WO2007034902A1 - 樹脂組成物、ワニス、樹脂膜および半導体装置 - Google Patents
樹脂組成物、ワニス、樹脂膜および半導体装置 Download PDFInfo
- Publication number
- WO2007034902A1 WO2007034902A1 PCT/JP2006/318790 JP2006318790W WO2007034902A1 WO 2007034902 A1 WO2007034902 A1 WO 2007034902A1 JP 2006318790 W JP2006318790 W JP 2006318790W WO 2007034902 A1 WO2007034902 A1 WO 2007034902A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- formula
- bis
- benzoxazole
- resin
- Prior art date
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- 239000011347 resin Substances 0.000 title claims abstract description 191
- 229920005989 resin Polymers 0.000 title claims abstract description 191
- 239000011342 resin composition Substances 0.000 title claims abstract description 65
- 239000004065 semiconductor Substances 0.000 title claims description 50
- 239000002966 varnish Substances 0.000 title claims description 22
- -1 dicarboxylic acid compound Chemical class 0.000 claims abstract description 169
- 239000002243 precursor Substances 0.000 claims abstract description 160
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 claims abstract description 147
- 150000001875 compounds Chemical class 0.000 claims abstract description 101
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 41
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 84
- 125000000524 functional group Chemical group 0.000 claims description 72
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical group C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 claims description 45
- 239000011229 interlayer Substances 0.000 claims description 44
- 239000000203 mixture Substances 0.000 claims description 37
- 229920002577 polybenzoxazole Polymers 0.000 claims description 29
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- 125000000962 organic group Chemical group 0.000 claims description 25
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 23
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 18
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 claims description 15
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 claims description 13
- 239000003960 organic solvent Substances 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 12
- 230000001681 protective effect Effects 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 10
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- 239000004971 Cross linker Substances 0.000 claims description 6
- 238000005530 etching Methods 0.000 claims description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- 238000007363 ring formation reaction Methods 0.000 claims description 4
- LBVBDLCCWCJXFA-UHFFFAOYSA-N adamantane-1,2-dicarboxylic acid Chemical group C1C(C2)CC3CC1C(C(=O)O)C2(C(O)=O)C3 LBVBDLCCWCJXFA-UHFFFAOYSA-N 0.000 claims description 3
- 125000002837 carbocyclic group Chemical group 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
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- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 claims 1
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- MPXKIFWZOQVOLN-UHFFFAOYSA-N 1-(1-adamantyl)adamantane Chemical compound C1C(C2)CC(C3)CC2CC13C(C1)(C2)CC3CC2CC1C3 MPXKIFWZOQVOLN-UHFFFAOYSA-N 0.000 description 43
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 30
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- ZICQBHNGXDOVJF-UHFFFAOYSA-N diamantane Chemical group C1C2C3CC(C4)CC2C2C4C3CC1C2 ZICQBHNGXDOVJF-UHFFFAOYSA-N 0.000 description 28
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 28
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 13
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 13
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 12
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- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 11
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N 1-naphthalen-1-ylnaphthalene Chemical group C1=CC=C2C(C=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 11
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- 230000009477 glass transition Effects 0.000 description 10
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 10
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02118—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer carbon based polymeric organic or inorganic material, e.g. polyimides, poly cyclobutene or PVC
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/22—Polybenzoxazoles
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/01—Hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02203—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being porous
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- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
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- H01L21/02205—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
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- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
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- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/0226—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
- H01L21/02282—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/314—Inorganic layers
- H01L21/316—Inorganic layers composed of oxides or glassy oxides or oxide based glass
- H01L21/31695—Deposition of porous oxides or porous glassy oxides or oxide based porous glass
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/269—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension including synthetic resin or polymer layer or component
Definitions
- the present invention relates to a resin composition, a varnish, a resin film and a semiconductor device.
- an oxide film (SiOx film) manufactured by a CVD method (chemical vapor deposition method) or the like is mainly used as an interlayer insulating film for semiconductor.
- inorganic insulating films such as oxide films have a high dielectric constant, and it is difficult to cope with speeding up and high performance of semiconductors. Therefore, application of an organic material is being studied as an interlayer insulating film having a low dielectric constant.
- the organic material used for the interlayer insulating film is required to be excellent in heat resistance, electrical characteristics and low in dielectric constant.
- polyimide resins have problems such as low heat resistance, high dielectric constant, and high hygroscopicity. Therefore, its use has been limited to some semiconductor devices such as bipolar semiconductor devices in terms of reliability.
- polyquinoline resin and polyquinoxaline resin which have higher heat resistance, lower dielectric constant and lower hygroscopicity than polyimide resin are thermoplastic resins, and therefore, they have a glass transition temperature higher than that of resin. When exposed to temperature, the resin pattern may be deformed, which may cause problems in semiconductor manufacturing.
- Patent Document 1 Japanese Unexamined Patent Application Publication No. 2000-195853
- An object of the present invention is to provide a resin composition having a low dielectric constant and excellent heat resistance.
- Another object of the present invention is to provide a resin film having a low dielectric constant and excellent heat resistance, and a semiconductor device using the same.
- a fat composition comprising a benzoxazole resin precursor having a first repeating unit obtained by reacting a bisaminophenol complex and a dicarboxylic acid complex, and a crosslinker.
- the benzoxazole resin precursor has a diamondoid structure, a V, a bisaminophenol compound, and a dicarboxylic acid composite without a diamondoid structure.
- the diamondoid structure is selected from a Adamantyl group, Diamantyl group, Triamantyl group, Tetramantyl group, Tetramantyl group, Pentamantyl group, Hexamantyl group, Heptamantyl group, Octamantyl group, Nonamantyl group, Decamantyl group, Undantyl mantyl group, Biadamantyl group, A group consisting of triadamantyl group, tetraadamantyl group, pentaadamantyl group, hexaadamantyl group, heptaadamantyl group, octaadamantyl group, nonadamantyl group, nonadamantyl group, decadamantyl group and undecaadamantyl group
- the resin composition according to any one of the items (1) to (5), which is at least one group selected.
- the dicarboxylic acid having a diamondoid structure is adamantanedicarboxylic acid, biadamantanedicarboxylic acid or tetraadamantanedicarboxylic acid.
- a resin composition comprising a benzoxazole resin precursor having a third repeating unit represented by the following formula (1) and a crosslinking agent.
- R and R each independently represent a hydrogen atom or an organic group, and k is 2 to 1,000.
- (Adm in the formula (2-1) and the formula (2-2) indicates a diamondoid structural unit based on an adamantane structure, a is 2 or more and 12 or less, p is 1 or more and 12 or less, i is 1 or more Top 12 or less. r is 0 or 1.
- Adm represents a diamondoid structural unit based on an adamantane structure, p is 1 or more and 12 or less; X is an ethynyl group or a propargyl ether group; Z is
- aromatic group binaphthalene group, naphthalene group, fluorene group, phenyl group, diphenyl ether group, biphenyl group, diphenyl sulfone group, diphenyl propane group, and di-phenyl propane group And an aromatic group having a valence of 3 or more (for example, a binaphthalene group or a naphthalene group as the aromatic group having a valence of 3 or more).
- R represents an organic group (as the organic group, a binaphthalene group, a naphthalene group, a fluorene group, a phenyl group, a diphenyl ether group, a biphenyl) Groups such as, but not limited to, groups, disulfone groups, diphenylpropane groups, and difluorhexane groups, etc.
- a resin composition comprising a benzoxazole precursor having a fourth repeating unit represented by the following formula (10) and a crosslinking agent.
- R and R each independently represent a hydrogen atom or an organic group, m is 2 to 1,00
- X is one group selected from the group consisting of the group represented by the above formula (2-1), the above formula (2-2) and the above formula (3); and in the formula (10) Y is the following formula (11 1) and formula (11
- Adm represents a diamondoid structural unit based on an adduct structure, and p is 1 or more. I is 1 or more and 12 or less.
- the hydrogen atom on the included carbocyclic ring may be substituted with an alkyl group and z or a fluoroalkyl group.
- a resin composition comprising a benzoxazole resin precursor having a fifth repeating unit represented by the following formula (13), and a crosslinking agent.
- [R and R in Formula (13) are each independently a hydrogen atom or an organic group, n is 2 to 1,00
- X is an ecul group or a propargyl ether group
- Z is SO 2
- Is a binaphthalene group, a naphthalene group, a fluorene group, a phenyl group or a diphenyl ether group A biphenyl group, a diphenyl sulfone group, a diphenyl propane group, and a diphenyl hexafluoro propane group and the like, but is not limited thereto;
- Ar is a trivalent or higher aromatic group As the aromatic group having a higher valency, to binaphthalene group, naphthalene group, fluorene group, fluoro group, diphenyl ether group, biphenyl group, diphenyl sulfone group, diphenyl propane group, and diphenyl group
- R is hydrogen or an organic group (for the organic group, it is a binaphthalene group, a naphthalene group, a fluorene group, a phenyl group, a diphenyl ether, etc.
- a group consisting of a group represented by at least one group selected
- Y is: the formula (111), the formula (112), the formula (12-1) and the above
- the hydrogen atom on the carbon ring contained in 2 may be substituted with an alkyl group and Z or a fluoroalkyl group.
- [R and R in Formula (17) are each independently a hydrogen atom or an organic group, n is 2 to 1,00
- X is a small number selected from the intermediate powers of the above-mentioned formulas (14) and (15)
- Y in the formula (17) is: the formula (4), the formula (6-1), the formula (6-2), the formula (7-1), the formula (7) 2) at least one group selected from among those represented by the above formula (8) and the above formula (9).
- the hydrogen atom on the carbon ring contained in 1 may be substituted with an alkyl group and Z or a fluoroalkyl group.
