Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/022—Quinonediazides
  • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
  • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
  • H10P52/00—Grinding, lapping or polishing of wafers, substrates or parts of devices
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W72/00—Interconnections or connectors in packages
  • H10W72/071—Connecting or disconnecting
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/10—Encapsulations, e.g. protective coatings characterised by their shape or disposition
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials

Definitions

• the present disclosure relates to a hybrid bonding insulating film forming material, a method for manufacturing a semiconductor device, and a semiconductor device.
• Non-Patent Document 1 discloses an example of three-dimensional mounting of a semiconductor chip.
• hybrid bonding technology used in W2W (Wafer-to-Wafer) bonding is used to perform fine bonding of wiring between devices. is being considered.
• Patent Document 1 discloses an example of a technique that can lower the bonding temperature by using a cyclic olefin resin.
• thermoplastic resin such as polyimide or polybenzoxazole
• the glass transition temperature of the resin needs to be lowered.
• lowering the glass transition temperature of the resin may cause problems in heat resistance. Therefore, there is a need for resin materials that can be bonded in a temperature range below the glass transition temperature.
• the present disclosure has been made in view of the above-mentioned conventional circumstances, and provides a hybrid bonding insulating film forming material that can be bonded in a temperature range below the glass transition temperature, and a semiconductor device using this hybrid bonding insulating film forming material. The purpose is to provide a method for producing the same.
• ⁇ 3> Prepare a first semiconductor substrate having a first substrate body, a first electrode and a first organic insulating film provided on one surface of the first substrate body, preparing a semiconductor chip having a semiconductor chip substrate body, a second organic insulating film and a second electrode provided on one surface of the semiconductor chip substrate body; bonding the first electrode and the second electrode and bonding the first organic insulating film and the second organic insulating film; A method for manufacturing a semiconductor device using the hybrid bonding insulating film forming material according to ⁇ 1> or ⁇ 2> for producing at least one of a first organic insulating film and a second organic insulating film.
• ⁇ 4> The method for manufacturing a semiconductor device according to ⁇ 3>, wherein the first electrode and the second electrode are bonded after the first organic insulating film and the second organic insulating film are bonded together.
• the semiconductor chip is prepared by dividing into pieces a second semiconductor substrate having a second substrate body, a plurality of second electrodes and a second organic insulating region provided on one surface of the second substrate body.
• ⁇ 6> The first organic insulating film and the second organic insulating film are bonded together at a temperature such that a temperature difference between the semiconductor chip and the first semiconductor substrate is within 10° C.
• the total thickness of the organic insulating film formed by bonding the first organic insulating film and the second organic insulating film is 0.1 ⁇ m or more ⁇ 3> to ⁇
• the first semiconductor substrate is The method for manufacturing a semiconductor device according to any one of ⁇ 3> to ⁇ 7>, wherein at least one of the one surface and the one surface of the semiconductor chip is polished.
• ⁇ 9> The method for manufacturing a semiconductor device according to ⁇ 8>, wherein the polishing includes chemical mechanical polishing.
• the polishing further includes mechanical polishing.
• ⁇ 11> At least one of the following is satisfied: the thickness of the first electrode is thicker than the thickness of the first organic insulating film, and the thickness of the second electrode is thicker than the thickness of the second organic insulating film.
• a first semiconductor substrate having a first substrate body, a first organic insulating film and a first electrode provided on one surface of the first substrate body,
• a semiconductor chip having a semiconductor chip substrate body, a second organic insulating film and a second electrode provided on one surface of the semiconductor chip substrate body, The first organic insulating film and the second organic insulating film are bonded, the first electrode and the second electrode are bonded,
• a semiconductor device wherein at least one of the first organic insulating film and the second organic insulating film is a cured product of the hybrid bonding insulating film forming material according to ⁇ 1> or ⁇ 2>.
• the present disclosure it is possible to provide a hybrid bonding insulating film forming material capable of bonding in a temperature range below the glass transition temperature, a semiconductor device using this hybrid bonding insulating film forming material, and a method for manufacturing the same. .
• FIG. 1 is a cross-sectional view schematically showing an example of a semiconductor device manufactured by a method for manufacturing a semiconductor device according to an embodiment.
