composition of 20% or more, as measured under Condition 1 below. can do.
  • (Condition 1) (i) The positive photosensitive resin composition is cured at 200° C. for 180 minutes to form the cured film, and a 6.5 mm x 20 mm x 10 ⁇ m thick sample is prepared from the cured film. (ii) Based on JIS K7161, perform a tensile test on the sample at 23° C. and a test speed of 5 mm/min to determine the tensile elongation rate.
  • the lower limit of the tensile elongation rate of the cured film of the positive photosensitive resin composition of this embodiment is 20% or more, preferably 25% or more, more preferably, from the viewpoint of suppressing brittle fracture. It is 30% or more, and even more preferably 40% or more.
  • the upper limit of the tensile elongation rate of the cured film is 100% or less, preferably 190% or less, more preferably 80% or less, and even more preferably is 70% or less.
  • the glass transition temperature (Tg) of the cured product of the positive photosensitive resin composition is preferably 200°C or higher, more preferably 220°C or higher, from the viewpoint of improving heat resistance. Further, from the viewpoint of suppressing deterioration of brittleness, the glass transition temperature of the cured product of the positive photosensitive resin composition is preferably 300°C or lower, more preferably 280°C or lower, and even more preferably 260°C or lower. .
  • the Tg of the cured product of the positive photosensitive resin composition is measured using a thermomechanical analyzer (TMA) on a predetermined test piece (width 3 mm x length 10 mm x thickness 0.005 to 0.015 mm). It is calculated from the results of measurements conducted using the following conditions: a starting temperature of 30°C, a measurement temperature range of 30 to 440°C, and a heating rate of 10°C/min.
  • TMA thermomechanical analyzer
  • a resin film is obtained by curing the photosensitive resin composition in this embodiment.
  • the resin film in this embodiment is a dried film or a cured film of a photosensitive resin composition. That is, the resin film is formed by drying or curing a photosensitive resin composition, preferably by making the photosensitive resin composition effective.
  • This resin film is used to form a resin film for electronic devices, such as a permanent film or a resist. Among these, it is preferable to use it in applications using permanent films from the viewpoints of obtaining a resin film at low temperatures, excellent workability, and obtaining a resin film with excellent reliability.
  • a resin film obtained using a photosensitive resin composition has excellent processability or reliability, which is required for a resin film useful for manufacturing electronic devices, etc. It is also possible to obtain.
  • the permanent film is composed of a resin film obtained by pre-baking, exposing and developing a photosensitive resin composition, patterning it into a desired shape, and then curing it by post-baking.
  • the permanent film can be used as a protective film for electronic devices such as a buffer coat film, an interlayer film such as an insulating film for rewiring, a dam material, and the like.
  • a resist is made by applying a negative photosensitive resin composition to an object to be masked by the resist using a method such as spin coating, roll coating, flow coating, dip coating, spray coating, or doctor coating. It is composed of a resin film obtained by removing the solvent from a resin composition.
  • FIG. 1 is a cross-sectional view showing a configuration example of an electronic device having a resin film according to the present embodiment.
  • the electronic device 100 shown in FIG. 1 can be an electronic device including the resin film described above.
  • one or more of the group consisting of the passivation film 32, the insulating layer 42, and the insulating layer 44 can be made of a resin film.
  • the resin film is preferably the above-mentioned permanent film.
  • the electronic device 100 is, for example, a semiconductor chip. In this case, for example, a semiconductor package can be obtained by mounting the electronic device 100 on a wiring board via the bumps 52.
  • the electronic device 100 includes a semiconductor substrate provided with semiconductor elements such as transistors, and a multilayer wiring layer (not shown) provided on the semiconductor substrate.
  • An interlayer insulating film 30 and an uppermost layer wiring 34 provided on the interlayer insulating film 30 are provided in the uppermost layer of the multilayer wiring layer.
  • the uppermost layer wiring 34 is made of aluminum Al, for example.
  • a passivation film 32 is provided on the interlayer insulating film 30 and the uppermost layer wiring 34. A part of the passivation film 32 is provided with an opening through which the uppermost layer wiring 34 is exposed.
  • a rewiring layer 40 is provided on the passivation film 32.
  • the rewiring layer 40 includes an insulating layer 42 provided on the passivation film 32, a rewiring 46 provided on the insulating layer 42, an insulating layer 44 provided on the insulating layer 42 and the rewiring 46, has.
  • An opening connected to the uppermost layer wiring 34 is formed in the insulating layer 42 .
  • the rewiring 46 is formed on the insulating layer 42 and in an opening provided in the insulating layer 42, and is connected to the uppermost layer wiring 34.