- a benzoxazole resin precursor having the third repeating unit represented by the above formula (1), and a benzoxazole resin having the fourth repeating unit represented by the above formula (10) A benzoxazole lipid precursor, which comprises the precursor or the benzoxazole lipid precursor having the fifth repeating unit represented by the above formula (13) as an essential component, and the third repeating unit, Of a benzoxazole fat precursor having the repeating unit, a benzoxazole fat precursor having the fifth repeating unit, and a benzoxazole having the sixth repeating unit represented by the above formula (17)
- a fat composition comprising a benzoxazole fat precursor composition comprising two or more selected from a fat precursor power, and a crosslinking agent.
- a varnish comprising the resin composition according to any one of (1) to (22) and an organic solvent capable of dissolving or dispersing these.
- a resin film characterized by comprising the resin composition according to any one of items (1) to (22).
- a resin composition having a low dielectric constant and excellent heat resistance can be obtained.
- a resin film having a low dielectric constant and excellent heat resistance and a semiconductor device using the same can be obtained.
- FIG. 1 is a cross-sectional view schematically showing an example of a semiconductor device of the present invention.
- 1 is a semiconductor substrate
- 2 is a silicon nitride film
- 3 is an interlayer insulating film
- 4 is a copper wiring layer
- 5 is a modifying layer
- 6 is a barrier layer
- 7 is a hard mask layer
- 100 is a semiconductor device. .
- the resin composition of the present invention comprises a benzoxazole resin precursor and a crosslinking agent.
- the benzoxazole resin precursor is a first repeating unit obtained by reacting a bisaminophenol compound with a dicarboxylic acid compound, which has a diamondoid structure in at least one of them. Is included.
- the fat composition of the present invention may contain a polybenzoxazole salt obtained by dehydrating and ring-closing reaction of the benzoxazole fat precursor described above.
- the resin film of the present invention is composed of the resin composition described above.
- a semiconductor device of the present invention has the above-described resin film.
- the benzoxazole fat precursor used in the present invention is at least either one or more of them. It comprises a first repeating unit obtained by reacting a bisaminophenol complex and a dicarboxylic acid complex having a cadmiumoid structure.
- a repeating unit obtained by reacting a bisaminophenol complex having a diamondoid structure with a dicarboxylic acid compound having no diamondoid structure, or a bisaminophenol complex having no diamondoid structure, and a diamondoid A repeating unit obtained by reacting a dicarboxylic acid complex having a structure, obtained by reacting a bisaminophenol complex having a diamondoid structure and a dicarboxylic acid complex having a diamondoid structure It contains the repeating unit.
- the diamondoid structure may have a functional group other than the diamondoid structure.
- an acetylene group is particularly preferred, which is preferably a functional group that forms a crosslink.
- the bisaminopheno-monoileide compound not having the diamondoid structure and the ⁇ dicarboxylic acid compound not having the diamondoid structure at least one has a functional group other than the diamondoid structure.
- a benzoxazole resin precursor having a diamondoid structure can be obtained, and the benzoxazole resin from which the benzoxazole resin precursor can also be obtained has heat resistance and a high elastic modulus. And low dielectric constant.
- the moisture resistance can be improved.
- the diamondoid structure is preferably a group having an alkyl group or a fluoroalkyl group, whereby the solubility in an organic solvent is further improved.
- the diamondoid structure in the present invention refers to a structural unit having an adamantane structure as the minimum unit, and as a group having this structure, for example, adamantyl group, diamantyl group, triamantyl group, tetramantyl group, pentamantyl group, hexamantyl group And groups having a polycyclic skeleton structure such as heptamantyl group, octamantyl group, nonamantyl group, decamantyl group, decamantyl group and undity mantyl group, and further, groups having a plurality of groups having the above-mentioned polycyclic skeleton structure, etc. It can be mentioned.
- Examples of the group having a plurality of groups having a polycyclic skeleton structure include groups having an oligo structure or a poly structure, and in the case of an adamantyl group as the group having a polycyclic skeleton structure, for example, di ( Biadamantyl groups such as 1, 3-adamantane) group and di (2, 2-adamantane) group, triadamantyl groups such as tri (1, 3- adamantane) group and tri (2, 2-adamantane) group, tetra Tetra-adamantyl groups such as (1, 3-adamantane) group and tetra (2, 2-adamantane) group; pentamantamanyl groups such as penta (1, 3-adamantane) group and penta (2, 2-adamantane) group; hepta Heptamantyl group such as (1, 3-adamantane) group and hepta (2, 2-adamantane) group, hex
- a group having the oligodamantane structure or a group having a polyadamantane structure substituted with the adamantyl group For example, bee (diamantane) group, tri-one (diamantane) group, tetra-one (diamantane) group, penta- one (diamantane) group, hexa- one (diamantane) group, hepta-one (diamantane) group, Groups having a plurality of diamantane groups such as mono (diamantane) group, nonar (diamantane) group, decah (diamantane) group and undecker (diamantane) group, etc., bee (triamantane) group, trii (triamantane) Group, tetra (triamantane)
- the benzoxazole resin precursor having these structures can maintain the heat resistance of the resulting polybenzoxazole resin, lower the dielectric constant, and improve the moisture resistance.
- Groups having the above-mentioned adamantane structure include alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and tert-butyl group, fluoromethyl group, fluoroethyl group, fluoropropyl group and fluorobutyl group. Even fluoroalkyl groups such as, etc. may be bonded.
- examples of the diamondoid structure having a diamondoid structure as the functional group other than the diamondoid structure include, for example, adamanchirechul group, aiamanchilechul group, a triamanchilechul group, and tetraman.
- a functional group having a diamondoid structure other than the above ethynyl group a functional group having an acetylene bond, biphenylene group, cyanato group, maleimido group, nadiimide group, vinyl group and cyclopentadiene group can be mentioned.
- a functional group having an acetylene bond, biphenylene group, cyanato group, maleimido group, nadiimide group, vinyl group and cyclopentadiene group can be mentioned.
- What has the said diamondoid structure as functional groups, such as a genyl group is mentioned.
- the diamondoid structure of functional groups other than the above-mentioned diamondoid structure is a methyl group, an ethyl group, an n propyl group, an isopropyl group, an n butyl group, an alkyl group such as isobutyl group and tert butyl group, a fluoromethyl group, a fluoroetyl group, a fluoroopro It may be bonded with a fluoroalkyl group such as a pill group and a fluorobutyl group.
- adamanchiruhe-ruetul group dimethyladamantchiferu-ruetul group, trimethyladamanthierue-ruetul group, biadamantylue-ruetul group, tetramethylbiadamantylje-ruetul group, pentamethylbiamantyljeh- Ruthel group, Adamamanthyl henoxy phe-ruetul group, Dimethyladamantyl phe-ruetul group, Trimethyladamantyl phe-ruetul group, Biadamantyl fenoxy phe ruetul group, tetramethyl biadamantyl hen
- a sieve-ruetul group a pentamethyl biadamantyl phenoxiphe-ruetul group and the like are preferable.
- examples of the functional group other than the diamondoid structure include Examples thereof include functional groups having a chilen bond, biphenyl group, cyanato group, maleimide group, nadiimide group, bule group and cyclopentagel group, and the like, and a group capable of crosslinking with the above-mentioned crosslinking agent is preferable.
- a group capable of crosslinking with the above-mentioned crosslinking agent is preferable.
- functional groups having an acetylene bond are preferred.
- Specific examples of the functional group having an acetylene bond include an ecthul group, a ferr etul group, a naphthylethynyl group, an anthryl etul group, a quinolyl ethul group, a quinoxalyl ether, an alkylethynyl group and a propargyl ether group. It can be mentioned.
- preferred is one or more functional groups selected from the medium powers of ethynyl group, phenylethynyl group and naphthylethynyl group.
- the heat resistance of the polybenzoxazole resin is improved because the crosslink density of the obtained polybenzoxazole resin can be improved by having a functional group in the benzoxazole resin precursor. is there. Furthermore, when the crosslink density of polybenzoxazole resin is improved, the nanofoam condenses when an interlayer insulating film is obtained by forming a nanofoam using strong polybenzoxazole resin. It becomes possible to maintain the shape without. Thereby, the dielectric constant of the interlayer insulating film can be reduced.
- the bisaminophenol compound having a diamondoid structure is a compound having a unit structure of diamond in the molecule, and a compound having a diamondoid structure in a bisaminophenol skeleton, and a bisaminophenol compound.
- the diamondoid structure is bonded to the skeleton directly or through another atom, and the like.
- Examples of the bisaminophenol compound include
- compounds having the minimum unit of a diamondoid structure such as damantane and bis (4-amino-3-hydroxy-phenoxyphenyl) adamantane can be mentioned, and among these, 1,3-bis (3-amino 4-hydroxyl- And the like.
- bis (3-amino-4-hydroxy-mono) diamantane, bis (3-hydroxy-4-amino-mono-phenyl) diamantane, bis (3-amino-1) are preferred.
- the compound having an oligo structure having a plurality of groups having a polycyclic skeleton structure for example, 6, 6, 1 bis (3 amino-4 hydroxyl one gel) 1, 1, 1 bi (diamantane) 6, 6'- Bis (3 amino-4-hydroxy monophenoxy) -1, 1 'bi (diamantane) 6, 6, 1 bis [4- (3-hydroxy mono 4-amino phenoxy) 1 Hue Nole] — 1, 1, — (1) (bimantane), etc. Forces are not limited to this as long as they are within the definition of diamondoid structure.
- the bonding position of the group having a polycyclic skeleton structure is not limited to this.