• FIG. 2 is a diagram sequentially showing a method for manufacturing the semiconductor device shown in FIG.
• FIG. 3 is a diagram showing in more detail the bonding method in the method of manufacturing the semiconductor device shown in FIG.
• FIG. 4 shows a method for manufacturing the semiconductor device shown in FIG. 1, and is a diagram showing the steps after the step shown in FIG. 2 in order.
• FIG. 5 is a diagram showing an example in which the method for manufacturing a semiconductor device according to an embodiment is applied to Chip-to-Wafer (C2W).
• C2W Chip-to-Wafer
• step includes not only a step that is independent from other steps, but also a step that cannot be clearly distinguished from other steps, as long as the purpose of the step is achieved.
• numerical ranges indicated using “ ⁇ ” include the numerical values written before and after " ⁇ " as minimum and maximum values, respectively.
• the upper limit or lower limit described in one numerical range may be replaced with the upper limit or lower limit of another numerical range described step by step.
• the upper limit or lower limit of the numerical range may be replaced with the values shown in the Examples.
• each component may contain multiple types of applicable substances.
• the content rate or content of each component is the total content rate or content of the multiple types of substances present in the composition, unless otherwise specified. means quantity.
• the particles corresponding to each component may include multiple types of particles.
• the particle diameter of each component means a value for a mixture of the plurality of types of particles present in the composition, unless otherwise specified.
• the term "layer” or “film” refers to the case where the layer or film is formed only in a part of the region, in addition to the case where the layer or film is formed in the entire region when observing the region where the layer or film is present.
• the average thickness of a layer or film is a value given as the arithmetic mean value of the thicknesses measured at five points of the target layer or film.
• the thickness of a layer or film can be measured using a micrometer or the like. In this disclosure, when the thickness of a layer or film can be measured directly, it is measured using a micrometer. On the other hand, when measuring the thickness of one layer or the total thickness of a plurality of layers, it may be measured by observing a cross section of the measurement target using an electron microscope.
• the hybrid bonding insulating film forming material of the present disclosure (hereinafter, the hybrid bonding insulating film forming material may be simply referred to as "insulating film forming material”) comprises a thermosetting polyamide having a phenolic hydroxyl group in the molecule; Contains a solvent.
• the insulating film forming material of the present disclosure may contain other components such as a crosslinking agent and a polymerization initiator as necessary. According to the present disclosure, it is possible to provide an insulating film forming material that can be bonded in a temperature range below the glass transition temperature. Although the reason is not clear, it is inferred as follows.
• the insulating film forming material of the present disclosure includes a thermosetting polyamide having a phenolic hydroxyl group in the molecule.
• a thermosetting polyamide having phenolic hydroxyl groups in its molecules is cured by a thermosetting reaction to produce a cured product, some of the phenolic hydroxyl groups are exposed on the surface of the cured product.
• cured products with phenolic hydroxyl groups exposed on the surface are pressed together while heating, a curing reaction occurs between the unreacted thermosetting polyamides contained in the cured products and having phenolic hydroxyl groups in their molecules.
• the curing reaction between thermosetting polyamides on the surface of the cured product can proceed even below the glass transition temperature.
• thermosetting polyamide having a phenolic hydroxyl group in the molecule used in the present disclosure examples include polybenzoxazole precursors, polyimide precursors (polyamic acid, etc.), and the like.
• the position of the phenolic hydroxyl group in the thermosetting polyamide is not particularly limited, and may be at the end of the thermosetting polyamide or within the main chain skeleton.
• thermosetting polyamide having a phenolic hydroxyl group in the molecule is a polybenzoxazole precursor and a polyimide precursor (polyamic acid)
• thermosetting polyamide having a phenolic hydroxyl group in the molecule is a polybenzoxazole precursor
• polyimide precursor polyamic acid
• the first insulating film forming material contains (a) a polybenzoxazole precursor as a thermosetting polyamide having a phenolic hydroxyl group in its molecule.
• a polybenzoxazole precursor as a thermosetting polyamide having a phenolic hydroxyl group in its molecule.
• one type of compound is sometimes simply referred to as component (a), component (b), component (c), and component (d), respectively.