  • the insulating layer 44 is provided with an opening connected to the rewiring 46 .
  • a bump 52 is formed in the opening provided in the insulating layer 44 via, for example, a UBM (under bump metallurgy) layer 50.
  • the electronic device 100 is connected to a wiring board or the like via bumps 52, for example.
  • Examples 1 to 7, Comparative Example 1 A photosensitive resin composition was prepared according to the formulation shown in Table 1. Specifically, first, each component formulated according to Table 1 was stirred and mixed in a nitrogen atmosphere, and then filtered through a polyethylene filter with a pore size of 0.2 ⁇ m to obtain a varnish-like photosensitive resin composition. . Details of each component listed in Table 1 are shown below.
  • Phenol resin (A)) (Biphenyl type phenolic resin (a1))
  • phenolic resin a1-1) 186.2 g (1.00 mol) of 4,4'-biphenol and 86.2 g (1.00 mol) of p-cresol were placed in a four-neck glass round-bottomed flask equipped with a thermometer, stirrer, raw material inlet, and dry nitrogen gas inlet.
  • Crosslinking agent (B) (Urea resin crosslinking agent (b1))
  • ⁇ Crosslinking agent b1-1 1,3,4,6-tetrakis(methoxymethyl)glycoluril, manufactured by Daito Chemix Co., Ltd., CROLIN-318
  • Crosslinking agent b1-2 1,3,4,6-tetrakis(butoxymethyl)glycoluril, manufactured by Sanwa Chemical Co., Ltd.
  • Nikalac MX-279 Crosslinking agent b1-3: 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolinone, manufactured by Sanwa Chemical Co., Ltd., Nikalac MX-280 (Epoxy resin crosslinking agent (b2))
  • Crosslinking agent b2-1 Phenoxy type epoxy resin, manufactured by Mitsubishi Chemical Corporation
  • Crosslinking agent b2-2 Epoxy resin (bisphenol A type phenoxy), manufactured by Mitsubishi Chemical Corporation, JER-1256 Crosslinking agent b2
  • Thermal acid generator (c1) (Thermal acid generator (c1)) ⁇ Thermal acid generator c1-1: Compound represented by formula (c1-1) (SAN-AID SI-150, manufactured by Sankegaku Co., Ltd.) (Photoacid generator (c2)) ⁇ Photoacid generator c2-1: 3-diazo-3,4- of 4,4'-(1- ⁇ 4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl ⁇ ethylidene)diphenol Dihydro-4-oxo-1-naphthalenesulfonic acid ester, manufactured by Daito Chemix Co., Ltd., DS-427,
  • Adhesion aid 3-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403E
  • surfactant Fluorine surfactant, manufactured by 3M Japan, FC4432 (10% GBL) (solvent)
  • Solvent 1 ⁇ -butyrolactone, manufactured by Sanwa Yuka Kogyo Co., Ltd.
  • Tg Glass transition temperature
  • CTE coefficient of linear expansion
  • a cured film of the photosensitive resin composition obtained in each example was produced at 180° C. for 120 minutes, and a test piece with a width of 3 mm x length of 10 mm x thickness of 10 mm was obtained from the obtained cured film.
  • the test pieces of each example were analyzed using a thermomechanical analyzer (TMA, manufactured by Seiko Instruments Inc., SS6000) under conditions of a starting temperature of 30°C, a measurement temperature range of 30 to 440°C, and a heating rate of 10°C/min. Measurements were carried out, and from the measurement results, Tg (°C) and linear expansion coefficient (ppm/°C) in the temperature range of 50 to 100°C were determined. The results are shown in Table 1.
  • the development time was adjusted so that the difference between the film thickness after pre-baking and the film thickness after development was 1.0 ⁇ m, and the puddle was applied twice.
  • the exposed area was dissolved and removed by development, it was rinsed with pure water for 10 seconds.
  • the resolution of the line pattern was evaluated using a pattern exposed with an energy of the minimum exposure amount + 100 mJ/cm 2 to form a pattern of 100 ⁇ m square via holes. Regarding the resolution, it was confirmed whether the openings were formed in a line pattern with an interval of 10 ⁇ m. Table 1 indicates that the opening is marked as "A", and the case of not opening is marked as "B".

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  • Spectroscopy & Molecular Physics (AREA)
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  • Phenolic Resins Or Amino Resins (AREA)
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JP2019053220A (ja) * 2017-09-15 2019-04-04 住友ベークライト株式会社 感光性樹脂組成物、半導体装置および電子機器

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