- the group having an adamantane structure in the above-mentioned bisphenol compound is an alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and tert-butyl group, and trifluoromethyl group.
- alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and tert-butyl group, and trifluoromethyl group.
- Fluoroalkyl groups such as fluoroethyl group, fluoropropyl group and fluorobutyl group etc. are combined, etc.! Examples of these compounds are
- These bisaminophenol compounds may be used alone or in combination of two or more.
- a Friedel-Crafts reaction of di-port moadamantane with phenol is preferable.
- a Friedel-Crafts reaction of di-port moadamantane with phenol is preferable.
- bis (3-amino-4-hydroxyphenyl) 1,3 adamantane can be synthesized.
- bis- (4-hydroxy-phenyl) -1,3-adamantane and 4-tol- 3-benzyloxy- 1-fluorobenzene are reacted with each other in ether to further deprotect the benzyloxy group and reduce the nitro group.
- examples of bisaminophor compounds having a diamondoid structure via an ethynyl group are:
- 3,3'-diamino-4,4'-dihydroxy 6,6 one-bisadamanthyl dithiophenyl sulfone, 3,3, -dihydroxy 4,4'-diamino- 6,6 one-bis-diamanthyl-thru-diphenyl Bisaminophenol compounds having a sulfone and an ethynyl-diphenyl sulfone such as 3,3'-diamino-4,4'-dihydroxy-2,2'-bis-triamitolethynyl-diphenyl sulfone:
- the group having an adamantane structure in the above-mentioned bisphenol compound is an alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and tert-butyl group, and trifluoromethyl group.
- alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and tert-butyl group, and trifluoromethyl group.
- Fluoroalkyl groups such as fluoroethyl group, fluoropropyl group and fluorobutyl group etc. are combined, etc.!
- a method for introducing a functional group having a diamondoid structure into a bisaminophenol complex for example, in the case of an etul group having a diamondoid structure, Mention may be made of the method of coupling reaction of ruadamantane with halogen compounds. Specifically, it is based on the coupling reaction of a halogeno compound having a phorsohydroxy-trobenzene structure with ethynylamantane, and the amination reaction is reduced without reducing the acetylene bond by the selection of the optimum catalyst. By carrying out the reaction, it is possible to introduce an adamantyletinyl group into the bisaminophenol compound.
- Examples of bisaminophenol complex having a functional group other than diamondoid structure include: 2, 2, 1 bis (one) 3 Hydroxy-4-aminophenoxyl) 6, 6, 1-bis-ethynyl-1, 1, -binaphthalene and 2, 2, 1-bis- (3 hydroxy-4 amino-phenoxy) 6, 6, 1-bis-phene-nore 1, 1, -binaphthalene Bisaminophenol compounds having étul (phe-norechi-le) -binaphthalene, etc .:
- bisaminophenol compounds having one or more functional groups selected from bisaminophenol compounds having ezul (ferretchul) naphthalene and bisaminophenol compounds having equul (ferretul) fluorene.
- the thing is preferable. This can improve the elastic modulus of polybenzoxazole resin at high temperature.
- a method of introducing a functional group other than the diamondoid structure into the bisaminophenol compound there can be mentioned, for example, a method of a coupling reaction to a nitrogen compound. Specifically, based on the coupling reaction of a halogenated compound having a phorsohydroxy-torobenzene structure with ethynylbenzene, a functionalization is carried out by performing an amination reaction without reducing an acetylene bond by selecting an optimum catalyst.
- the groups can be introduced into bisaminophenol compounds.
- the term "having no functional group other than the diamondoid structure and the diamondoid structure” as used herein means that the "bisaminophenol compound" does not include the (1) diamondoid structure, and (2) It means that it does not contain any functional groups other than amino group and phenolic hydroxyl group which bisaminophenol is essentially possessed. Examples of bisaminophenoli compounds having no diamondoid structure and no functional group other than diamondoid structure are shown below.
- Bisaminophenol compounds having a dihydroxy diphenyl ether such as 3,3'-diamino-4,4'-dihydroxy-diphenyl ether:
- a fluorene skeleton such as 9, 9-bis (3-amino-1-hydroxy-monophenyl) fluorene and 9, 9-bis (4-amino- 4-hydroxy-monophenoxy) fluorene is Compounds having :,
- Examples thereof include compounds having a fluorine or fluorinated alkyl group such as 2,2 bis (3 amino 4 hydroxyphenyl) hexafluoropropane. These bisaminophenol compounds may be used alone or in combination of two or more.
- compounds having dihydroxybenzene, compounds having dihydroxy-diphenyl ether, compounds having a fluorene skeleton, compounds having a binaphthalene skeleton Medium power of selected compounds One or more kinds of selected bisaminophenol compounds Things like it! /.
- the dicarboxylic acid having the diamondoid structure is not particularly limited, it is one having a unit structure of the diamondoid in the molecule. Thereby, the modulus of elasticity of polybenzoxazole resin can be further improved.
- a dicarboxylic acid having a diamondoid structure includes one having a diamondoid structure in the dicarboxylic acid skeleton and one having a diamondoid structure bonded to the backbone of the dicarboxylic acid directly or through another atom. including.
- dicarboxylic acids having a diamondoid structure and having no functional group other than a diamondoid structure include, for example, 1,3 madamantan-dicarboxylic acid, 2,2 madamantan dicanolebonic acid, 1,2,3 Adamantan Dikanerene acid such as dicanorebonic acid Nore Venoic acid :,
- Diamantan dicanolebonic acids such as 1, 6 diamantane dicanolebonic acid, 4, 9-diamantane dicanolenic acid and 2, 2 di-amantan dicanolebonic acid:
- Triamantan dicarboxylic acids such as 1,3 triamantane dicarboxylic acid and 1,6 triamantane dicarboxylic acid: Tetramantane dicarboxylic acids such as 1, 3-tetramantane dicarboxylic acid, 1, 6-tetramantane dicarboxylic acid and 1, 8- tetramantane dicarboxylic acid:
- examples of the compound having an oligo structure having a plurality of groups having a polycyclic skeleton structure include, for example, 1,1′-bi (diamantane) -6,6′-dicarboxylic acid, 6, 6 ′ bis (4 1 Force Noleboxy Fewiniore) 1,1'-bi (diamantane), 6, 6 'bis (4-carboxy-phenoxy)-1, 1'-bi (diamantane), 6, 6'- bis [4- (4-(4 —Power (Ruboxy-Phenoxy))] [1] 1'-bi (diamantane) and the like are also included, but any structure within the definition of the diamondoid structure is not limited thereto. Also, the bonding position of the group having a polycyclic skeleton structure is not limited in the same manner.
- the group having an adamantane structure in the above dicarboxylic acids is an alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and tert-butyl group, fluoromethyl group, fluoroethyl group, fluoropropyl group.
- fluoroalkyl groups such as fluorobutyl group may be bonded.
- adamantanedicarboxylic acid 1, 1,-biadamantane-3, 3, Dicarboxylic acid, 5,7-dimethylamantane 1,3 dicarboxylic acid, 5,5 ', 7,7,7-tetramethyl-1,1,1-biadamantane-3,3,3-dicarboxylic acid, tetraadamantane dicarboxylic acid etc. More preferred is damantane dicarboxylic acid.
- Groups having an adamantane structure in these dicarboxylic acids are alkyl groups such as methyl group, ethyl group, n propyl group, isopropyl group, n propyl group, isobutyl group and tert butyl group (specifically made),
- a fluoroalkyl group such as a fluoromethyl group, a fluoroethyl group, a fluoropropyl group or a fluorobutyl group may be bonded together.
- dicarboxylic acids may be used alone or in combination of two or more.
- a method of introducing a functional group having a diamondoid structure into the dicarboxylic acid compound for example, a bis- (4bromo-phenyl) -1,1 can be obtained from the Friedel-Krafts reaction of dibuta moadamantane with bromobenzene. 3
- adamantane By synthesizing adamantane, converting a bromo group to alkyl lithium with alkyllithium, and treating with carbon dioxide gas and acid, bis- (4-power ruboxyl monophenyl) -1,3-adamantane can be synthesized. .
- the dicarboxylic acid when the dicarboxylic acid has a diamondoid structure at a functional group other than the diamondoid structure, it means that the diamond structure is bonded to the dicarboxylic acid skeleton via another atom.
- examples of dicarboxylic acids having a diamondoid structure via an ectol group include, for example, 3-adamantyl etulphthalic acid, 4 amantirietulfurtalic acid, 5 amantirietululisophthalic acid, etc.
- Etull phthalic acid such as ethyl-terephthalic acid such as acetyl isophthalic acid, 2 amanchir-te- terephthalic acid and 3-amanti-le-terrephthalic acid:
- Bis (carboxy-methyl-no-lef-nore) propanes such as 2, 2 bis- (2 carboxy-3 amityletyl phenyl) propane and 2, 2- bis (2- carboxy (4) amantil chele propane): ,
- Ruffenoxyfew-ruetul group tetramantoxy fenoxyfew-ruetul group, pentamantylphenoxyfew-ruetul group, Hexamantylphenoxyfew-ruetul group, heptamantylphenoxyfew-ruetichinyl group, Oktamantyl group Enoxysher-Letul group, Nonamantyru-enoxishoe-Luetul-group, Decamantilf Nokishifue - Ruechuru group and Unde force Manzi Rufuenokishifue - Ruechuru groups such as groups, bicycloalkyl adamantyl phenoxyethanol Hue - Ruechi - Group, triadamanyl phenoxiphe leucetul group, tetraadamanty phi enokisiti group, pentaadamantyl fenoxiphe luteru group, hexad
- a group of adamanchil-huetul group, a biadamantyl-huetul group, a damantyl-phenoxyle-ruetul group, a biadamantyl-phenoxyto-thyl group and the like are more preferable.