• the first insulating film forming material may include a polyimide precursor having a phenolic hydroxyl group in its molecule, or may include a polyimide precursor having no phenolic hydroxyl group in its molecule.
• the first insulating film forming material contains at least one of a polyimide precursor having phenolic hydroxyl groups in the molecule and a polyimide precursor having no phenolic hydroxyl groups in the molecule, the polyimide precursor having phenolic hydroxyl groups in the molecule
• the proportion of the polybenzoxazole precursor that has a phenolic hydroxyl group in the molecule in the total of the benzoxazole precursor, the polyimide precursor that has a phenolic hydroxyl group in the molecule, and the polyimide precursor that does not have a phenolic hydroxyl group in the molecule is , preferably 50% by mass or more and less than 100% by mass, more preferably 60% by mass to 90% by mass, even more preferably 65% by mass to 80% by mass.
• the type of polybenzoxazole precursor is not particularly limited.
• the polybenzoxazole precursor preferably has a structural unit represented by the following formula (II).
• U is a tetravalent organic group
• V is a divalent organic group.
• At least a portion of the amide unit containing a hydroxy group in formula (II) is converted into an oxazole ring having excellent heat resistance, chemical resistance, and electrical properties by dehydration ring closure in the heating step.
• the amide unit containing a hydroxy group is effective in improving the solubility of the polymer in an alkaline aqueous solution.
• the polymer having the structural unit represented by formula (II) may contain only one type of structural unit, or may contain two or more types of structural units. When it is a copolymer having two or more types of structural units, it may be a polymer having at least two types of structural units represented by formula (II), and a polymer having a structure represented by formula (III). It may be.
• a polymer having a structural unit represented by formula (II) has at least two types of structural units represented by formula (II)
• the combination of structural units represented by formula (II) is particularly limited. For example, structural units in which the divalent organic group represented by V is a divalent aromatic group, and structural units in which V is a divalent organic group having an aliphatic structure having 6 to 30 carbon atoms. It may be a combination with.
• U is a tetravalent organic group
• V and W are each independently a divalent organic group.
• j and k are mole fractions, and the sum of j and k is 100 moles.
• % j is 60 to 99.9 mol%
• k is 0.1 mol% to 40 mol% (preferably j is 80 mol% to 99.9 mol%, k is 0.1 mol% to 20 mol%). %).
• the tetravalent organic group represented by U is a residue of diamines used in the synthesis of polyhydroxyamide.
• the tetravalent organic group represented by U is preferably a tetravalent aromatic group or an organic group having 6 to 40 carbon atoms, and preferably a tetravalent aromatic group having 6 to 40 carbon atoms. More preferred.
• the tetravalent aromatic group one in which all four bonding sites are present on an aromatic ring is preferable. Note that the aromatic group refers to a group containing an aromatic ring.
• Examples of diamines that provide a tetravalent organic group represented by U include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, and bis(3 -amino-4-hydroxyphenyl)propane, bis(4-amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 2 , 2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-amino-3-hydroxyphenyl)-1,1 , 1,3,3,3-hexafluoropropane and the like, but are not limited to these.
• the divalent organic group represented by W in formula (III) is a residue of diamines used in the synthesis of polyhydroxyamide.
• the divalent organic group represented by W is preferably a divalent aromatic group, a divalent aliphatic group, or an organic group having 4 to 20 carbon atoms, and an aromatic group having 4 to 20 carbon atoms. More preferably, it is a group.
• the divalent organic group represented by W is a residue of diamines other than the diamines that provide the tetravalent organic group represented by U.
• Examples of diamines that provide a divalent organic group represented by W include 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, and 4,4'-diaminodiphenyl sulfide.
• benzicine m-phenylenediamine, p-phenylenediamine, 1,5-naphthalenediamine, 2,6-naphthalenediamine, bis(4-aminophenoxyphenyl)sulfone, bis(3-aminophenoxyphenyl)sulfone, bis(4-aminophenoxyphenyl)sulfone,
• aromatic diamine compounds such as -aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, and 1,4-bis(4-aminophenoxy)benzene.
• diamines having silicone groups LP-7100, X-22-161AS, X-22-161A, X-22-161B, X-22-161C and (manufactured by a company, product name), etc., but is not limited to these.
• the divalent organic group represented by V is a residue of a dicarboxylic acid or a dicarboxylic acid derivative (hereinafter referred to as dicarboxylic acids) used in the synthesis of polyhydroxyamide.
• the divalent organic group represented by V is preferably a divalent aromatic group or an organic group having 6 to 40 carbon atoms. From the viewpoint of heat resistance, a divalent aromatic group having 6 to 40 carbon atoms is preferable, and a divalent aromatic group in which both of the two bonding sites are present on an aromatic ring is preferable. preferable.
• V is a divalent organic group having an aliphatic structure with 6 to 30 carbon atoms. It is preferable that
• Dicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, those having an aliphatic straight chain structure include malonic acid, dimethylmalonic acid, ethylmalonic acid, Isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid , hexafluoroglutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipine Acid, 3-methyladipic acid, pimelic
• dicarboxylic acids represented by the following formulas, but are not limited thereto. These compounds can be used alone or in combination of two or more. (In the formula, each Z is independently a hydrocarbon group having 1 to 6 carbon atoms, and i is an integer of 1 to 6.)
• component (a) there are no particular limitations on the method for producing component (a).
• it can be synthesized by using dicarboxylic acids, hydroxy group-containing diamines, and, if necessary, diamines other than the hydroxy group-containing diamines.
• it can be synthesized by converting a dicarboxylic acid derivative into a dihalide derivative and then reacting it with diamines.
• dihalide derivative dichloride derivatives are preferred.
• Dichloride derivatives can be synthesized by reacting dicarboxylic acids and a halogenating agent in a solvent, or by performing a reaction in an excess of the halogenating agent and then distilling off the excess.
• a halogenating agent thionyl chloride, phosphoryl chloride, phosphorus oxychloride, phosphorus pentachloride, etc., which are commonly used in the acid chloridation reaction of carboxylic acids, can be used.
• As the reaction solvent N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N,N-dimethylacetamide, N,N-dimethylformamide, toluene, benzene, etc. can be used.
• the amount of these halogenating agents used is preferably 1.5 mol to 3.0 mol, and 1.7 mol to 2.5 mol, per 1.0 mol of the dicarboxylic acid derivative. is more preferable, and when the reaction is carried out in a halogenating agent, the amount is preferably 4.0 mol to 50 mol, and more preferably 5.0 mol to 20 mol.
• the reaction temperature is preferably -10°C to 70°C, more preferably 0°C to 20°C.
• the reaction between the dichloride derivative and diamines is preferably carried out in an organic solvent in the presence of a dehydrohalogenating agent.
• a dehydrohalogenating agent organic bases such as pyridine and triethylamine can be used.
• organic solvent N-methyl-2-pyrrolidone, N-methyl-2-pyridone, N,N-dimethylacetamide, N,N-dimethylformamide, etc. can be used.
• the reaction temperature is preferably -10°C to 30°C, more preferably 0°C to 20°C.
• diamines examples include aromatic diamines, aliphatic diamines, and alicyclic diamines.
• Component (a) may be developed with an alkaline aqueous solution. Therefore, it is preferable that it is soluble in an alkaline aqueous solution.
• the alkaline aqueous solution include organic ammonium aqueous solutions such as tetramethylammonium hydroxide (TMAH) aqueous solutions, metal hydroxide aqueous solutions, and organic amine aqueous solutions.
• TMAH tetramethylammonium hydroxide
• metal hydroxide aqueous solutions metal hydroxide aqueous solutions
• organic amine aqueous solutions Generally, it is preferable to use a TMAH aqueous solution having a concentration of 2.38% by mass. Therefore, it is preferable that component (a) is soluble in the TMAH aqueous solution.
• component (a) being soluble in an alkaline aqueous solution.
• a resin film having a thickness of about 5 ⁇ m is formed by spin coating onto a substrate such as a silicon wafer. This is immersed in any one of a TMAH aqueous solution, a metal hydroxide aqueous solution, and an organic amine aqueous solution at 20°C to 25°C.
• TMAH aqueous solution a metal hydroxide aqueous solution
• organic amine aqueous solution at 20°C to 25°C.