- the group having an adamantane structure in the above dicarboxylic acid compounds is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an n-butyl group, an isobutyl group and an alkyl group such as tert-butyl group, a fluoromethyl group, a fluoroethyl group, a fluoropropyl group. And a fluoroalkyl group such as fluorobutyl group may be bonded.
- dimethyladamantyl ferret group trimethyladamantyl ferret group, tetramethyl biadamantyl ferret group, pentamethyl biadamantyl ferret group, dimethyladamantyl ferret group, trimethyl
- a dadamantyl fel-ruetul group, a tetramethylbiadamantyl fenoxy phi-ruetul group, and a pentamethylbiadamantyl fenoxyphenyl-ruetul group are preferable.
- dicarboxylic acids having a functional group other than a diamondoid structure include, for example, 3-ethyl-phthalic acid, 4-ethyl phthalic acid, 5-ethyl isophthalic acid such as 5-ethyl isophthalic acid, 2 ethyl terephthalate, and 3 ethyl terephthalic acid.
- Etulte such as Ettal phthalic acid such as lepthalic acid :,
- Echininole naphthalene dihydric norebonic acid such as 2 ethynyl-1, 5 naphthalene dicarboxylic acid and 3 ethynyl-1, 5 naphthalene dikanole levonic acid:
- Jetul biphenyl dicarboxylic acids such as 4, 4 'jetyl diru 2, 2, biphenyl dicarboxylate and 5, 5' jetyl di
- 2-biphenyl dicarboxylic acid 2, 2 bis (2 Bis (carboxy-butyl ether) propane, such as carboxy-3 hydroxyethyl ester) and 2,2 bis (2-carboxylic acid) propane:
- Phenyl phthalic acid such as 3 phthalic acid such as 3 phthalic acid and 5 phthalic acid, 2 phthalic acid such as 2 phthalic acid and 3 phthalic acid such as 3 phthalic acid Terephthalic acid
- Ferretul naf tarendi force norebonic acid such as 2-ferretul-1,5 naphthalene dicarboxylic acid
- Dicarboxylic acids having an acetylene backbone in the molecule such as tolan dicarboxylic acids such as 4,4 'tolan dicarboxylic acid and 3, 4' tolan dicarboxylic acid:
- dicarboxylic acids having a biphenyl skeleton such as 1,2 biphenyl dicarboxylic acid and 1,3 biphenyl dicarboxylic acid, and the like, which may be used alone or in combination of two or more kinds.
- dicarboxylic acids having a biphenyl skeleton such as 1,2 biphenyl dicarboxylic acid and 1,3 biphenyl dicarboxylic acid, and the like, which may be used alone or in combination of two or more kinds.
- One or more selected dicarboxylic acids are preferred. This can further improve the crosslink density of the finally obtained polybenzoxazole resin.
- a method for introducing a functional group other than the diamondoid structure into the dicarboxylic acid for example, the method described in JP-A-2002-201158 can be mentioned.
- functional groups can be introduced using halogenated dicarboxylic acid esters or dicarboxylic acid esters in which a hydroxyl group is introduced.
- a phenyl dicarboxylic acid ester as a starting material is used as a coupling reaction with phenylacetylene to obtain a phenyltetracarboxylic acid ester, which is further deesterified by alkaline hydrolysis.
- phenyltetracarboxylic acid is further deesterified by alkaline hydrolysis.
- tolan dicarboxylic acid for example, a method of producing stilbene from a benzoate ester derivative and thereafter preparing a tolan skeleton and synthesizing it, introducing the tolan skeleton using a benzoate ester derivative and a phenylethynyl derivative Heck reaction It can be obtained by a method such as synthesis according to
- examples of the dicarboxylic acid having a biphenyl ring structure include the methods described in Journal of Polymer Science: Polymer Letters Edition, Vol. 16, o5d D56 (9178). Specifically, iodination of dimethyl 4,4'-biphenyldibasic, biphenyl-enylation with deiodine, and deesterification to obtain 2,7-biphenyldicarboxylic acid can be obtained. it can.
- the dicarboxylic acid "having no functional group other than the diamondoid structure and the diamondoid structure" means (1) it does not contain the diamondoid structure and (2) the dicarboxylic acid is essential. Meaning that it does not contain any functional group other than the carboxy group which it has.
- dicarboxylic acid examples include phthalic acids such as isophthalic acid, terephthalic acid, 2-fluoroisophthalic acid and 2,3,5,6-tetrafluoroterephthalic acid, 4,4, bicarboxylic dicarboxylic acid, 3, 4'-biphenyldicarboxylic acid, 3,3'-biphenyldicarboxylic acid, 4,4'-bis (4carboxyphenoxy) biphenyl and 4,4'-bis (3-carboxyphenoxy) biphenyl etc
- Naphthalene dicarboxylic acids such as biphenyl dicarboxylic acid, 1,4 naphthalene dicarboxylic acid, 2,3 naphthalene dicarboxylic acid and 2,6 naphthalene dicarboxylic acid, 4,4-sulfo-bis-benzoic acid 3,4, -Sulfo-bisbis-safonic acid, 3, 3, sulfo- bis-benzoic acid, 4, 4, monohydroxy
- Benzazole fat precursor having a first repeating unit is a bisaminophenol compound having a diamondoid structure. Reaction with a dicarboxylic acid having no diamondoid structure, reaction with a bisaminophenol compound having no diamondoid structure, and dicarboxylic acid having a diamondoid structure, or The force that can be obtained by the reaction of the bisaminophenol complex having the diamondoid structure with the dicarboxylic acid having the diamondoid structure. Examples of this reaction method include the acid chloride method.
- the dicarboxylic acid is reacted with an excess amount of sodium chloride at room temperature to about 130 ° C., and the excess sodium hydroxide is added. After evaporation under heating and reduced pressure, the residue is recrystallized with a solvent such as hexane to give dicarboxylic acid chloride.
- a catalyst such as N, N'-dimethylformamide
- the dicarboxylic acid chloride and the bisaminophenol compound are dissolved in a polar solvent such as N-methyl-2-pyrrolidone, N, N, -dimethylacetoamide, and the like, in the presence of an acid acceptor such as pyridine, By reacting at about -30 ° C. to room temperature, it is possible to obtain a benzoxazole resin precursor having a first repeating unit (a benzoxazole resin precursor having a functional group in a side chain).
- the number of repeating units of the first repeating unit is not particularly limited, but is preferably 2 to 1,000, particularly preferably 5 to L00. Repeat unit When the number is in the above range, the solubility and the workability are particularly excellent.
- the active ester method can be used instead of the acid chloride method.
- benzotriazolyl ester is produced by the reaction of the above dicarboxylic acid chloride with 1-hydroxybenzotriazole, and this ester and the above bisaminophenol are similarly treated as described above at room temperature or higher. It is sufficient to react at the temperature of
- the bisaminophenol complex, the dicarboxylic acid complex or both of them may be used. What has a group crosslinkable with the said crosslinking agent may be used.
- the benzoxazole fat precursor having the first repeating unit may further include the second repeating unit.
- the second repeating unit is obtained by reacting a bisaminophenol complex with no diamondoid structure and a dicarbonic acid compound with no diamondoid structure.
- the benzoxazole resin precursor having the second repeating unit is one which forms a polybenzoxazole resin having no diamondoid structure.
- the first repeating unit and the second repeating unit may constitute a benzoxazole resin precursor in the form of a copolymer or a simple mixture. Furthermore, in the case of a copolymer, the first repeating unit and the second repeating unit may be any of a random copolymer, an alternating copolymer, and a block copolymer.
- a bisaminophenol-free composite which does not have a diamondoid structure used for a benzoxazole fat precursor having a second repeating unit, and a dicarboxylic acid which does not have a diamondoid structure As the compound, a bisaminophenol compound not having the diamondoid structure described in 1 2), which is used for the benzoxazole resin precursor having the first repeating unit, and the diamond described in 1-4) It is possible to use a dicarboxylic acid compound which does not have an id structure.
- the number of repeating units of the second repeating unit is not particularly limited, but is preferably 2 to 1,000, and particularly preferably 5 to 100. When the number of repeating units is within the above range, particularly, the solubility and the workability are excellent.
- the active ester method can be used instead of the acid chloride method.
- benzotriazolyl ester is produced by the reaction of the above dicarboxylic acid chloride with 1-hydroxybenzotriazole, and this ester and the above bisaminophenol are similarly treated as described above at room temperature or higher. It is sufficient to react at the temperature of
- benzoxazole fat precursor used in the present invention will be described in detail as having a third repeating unit represented by the above general formula (1).
- the benzoxazole resin precursor having the third repeating unit is a benzoxazole resin precursor including a diamondoid structure derived from a bisaminophenol compound.
- the number (k) of repeating units of the third repeating unit is not particularly limited, but is preferably an integer of 2 to 1, 000 and particularly preferably an integer of 5 to 600. An integer up to 80 is preferred. When the number of the repeating units is within the above range, the workability at the time of dissolving the benzoxazole resin precursor in a solvent is excellent.
- a method for obtaining a benzoxazole fat precursor having the third repeating unit is represented by the following general formula (18), and as X in the formula, the above general formulas (2-1), (2) Medium power of groups represented by 2) and (3) A bisaminophenol compound having a selected group and a compound represented by the following general formula (19), wherein Y in the formula is the above general formula (4), (6-1), (6-2), (7-1), (7-2), (8) and a dicarboxylic acid having a group selected from the groups represented by (9) It can be synthesized by reacting with a compound, for example, a bisaminophenol compound having the diamondoid structure, a dicarboxylic acid not having the functional group, and the diamond compound.