• the molecular weight of the resin soluble in the alkaline aqueous solution of component (a) is preferably a weight average molecular weight of 10,000 to 100,000 in terms of polystyrene, more preferably 12,000 to 100,000. , 14,000 to 85,000 is more preferable.
• the weight average molecular weight of component (a) is 10,000 or more, appropriate solubility in an alkaline developer can be ensured. Further, when the weight average molecular weight of component (a) is 100,000 or less, good solubility in a solvent tends to be obtained, and it is possible to suppress increase in viscosity of the solution and decrease in handling properties.
• the weight average molecular weight can be measured by gel permeation chromatography, and can be determined by conversion using a standard polystyrene calibration curve. Further, the dispersity obtained by dividing the weight average molecular weight by the number average molecular weight is preferably 1.0 to 4.0, more preferably 1.0 to 3.5.
• the first insulating film forming material may contain a photosensitive agent as the component (b) together with a polybenzoxazole precursor or a copolymer of the polybenzoxazole precursor as the component (a).
• This photosensitizer is one that reacts to light and has a function for developing a film formed from the composition.
• the photosensitizer used as component (b) in the present disclosure it is preferably one that generates acid or radicals when exposed to light.
• the photosensitive agent (b) is more preferably one that generates acid when exposed to light (photoacid generator).
• the photoacid generator has the function of generating an acid upon irradiation with light and increasing the solubility of the irradiated area in an alkaline aqueous solution.
• photoacid generators include o-quinonediazide compounds, aryldiazonium salts, diaryliodonium salts, triarylsulfonium salts, and o-quinonediazide compounds are preferred due to their high sensitivity.
• the above o-quinonediazide compound can be obtained, for example, by subjecting an o-quinonediazide sulfonyl chloride to a hydroxy compound, an amino compound, etc. to a condensation reaction in the presence of a dehydrochlorination agent.
• the o-quinonediazide sulfonyl chloride include benzoquinone-1,2-diazide-4-sulfonyl chloride, naphthoquinone-1,2-diazide-5-sulfonyl chloride, and naphthoquinone-1,2-diazide-4-sulfonyl chloride. etc. can be used.
• hydroxy compound examples include hydroquinone, resorcinol, pyrogallol, bisphenol A, bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)hexafluoropropane, and 2,3,4-trihydroxybenzophenone.
• amino compound examples include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenyl Sulfide, o-aminophenol, m-aminophenol, p-aminophenol, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis(3 -amino-4-hydroxyphenyl)propane, bis(4-amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, bis (3-amino-4-hydroxyphenyl)hex
• the o-quinonediazide sulfonyl chloride and the hydroxy compound and/or amino compound are blended such that the total of the hydroxy group and the amino group is 0.5 equivalent to 1 equivalent per 1 mole of the o-quinone diazide sulfonyl chloride. It is preferable.
• the preferred ratio of dehydrochlorination agent to o-quinonediazide sulfonyl chloride is in the range of 0.95/1 to 1/0.95.
• the preferred reaction temperature is 0°C to 40°C, and the preferred reaction time is 1 hour to 10 hours.
• reaction solvent for the above reaction solvents such as dioxane, acetone, methyl ethyl ketone, tetrahydrofuran, diethyl ether, and N-methyl-2-pyrrolidone are used.
• dehydrochlorination agents include sodium carbonate, sodium hydroxide, sodium hydrogen carbonate, potassium carbonate, potassium hydroxide, trimethylamine, triethylamine, and pyridine.
• the component (b) is one that generates radicals or a compound that can be crosslinked or polymerized by the action of an acid.
• the first insulating film-forming material can be used as a negative photosensitive resin composition by using an acid-generating component as the component (b), that is, as a photopolymerization initiator. .
• This negative photosensitive resin composition has the function of reducing the solubility of the light irradiated area in an alkaline aqueous solution through a crosslinking reaction caused by light irradiation.
• the blending amount of component (b) is determined based on the dissolution rate difference between exposed and unexposed areas and the allowable range of sensitivity. It is preferably 5 parts by mass to 100 parts by mass, more preferably 8 parts by mass to 40 parts by mass, based on 100 parts by mass.