- These combinations can be freely selected to obtain desired properties (for example, the dielectric constant), but in order to obtain a lower dielectric constant in a resin film, a resin having fine pores can be selected.
- a combination of the bisaminophenol complex having the diamond doido structure and the dicarboxylic acid having the functional group is more preferable.
- R and R each independently represent a hydrogen atom or an organic group
- the active ester method may be used instead of the acid chloride method.
- benzotriazolyl ester is produced by the reaction of the above dicarboxylic acid chloride with 1-hydroxybenzotriazole, and this ester and the above bisaminophenol are similarly treated as described above at room temperature or higher. It is sufficient to react at the temperature of
- benzoxazole resin precursor used in the present invention is represented by the general formula (10). Having a repeating unit.
- the benzoxazole fat precursor having the third repeating unit is not particularly limited, but preferably has the fourth repeating unit represented by the general formula (10).
- the number (m) of repeating units of the fourth repeating unit is not particularly limited, but is preferably an integer of 2 to 1, 000 and particularly preferably an integer of 5 to 600. An integer up to 80 is preferred. When the number of the repeating units is within the above range, the workability at the time of dissolving the benzoxazole resin precursor in a solvent is excellent.
- the third repeating unit and the o-th repeating unit of o C 4 ⁇ may constitute a benzooxiazole pre-H 2 -dentate in the form of a copolymer or a simple mixture. Furthermore, in the case of the copolymer, the third repeating unit and the fourth repeating unit may be any of a random copolymer, an alternating copolymer, and a block copolymer.
- a benzoxazole fat precursor having the fourth repeating unit it can be represented by the above general formula (18), and as X in the formula, the above general formulas (2-1), (2) Medium power of the groups represented by 2) and (3) and a bisaminophenol compound having a selected group and a compound represented by the following general formula (20), wherein Y in the formula is the above general formula (11 1), (11-2), (12-
- the compound can be synthesized by reacting a dicarboxylic acid compound having a group selected from the groups represented by 1) and (12-2) with, for example, the bisaminophenol compound having a diamondoid structure. And a method of reacting the above-mentioned dicarboxylic acid having a diamondoid structure according to the acid chloride method as described above.
- the active ester method can be used instead of the acid chloride method.
- benzotriazolyl ester is produced by the reaction of the above dicarboxylic acid chloride with 1-hydroxybenzotriazole, and this ester and the above bisaminophenol are similarly treated as described above at room temperature or higher. It is sufficient to react at the temperature of 5.
- Benzoxazole resin precursor having a fifth repeating unit having a fifth repeating unit
- the benzoxazole fat precursor used in the present invention has a repeating unit represented by the above general formula (13). Furthermore, the benzoxazole fat precursor having the third repeating unit and the fourth repeating unit is not particularly limited, but may have the fifth repeating unit represented by the general formula (13). Is preferred.
- the number (m) of repeating units of the fifth repeating unit is not particularly limited, but is preferably an integer of 2 to 1, 000 and particularly preferably an integer of 5 to 600. An integer up to 80 is preferred. When the number of the repeating units is within the above range, the workability at the time of dissolving the benzoxazole resin precursor in a solvent is excellent.
- the third repeating unit and the fourth repeating unit and the fifth repeating unit may be in the form of a copolymer or a simple mixture, and may be a benzoxazole resin precursor. Furthermore, in the case of a copolymer, the third repeating unit and Z or the fourth repeating unit and the fifth repeating unit may be any of a random copolymer, an alternating copolymer, and a block copolymer. Also good.
- the compound can be synthesized by reacting with a dicarboxylic acid compound having a group selected from among the groups represented by 2 and (12 2), for example, a bisaminophenoyl compound not having the diamondoid structure.
- Z or a method in which a bisaminophenol compound having a functional group other than the diamondoid structure and a dicarboxylic acid having the diamondoid structure are reacted by the acid chloride method as described above.
- These combinations can be freely selected to obtain the target characteristics (for example, the dielectric constant) in the same manner as described above, but in order to obtain a lower dielectric constant in the resin film, fine pores are required.
- a combination of a bisaminophenol compound having a functional group other than the diamondoid structure and a dicarboxylic acid having the diamondoid structure is more preferable. preferable.
- R and R in the formula (21) each independently represent a hydrogen atom or an organic group
- the active ester method may be used instead of the acid chloride method.
- benzotriazolyl ester is produced by the reaction of the above dicarboxylic acid chloride with 1-hydroxybenzotriazole, and this ester and the above bisaminophenol are similarly treated as described above at room temperature or higher. It is sufficient to react at the temperature of
- benzoxazole resin precursor having the third repeating unit, the fourth repeating unit, and the fifth repeating unit is not particularly limited, but is represented by the general formula (17) It is preferable to have a sixth repeating unit.
- the number (n) of repeating units of the sixth repeating unit is not particularly limited, but is preferably an integer of 2 to 1000, and particularly preferably an integer of 5 to LOO.
- the number of repeating units is in the above-mentioned range, the workability at the time of dissolving the benzoxazole resin precursor in a solvent is excellent.
- the third repeating unit, the fourth repeating unit, and the Z or fifth repeating unit and the sixth repeating unit are each in the form of a copolymer or a mere mixture of benzooxazole lipid precursors. You may configure. Furthermore, in the case of a copolymer, the third repeating unit, the fourth repeating unit, and the Z or fifth repeating unit and the sixth repeating unit may be random copolymers, alternating copolymers, block copolymers, etc. It may be any combination.
- a bisaminophenol compound having a group selected from the group represented by the general formula (19), and Y in the formula is a group represented by the general formula (4), (6- 1), It can be synthesized by reacting with a dicarboxylic acid having a group selected from the groups represented by (6-2), (7-1), (7-2), (8) and (9).
- a bisaminophenol complex having no functional group, a dicarboxylic acid having no functional group, and a dicarboxylic acid compound having a functional group other than Z or a diamondoid structure other than the diamondoid structure is a group represented by the general formula (4), (6- 1), It can be synthesized by reacting with a dicarboxylic acid having a group selected from the groups represented by (6-2), (7-1), (7-2), (8) and (9).
- the active ester method may be used instead of the acid chromatography method.
- benzotriazolyl ester is produced by the reaction of the above dicarboxylic acid chloride with 1-hydroxybenzotriazole, and this ester and the above bisaminophenol are as described above at room temperature or higher. It is sufficient to react at temperature.
- a benzoxazoyl sebum precursor having the third repeating unit represented by the above formula (1), and a benzoxazole tallow resin having the fourth repeating unit represented by the above formula (10) A precursor, a benzoxazole resin precursor having the fifth repeating unit represented by the above formula (13), and a benzooxazole resin precursor having the sixth repeating unit represented by the above formula (17);
- a benzoxazole resin precursor having the third repeating unit represented by the above formula (1), or the above formula (10) is used.
- the benzoxazole fat precursor having the sixth repeating unit The composition comprising two or more selected from the force is a resin having excellent heat resistance and low dielectric constant, which is the object of the present invention, and from it Preferred for obtaining the obtained resin film.
- the fourth repeating unit is preferred for imparting adhesion, while the sixth repeating unit preferred for imparting a high modulus of elasticity, but both of them impair the target characteristics of the present invention. It can be used to an extent.
- polybenzoxazole sebum is obtained by dehydration ring closure reaction of a benzoxazoyl sebum precursor as described above.
- the reactions are, for example, condensation reactions and crosslinking reactions.
- the polybenzoxazole resin When the polybenzoxazole resin is used as an interlayer insulating film to be described later, a thermal group having a substituent capable of reacting with a carboxyl group, an amino group or a hydroxyl group of the benzoxazole resin precursor. What is obtained by reacting a reactive oligomer having degradability can be used. In addition, organic compounds which decompose or scatter at high temperature can be used by reaction or blending. As a result, when the interlayer insulating film is formed, the nanofoam can be easily formed.
- Examples of the substituent capable of reacting with the carboxyl group include, for example, an amino group, a hydroxyl group and an isocyanate group.
- examples of the substituent capable of reacting with the amino group include, for example, a carboxyl group, an isocyanate group, a glycidyl group, a maleic anhydride group, a maleimide group, an acid anhydride group and an allilate group.
- carbo examples include xyl and glycidyl groups.
- Examples of the base fat of the reactive oligomer include polyoxyalkylene, polymethyl methacrylate, poly (X-methylstyrene, polystyrene, polyester, polyether ester, polyprotonic acid, polyurethane, polycarbonate and the like.
- polyoxyalkylenes or polycarbonates are preferred, which can form particularly fine nanofoams.
- the number average molecular weight of the reactive oligomer is not particularly limited, but is preferably 100 to 40,000, particularly preferably 200 to 200,000 S. When the number average molecular weight is within the above range, nanoforms are less likely to aggregate and fine and uniform nanoforms can be formed.
- the glass transition temperature of the polybenzoxazole resin is not particularly limited !, but is preferably 400 ° C or more, particularly preferably 420 ° C or more, and most preferably 450 to 500 ° C. When the glass transition temperature is within the above range, the linear expansion coefficient of a resin film obtained from benzoxazole resin can be reduced.
- the crosslinking agent used in the present invention may be, for example, a compound having 2 or more and 10 or less crosslinking groups in one molecule, as long as it has two or more groups causing a crosslinking reaction in one molecule.
- crosslinking group examples include a functional group having an acetylene bond, a functional group having a vinyl bond, a biphenylene group, a cyanato group, a maleimide group, a nadiimide group, a vinyl group and a cyclopentajenyl group.
- functional groups having an acetylene bond are preferable.
- the functional group having an acetylene bond an ethynyl group;
- Huetuetul group Naphthlethur group, Anthryl etsul group, 3 Phew-ru 2 propyol group, 4 Phew-ru 3-peptyl group, 6-phe-ru 5-Hexyl group and 8 —Aromatic substituted etul groups such as —7-octyl groups;
- Nitrogen-containing aromatic substituted ethynyl groups such as quinolyl ethynyl group and quinoxalyl etul group; 1 alkyl ether such as 1 propyyl group, 1-butyl group, 2-butyl group, 1-hexyl group, 2-hexyl group, 3-hexynyl group and 4-hexynyl group
- 1 alkyl ether such as 1 propyyl group, 1-butyl group, 2-butyl group, 1-hexyl group, 2-hexyl group, 3-hexynyl group and 4-hexynyl group
- a linear aliphatic substituted ethur group such as a group
- Cyclohexyletul group bicyclo [2,2,1] heptyletul group, adamantryl group, 3-cyclohexyl-2-propyl group, 4-cyclohexyl 3-teptyl group, 6-cyclohexyl 5-alkyl And cycloaliphatic substituted ethur groups such as 8-cyclohexyl 7-octyl groups;
- Propargyl ether group 2 propyoxy group, 2 buturooxy group, 3 buturooxy group, 2 hydroxy group, 3 hexoxy group, 4 1 hydroxy group, 5 hexoxy group, 2 heptoxy group, 3
- An alkyloxy group such as a hepta-loxy group, a 41-peptoxy group, a 5-s-methoxy group, and a 6-hepta- loxy group;
- phenyl substituted groups such as 1,3 pentadiyl groups, 4-cyclohexyl, 1,3 butadiynyl groups and 2,4 pentadialkyloxy groups.
- the hydrogen atom in the group containing an acetylene bond may be substituted by a group such as a fluorine atom, a methyl group, a methoxy group and a trifluoromethyl group.
- a group such as a fluorine atom, a methyl group, a methoxy group and a trifluoromethyl group.
- eteur group ferr etul group, (4 methyl phenyl) etul group, naphthylethyl group, phenyl butyryl group, t-butyl ethynyl group, adamantyletul group and 3,5 dimethyl
- the bridging group selected is preferred.
- a plurality of crosslinking groups in one molecule may be the same as or different from one another.
- a method by heating a method of irradiating active energy ray such as microwave, visible light, UV light and X-ray, and actinic radiation such as electron beam can be mentioned.
- the crosslinking group causes a crosslinking reaction by a method such as a method of heating, a method of irradiating active energy rays such as microwaves, visible light, UV light and X-rays, and actinic radiation such as an electron beam.
- a method of heating such as a method of heating, a method of irradiating active energy rays such as microwaves, visible light, UV light and X-rays, and actinic radiation such as an electron beam.
- active energy rays such as microwaves, visible light, UV light and X-rays
- actinic radiation such as an electron beam.
- Benzoxazole having the above-mentioned crosslinking group It is also possible to improve the heat resistance by improving the crosslink density of polybenzoxazole resin obtained by crosslinking the resin precursor.
- an interlayer insulating film is obtained by forming a nanofoam using strong polybenzoxazole resin
- the crosslink density of polybenzoxazole resin is improved, the nanoform is aggregated or the like. It becomes possible to maintain the shape without. Thereby, the dielectric constant of the interlayer insulating film can be reduced.
- crosslinking agent As a specific example of such a crosslinking agent, one having a structure represented by the following formula (22) can be mentioned.
- A- (B) p Formula (22) In the formula, A is an organic group. B is a crosslinking group in the crosslinking agent, and p is an integer of 2 or more, preferably 2 or more and 10 or less.
- Examples of the organic group as A in the above formula (22) include a binaphthalene group, a naphthalene group, a fluorene group, a fur group, a diphenyl ether group, a biphenyl group, a diphenyl sulfone group, a diphenyl propane group and Aromatic groups such as diphenyl hexafluoropropane, adamantyl group, 3,5-diphenyladamantyl group, 3,5,7-triphenyladamantyl group, 3,5,7 9 Laf-erdamantyl group 1, 1,-biadamantyl group, 1, 2, monobiadamantyl group, 2, 2, monobiadamantyl group and 3, 3, di-phene-ru 1, 1, biadamantyl group, 3, 3 ', 5,5, 5-Tetraphenyl-1, 1,-Biadamantyl group and 3, 3', 5, 5 ', 7, 7'-Hexaphene 1, 1 '-Bi
- the hydrogen atom in the organic group may be substituted with a fluorine atom, a methyl group, a methoxy group and a trifluoromethyl group.
- A, A and A are each an organic group. Also, R to R are each an organic group
- At least two groups in R force R At least two groups in R force R, at least two groups in R force R
- R and R are bridging groups.
- Examples of the organic group of the above A to A include binaphthalene group, naphthalene group, fluorene group,
- a force such as di-phenyl group, di-phenyl ether group, bi-phenyl group, di-phenyl sulfone group, di-phenyl-p-pan group, and di-phenyl hexafluoropropane group, etc. is not limited thereto. These groups may have a diamondoid structure.
- an ecul group As the organic group of the above R to R 5, an ecul group, a ferr etul group, a naphtyl
- anthryl cetul group anthryl cetul group, quinolyl ethul group, quinoxalyl ether group, alkyl ether group, propargyl ether group, phenyl group, biphenyl group, cyanato group, maleimido group, nadiimide group, vinyl
- a group, a cyclopentagenyl group, etc. are listed is not limited to these.
- a resin having a network structure formed by reacting crosslinking agents with one another using a bifunctional or higher crosslinking agent, preferably a trifunctional or higher crosslinking agent may be used.
- the fat composition of the present invention can be obtained by mixing the above-mentioned components, and the proportion of the benzoxazole fat precursor and the crosslinking agent is 100 parts by weight of the benzoxazole fat precursor.
- the proportion of the benzoxazole fat precursor and the crosslinking agent is 100 parts by weight of the benzoxazole fat precursor.
- 1 to: LOO parts by weight of the crosslinking agent is preferred, and more preferably 5 to 50 parts by weight of the crosslinking agent.
- the benzoxazole fat precursor does not have a functional group that can crosslink with the crosslinking agent.
- Benzoxazole resin precursor composition with / can be used, and furthermore, it can also be mixed using a resin consisting of the above-mentioned trifunctional or higher crosslinking agent.
- a surfactant in addition to the above-mentioned components, if necessary, a surfactant, a coupling agent represented by a silane system, a radical initiator which generates oxygen radicals or sulfur radicals by heating, Additives such as catalysts such as disulfides can be used.
- R and R in the general formulas (1), (10), (13), (17) and (20) may be added to the benzoxazole fat precursor and the diamine mixture. At least as R
- one of them has a hydrogen atom
- it can be used as a positive photosensitive resin composition by using it together with a naphthoquinone diazide compound as a photosensitizer.
- the resin composition is preferably used as a varnish for producing a resin film or the like by dissolving or dispersing the resin film or the like in an organic solvent capable of dissolving or dispersing the resin film or the like.
- organic solvent include N-methyl-2-pyrrolidone, y-butyrolataton, N, N-dimethylacetoamide, dimethylsulfoxide, jetylene glycol dimethyl ether, diethylene glycol jetyl ether, diethylene glycoloresibutinouretenole, propylene glycol monomethyl.
- the proportion of the above-mentioned resin composition and the above-mentioned organic solvent is not particularly limited as long as it can completely dissolve or disperse the resin composition, and it may be suitably adjusted according to its use.
- the solvent content in the varnish is preferably about 70 to 95% by weight.
- the resin composition or varnish of the present invention can be applied to the resin composition or varnish using known methods, such as injection molding, transfer molding, compression molding, extrusion molding, cast molding, and coating methods. It can be a molded article.
- the form may be any form, such as the form of an intermediate molded article before the resin composition is made into a final molded article, or the form of the final molded article, for example, It may be an intermediate molded product before forming a fat film and causing a crosslinking reaction, or a molded product obtained by curing the same.
- the molded article can be made into a final molded article by crosslinking the benzoxazole resin precursor having a crosslinking group or the resin thereof with a crosslinking agent.
- Examples of the method of the crosslinking reaction include a method of heating, a method of irradiating active energy rays such as microwaves, visible light, UV light and X-rays, and actinic radiation such as electron beams.
- the resin film of the present invention is composed of the above-described resin composition. Thereby, the adhesion and the dimensional stability are excellent.
- the resin film may be, for example, an interlayer insulating film or surface protective film for a semiconductor, an interlayer insulating film of a multilayer circuit, a cover coat of a flexible copper clad plate, a solder resist film, a liquid crystal alignment film, an etching protective film (etching stopper), Adhesive etc. are mentioned. Among these, it is suitably used as an interlayer insulating film for semiconductors, a surface protective film, and an etching protective film.
- the interlayer insulating film is not particularly limited.
- the interlayer insulating film has micropores (nanofoam). This is preferable.
- the average pore diameter of the nanofoam is not particularly limited, but is preferably 6 nm or less and most preferably 3 nm or less, from 1 nm or less is preferable.
- the average pore size is in the above range, the dielectric properties are excellent particularly in pattern formation with high compatibility in the process.
- Examples of the method of measuring the average pore diameter include small angle X-ray scattering method, positron annihilation method, gas adsorption method and ellipsometric porosimetry method.
- the benzoxazole resin precursor described above is used as the polybenzoxazole resin precursor constituting the resin composition. It is preferable to use one obtained by reacting a carboxyl group, an amino group or a hydroxyl group of the above with a reactive oligomer having a substituent capable of reacting. Thereby, nanofoam can be easily formed in the interlayer insulating film. Also, decomposition at high temperature! , Can react or blend flying organic compounds to form a nanofoam.
- a foaming agent for forming nanofoam may be added to the above-mentioned fat composition.
- foaming agent examples include carbon nanotubes and fullerenes having a hollow structure, caged silsesquioxane, cyclodextrin, organic compounds having a high melting point, organic compounds having low volatility, surfactants, azobis compounds, organic oxide And dendrimers and hyperbranched polymers.
- surfactants or hyperbranched polymers organic compounds having a high melting point, and organic compounds having a low volatility are preferable. This makes it possible to uniformly disperse the blowing agent in polybenzoxazole resin. Ru. If the foaming agent can be uniformly dispersed, it is possible to obtain fine nanofoam by further heating and extraction treatment.
- the porosity of the interlayer insulating film is not particularly limited, but is preferably 5 to 70%, particularly preferably 7 to 50%. When the porosity is less than the lower limit, a sufficient decrease in dielectric constant may not be exhibited, and when the upper limit is exceeded, the mechanical strength of the film may be reduced, and the modulus of elasticity and adhesiveness may be reduced.
- the thickness of the interlayer insulating film is not particularly limited, but is preferably 0.10 to 20 m, particularly preferably 0.05 to 10 111, and most preferably 0.1 to 0.7 m. . When the thickness is within the above range, process suitability is excellent.
- a varnish is produced by dissolving a resin composition containing the benzoxazole resin precursor in an organic solvent such as N-methyl 2-pyrrolidone.
- the varnish is applied to a suitable support such as a silicon wafer or a ceramic substrate to form a coating.
- suitable support such as a silicon wafer or a ceramic substrate.
- the coating method include spin coating using a spinner, spray coating using a spray coater, immersion, printing, roll coating, and the like. Thereafter, the coated film is dried, heat-treated, and solvent removal is followed by condensation reaction and crosslinking reaction to form polybenzoxazole resin, and an interlayer insulating film composed of a resin composition containing it. can do.
- the benzoxazole fat precursor converted to fat is dissolved in an organic solvent, a varnish is prepared in advance as the benzoxazole fat, and the interlayer is formed by the same method. An insulating film can be obtained. At that time, since the step of converting the benzoxazole resin precursor into a resin is not necessary for the heat treatment of the coating film, the heat treatment time can be shortened.
- the interlayer insulating film may be further subjected to heat treatment to form an interlayer insulating film having fine pores.
- the resin film is the protective film for the semiconductor
- the interlayer insulating film for example, propylene carbonate, diacetone alcohol, N methyl-2-pyrrolidone and the like are used.
- a varnish is prepared by dissolving in an organic solvent such as, and the varnish is applied to a suitable support such as a silicon wafer or a ceramic substrate.
- spin coating using a spinner spin coating using a spinner, spray coating using a spray coater, immersion, printing, mouth Coating etc. Then, it is dried, heat-treated, and solvent removal is followed by a condensation reaction and a crosslinking reaction to form a polybenzoxazole resin, which can be used as a protective film composed of a resin composition containing it.
- the thickness of the protective film is not particularly limited, but in particular, 0.50 to 70 / z m is preferable.
- the thickness is in the above-mentioned range, in particular, both the protective properties and the moldability of the semiconductor device are excellent.
- FIG. 1 is a cross-sectional view schematically showing an example of the semiconductor device of the present invention.
- the semiconductor device 100 includes a semiconductor substrate 1 on which elements are formed, a silicon nitride film 2 provided on the upper side (upper side in FIG. 1) of the semiconductor substrate 1, and an interlayer insulating film 3 provided on the silicon nitride film 2. And the copper wiring layer 4 covered with the barrier layer 6.
- the interlayer insulating film 3 is formed with a recess corresponding to the pattern to be wired, and a copper wiring layer 4 is provided in the recess.
- the interlayer insulating film 3 is formed with nanofoam (fine pores) (not shown). Further, a reformed layer 5 is provided between the interlayer insulating film 3 and the copper wiring layer 4. Further, a hard mask layer 7 is formed on the upper side of the interlayer insulating film 3 (the side opposite to the silicon nitride film 2).
- nanofoam is formed in interlayer insulating film 3.
- the present invention is not limited to this.
- the semiconductor device 100 using the interlayer insulating film 3 has been described in the present embodiment, the present invention is not limited to this.
- the semiconductor device of the present invention uses the above-described interlayer insulating film, the semiconductor device of the present invention is excellent in dimensional accuracy and can sufficiently exhibit insulating properties, thereby providing excellent connection reliability.
- the interlayer insulating film as described above is excellent in adhesion to the wiring layer, connection reliability of the semiconductor device can be further improved.
- the interlayer insulating film as described above is excellent in dielectric characteristics, the signal loss of the semiconductor device can be reduced. Further, since the interlayer insulating film as described above is excellent in dielectric characteristics, the wiring delay can be reduced.
- IR Infrared spectroscopy
- MS Mass spectrometry
- the five-necked 500 mL flask equipped with a thermometer, stirrer, reflux tube, nitrogen inlet tube and exhaust tube to a trap containing a 30% aqueous sodium hydroxide solution is cooled in an ice bath and the flask There were added 1.47 g (0.222 mol) of 1,3 dib-opening moadamantane, 200 ml of phenol, and 2. 6 g (0.Ol mol) of aluminum bromide, followed by stirring at 0 ° C. for 6 hours. Furthermore, the reaction was carried out by heating at 60 ° C. for 4 hours.
- the reaction product was poured into acidic ice water 2, OOOL and after the ice melted, the organic layer was taken out, washed with pure water and a saturated aqueous sodium chloride solution, and then poured into methanol to precipitate a product.
- the obtained product was dried under reduced pressure to obtain 3.5 g of a product.
- the absorption of hydroxyl group is at 3, 550 to 3, 200 cm 1 , the molecular weight is 3
- the obtained recrystallized product was dried under reduced pressure to obtain 30 g of a product.
- the product has 1, 3-bis (3 amino- 4 hydroxy mono-) adamantane (diamond-one structure) It was shown to be a bisaminophenol compound.
- Dicarboxylic acid having a functional group (5-phenylether isophthalic acid) according to the following steps Acid dichloride) was obtained.
- the number average molecular weight (Mn) of the obtained benzoxazole resin precursor was determined as polystyrene conversion using GPC manufactured by Tosoh Co., Ltd. and was 200,000.
- the solution was dissolved in 200 g of dehydrated N-methyl-2-pyrrolidone, cooled to 15 ° C., and 53.0 g (0.22 mol) of 4-phenyl benzoyl chloride was added little by little under stirring. After stirring for 1 hour, the temperature was returned to room temperature and stirred at room temperature for 5 hours. Thereafter, the reaction solution was dropped little by little into 4 liters of distilled water, and the precipitate was recovered. The precipitate was washed with methanol and dried in a vacuum drier for 24 hours. The resulting product was subjected to 3 ⁇ 4 NMR, IR, and MS measurements to confirm the synthesis of 9,9 bis ⁇ 3- (4 ferretul benzoic acid amide) -4-hydroxyphenyl ⁇ fluorene.
- the number average molecular weight (Mn) of the obtained benzoxazole resin precursor was determined as polystyrene using a Tosoh Co., Ltd. GPC, and was 16, 000.
- the number average molecular weight (Mn) of the obtained benzoxazole resin precursor was determined as polystyrene conversion using GPC manufactured by Tosoh Co., Ltd. As a result, it was 17,000.
- a resin film was obtained in the same manner as in 5) of Example 1 except that The number average molecular weight (Mn) of the obtained benzoxazole resin precursor was found to be 15,000 by polystyrene conversion using GPC manufactured by Tosoh Corporation.
- the number average molecular weight (Mn) of the obtained benzoxazole resin precursor was found to be 15,000 by polystyrene conversion using GPC manufactured by Tosoh Corporation.
- Example 1 lO mol
- the reaction was carried out to obtain 10 g of a benzoxazole fat precursor, and a fat film was obtained in the same manner as in 5) of Example 1 except that the above benzoxazole fat precursor was used.
- the number average molecular weight (Mn) of the obtained benzoxazole resin precursor was found to be 15,000 by polystyrene conversion using GPC manufactured by Tosoh Corporation.
- the number average molecular weight (Mn) of the obtained benzoxazole resin precursor was found to be 15,000 by polystyrene conversion using GPC manufactured by Tosoh Corporation.
- Example 2 The reaction is carried out in the same manner as in 3) of Example 1 except that 22.6 g (0.05 mol) of di-biamantane) -dicarboxylic acid dichloride is used to obtain a benzoxazoyl monobasic resin precursor.
- a resin film was obtained in the same manner as in 5) of Example 1 except that 10 g of fat precursor was used.
- the number average molecular weight (Mn) of the obtained benzoxazole resin precursor was determined as polystyrene using a Tosoh Co., Ltd. GPC, and was 18,000.
- Example 10 [0133] 1) Production of resin film
- Example 11 In 5) of Example 1, in place of 10 g of benzoxazole fat precursor, 10 g of benzoxazole fat precursor obtained in Example 3; external crosslinker 9, 9-bis ⁇ 3- (4 Instead of 2 g of 7-, 7-bis (3, 5-jetl-1), 3, 3 ', 5, 5,- A resin film was obtained in the same manner as in 5) of Example 1 except that 2 g of tetramethyl-1, 1 and biadamantane was used.
- Example 11 In 5) of Example 1, in place of 10 g of benzoxazole fat precursor, 10 g of benzoxazole fat precursor obtained in Example 3; external crosslinker 9, 9-bis ⁇ 3- (4 Instead of 2 g of 7-, 7-bis (3, 5-jetl-1), 3, 3 ', 5, 5,- A resin film was obtained in the same manner as in 5) of Example 1 except that 2 g of tetramethyl-1, 1 and biadamantane was used.
- Example 11 In 5) of Example 1, in place of 10
- the precipitate is washed with methanol, dried in a vacuum drier for 24 hours, and 7, 7'-bis (3, 5-jeturfell) -l, 3, 3 ', 5, 5, 1-tetramethyll- 1 , 1, One biadamantane polymer was obtained.
- Example 5 In 5) of Example 1, in place of 10 g of benzoxazole fat precursor, 10 g of benzoxazole fat precursor obtained in Example 3; external crosslinker 9, 9-bis ⁇ 3- (4 7-bis- (3,5-tetrachloro-1-phenyl) -3,3-5,5,5 instead of 2 g of 4-hydroxyphenyl ⁇ fluorene A resin film was obtained in the same manner as in 5) of Example 1 except that 2 g of, -tetramethyl-1,1'-biadamantane polymer was used.
- Example 5 In 5) of Example 1, in place of 10 g of benzoxazole fat precursor, 10 g of benzoxazole fat precursor obtained in Example 3; external crosslinker 9, 9-bis ⁇ 3- (4 —Fue-ruetul benzoic acid amide) -4-hydroxyphenyl ⁇ fluorene 2 g instead of 3 A resin film was obtained in the same manner as in 5) of Example 1 except that 2 g of 3 ', 5, 5', 5'-tetraethyl-1, 1'-biadamantane was used.
- Example 5 In place of 10 g of benzoxazole fat precursor, 10 g of the benzoxazole fat precursor obtained in Example 3 and an external crosslinking agent 9, 9 bis ⁇ 3- (4- In this example, 2 g of 7, 7, 7-dechul 3, 3 ', 5, 5-tetramethyl-1, 1-biadamantane was used in place of 2 g of phe-ruetul benzoic acid amide)-4-hydroxyphenyl ⁇ fluorene. A resin film was obtained in the same manner as 1) -5).
- Example 11-1 instead of 7, 7, 7-bis (3, 5 jetulfur)-3, 3 ', 5, 5-tetramethyl-1, 1 one biadamantane 57.5 g (0. l mol) In addition, 7, 7-diethyl-3,3'5,5,5- tetramethyl-1,1,1-biadamantane 37.5 g (0. lmol) except that 1) of Example 11 was used. In the same manner as in the above, an external crosslinking agent 7, 7'-jet-1, 3 ', 5, 5-tetramethyl-1, 1-1 biadamantane polymer was obtained.
- Example 5 In 5) of Example 1, in place of 10 g of benzoxazole fat precursor, 10 g of the benzoxazole fat precursor obtained in Example 3 and an external crosslinking agent 9, 9 bis ⁇ 3- (4- Using 2 g of the above-mentioned 7, 7, 7-getul-3, 5, 5, tetramethyl-1, 1-1 biadamantane polymer instead of 2 g of (few-ruetul benzoic acid amide)-4-hydroxyphenyl ⁇ fluorene A resin film was obtained in the same manner as in 5) of Example 1 except for the above.
- the number average molecular weight (Mn) of the obtained benzoxazole resin precursor was determined as polystyrene conversion using GPC manufactured by Tosoh Co., Ltd. As a result, it was 17,000.
- the heat resistance was evaluated by the glass transition temperature and the thermal decomposition temperature.
- the glass transition temperature of the obtained resin film was measured using a dynamic viscoelasticity measuring apparatus (DMS 6100 manufactured by Seiko Instruments Inc.) under a nitrogen gas flow of 300 mL Zmin., Temperature rising rate 3 ° C. Z min., Frequency 1 Hz The temperature was measured according to the conditions, and the peak top temperature of tan ⁇ was taken as the glass transition temperature.
- DMS 6100 dynamic viscoelasticity measuring apparatus
- the thermal decomposition temperature of the obtained resin film was measured using a TGZDTA measuring device (TGZDTA 220 manufactured by Seiko Instruments Inc.) under the conditions of a temperature increase rate of 10 ° C. Z min.
- the thermal decomposition temperature was determined as the temperature at which the weight loss reached 5%.
- Relative permittivity (capacity measurement value X film thickness) Z (vacuum permittivity X measurement area)
- Examples 1 to 14 had high glass transition temperatures and thermal decomposition temperatures, and were excellent in heat resistance.
- Examples 1 to 14 were shown to be excellent in workability and dielectric properties that are soluble in a solvent and that the dielectric constant is low !.
- the benzoxazole resin precursor obtained in Example 1 was dissolved in N-methyl-2-pyrrolidone and filtered through a Teflon (registered trademark) filter to obtain a varnish for coating.
- a silicon nitride layer is formed on a semiconductor substrate, the coating varnish obtained above is applied on the silicon nitride layer, and heat treatment is performed at 250 ° C. for 1 hour and 420 ° C. for 1 hour.
- An interlayer insulating film having a thickness of 0.3 // m was formed.
- a metal wiring was formed to form a predetermined pattern in the interlayer insulating film, to obtain a semiconductor device.
- Example 15 was shown to have high glass transition temperature and thermal decomposition temperature and excellent heat resistance.
- Example 15 is soluble in a solvent, and particularly excellent in workability and dielectric properties particularly low in dielectric constant !.
- the degree of wiring delay was compared between a semiconductor device obtained using the interlayer insulating film of Example 15 and a semiconductor device having an SiO insulating film with the same configuration as this semiconductor device.
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
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EP06798229A EP1953181A4 (en) | 2005-09-21 | 2006-09-21 | RESIN COMPOSITION, VARNISH, RESIN FILM, AND SEMICONDUCTOR DEVICE |
JP2007536565A JP5169219B2 (ja) | 2005-09-21 | 2006-09-21 | 樹脂組成物、ワニス、樹脂膜および半導体装置 |
US11/992,136 US8178631B2 (en) | 2005-09-21 | 2006-09-21 | Resin composition, varnish, resin film and semiconductor device |
CN2006800348386A CN101268119B (zh) | 2005-09-21 | 2006-09-21 | 树脂组合物、清漆、树脂膜及半导体装置 |
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JP2005274729 | 2005-09-21 | ||
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US (1) | US8178631B2 (ja) |
EP (1) | EP1953181A4 (ja) |
JP (1) | JP5169219B2 (ja) |
KR (1) | KR101021163B1 (ja) |
CN (1) | CN101268119B (ja) |
WO (1) | WO2007034902A1 (ja) |
Cited By (6)
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JP2008231174A (ja) * | 2007-03-19 | 2008-10-02 | Fujifilm Corp | 膜形成用組成物、絶縁膜及び電子デバイス |
EP2014636A1 (en) * | 2007-07-05 | 2009-01-14 | Daicel Chemical Industries, Ltd. | Ethynylphenylbiadamantane derivatives |
JP2009023983A (ja) * | 2007-06-21 | 2009-02-05 | Daicel Chem Ind Ltd | エチニル基含有有橋脂環式化合物、絶縁膜形成材料、絶縁膜及びその製造方法 |
JP2009029766A (ja) * | 2007-06-25 | 2009-02-12 | Daicel Chem Ind Ltd | N−置換ベンズイミダゾール環含有有橋脂環式化合物、n−置換ベンズイミダゾール環含有重合体、薄膜及びその製造方法 |
EP2003123A3 (en) * | 2007-06-14 | 2009-03-04 | Daicel Chemical Industries, Ltd. | Thin-film materials, thin films and producing method thereof |
EP2177545A4 (en) * | 2007-07-30 | 2011-11-02 | Sumitomo Bakelite Co | POLYMER FOR FORMING INSULATING FILM, COMPOSITION FOR FORMING INSULATING FILM, INSULATING FILM, AND ELECTRONIC DEVICE COMPRISING INSULATING FILM |
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KR20090004969A (ko) * | 2006-03-29 | 2009-01-12 | 스미토모 베이클리트 컴퍼니 리미티드 | 수지 조성물, 바니시, 수지막 및 그것을 이용한 반도체 장치 |
KR101333698B1 (ko) * | 2009-11-10 | 2013-11-27 | 제일모직주식회사 | 포지티브형 감광성 수지 조성물 |
JP2011254041A (ja) * | 2010-06-04 | 2011-12-15 | Renesas Electronics Corp | 半導体装置 |
KR20120066923A (ko) | 2010-12-15 | 2012-06-25 | 제일모직주식회사 | 신규 페놀 화합물 및 이를 포함하는 포지티브형 감광성 수지 조성물 |
KR101423539B1 (ko) | 2010-12-20 | 2014-07-25 | 삼성전자 주식회사 | 포지티브형 감광성 수지 조성물 |
WO2016167342A1 (ja) * | 2015-04-17 | 2016-10-20 | 国立研究開発法人産業技術総合研究所 | 架橋ポリマー構造体及びその使用 |
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JP2009023983A (ja) * | 2007-06-21 | 2009-02-05 | Daicel Chem Ind Ltd | エチニル基含有有橋脂環式化合物、絶縁膜形成材料、絶縁膜及びその製造方法 |
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Also Published As
Publication number | Publication date |
---|---|
EP1953181A4 (en) | 2011-08-31 |
KR101021163B1 (ko) | 2011-03-15 |
CN101268119A (zh) | 2008-09-17 |
US20090214860A1 (en) | 2009-08-27 |
KR20080053382A (ko) | 2008-06-12 |
JP5169219B2 (ja) | 2013-03-27 |
EP1953181A1 (en) | 2008-08-06 |
US8178631B2 (en) | 2012-05-15 |
CN101268119B (zh) | 2011-08-17 |
JPWO2007034902A1 (ja) | 2009-03-26 |
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