• the first insulating film forming material contains a solvent.
• Solvents include ⁇ -butyrolactone, ethyl lactate, propylene glycol monomethyl ether acetate, benzyl acetate, n-butyl acetate, ethoxyethyl propionate, methyl 3-methoxypropionate, N-methyl-2-pyrrolidone, N,N -Dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, hexamethylphosphorylamide, tetramethylenesulfone, cyclohexanone, cyclopentanone, diethylketone, diisobutylketone, methylamylketone, 3-methoxy-N,N-dimethylpropanamide etc.
• solvents can be used alone or in combination of two or more. Further, although there is no particular restriction on the amount of the solvent used, it is generally preferable to adjust the proportion of the solvent in the first insulating film forming material to 20% by mass to 90% by mass.
• the first insulating film forming material may contain component (d).
• the heterocyclic compound refers to a cyclic compound in which a ring is composed of atoms of two or more elements (in addition to carbon, nitrogen, oxygen, sulfur, etc.).
• heterocyclic compounds include triazole ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, and pyrimididine ring.
• a pyrazine ring a piperidine ring, a piperidine ring, a piperazine ring, a morpholine ring, a 2H-pyran ring, a 6H-pyran ring, a triazine ring, among others, a triazole ring containing a carbon atom and a nitrogen atom, a pyrrole ring, Compounds having a pyrazole ring, thiazole ring, imidazole ring and tetrazole ring are preferred.
• thioureas include monomethylthiourea, thiourea, dimethylthiourea, diethylthiourea, dibutylthiourea, etc., but are not limited to these.
• heterocyclic compounds and compounds having a mercapto group include pyrrole, 3-methylpyrrole, 2,4-dimethylpyrrole, 2,5-dimethylpyrrole, 2-ethylpyrrole, and indole.
• At least one selected from the group consisting of 1H-tetrazole, 5-substituted-1H-tetrazole, 1-substituted-1H-tetrazole and derivatives thereof is preferred, and 1,2,3-triazole, 1 , 2,4-triazole and its derivatives, 1,2,3-benzotriazole, 5-substituted-1H-benzotriazole, 6-substituted-1H-benzotriazole, 5,6-substituted-1H-benzotriazole and its derivatives.
• At least one selected from the following is more preferred, and 5-methyl-1H-benzotriazole, 1H-tetrazole, 5-methyl-1H-tetrazole, and 5,5'-bis-1H-tetrazole are particularly preferred.
• Component (d) is used to prevent corrosion between the photosensitive resin and the substrate (for example, copper and copper alloy) and to improve adhesion.
• the blending amount of component (d) is usually 0.1 parts by mass to 10 parts by mass per 100 parts by mass of component (a) (base resin), and when two or more kinds are combined, the total amount is 0.1 parts by mass.
• the amount is 1 part by mass to 10 parts by mass. More preferably, the amount is in the range of 0.2 parts by mass to 5 parts by mass. If it is 0.1 part by mass or more, it tends to ensure the effect of improving the adhesion to the metal layer, and if it is 10 parts by mass or less, the effect of improving the adhesion depending on the amount of component (d) added can be enjoyed. There is a tendency.
• the first insulating film forming material preferably contains a crosslinking agent that can be crosslinked or polymerized by heating.
• a compound that is a crosslinking agent reacts with the polybenzoxazole precursor or polybenzoxazole, that is, forms a bridge, in the step of applying heat, exposing, and developing the first insulating film forming material.
• the compound itself that is a crosslinking agent polymerizes. This prevents the brittleness of the film, which is a concern when curing at a relatively low temperature, for example, 200° C. or lower, and improves mechanical properties, chemical resistance, flux resistance, and the like.
• Component (e) is not particularly limited as long as it is a compound that crosslinks or polymerizes in the heat treatment step, but it is preferably a compound having a methylol group, an alkoxymethyl group, an epoxy group, or a vinyl ether group in the molecule.
• Compounds in which these groups are bonded to a benzene ring, or melamine resins and urea resins in which the N-position is substituted with a methylol group and/or an alkoxymethyl group are preferred.
• Compounds in which these groups are bonded to a benzene ring having a phenolic hydroxyl group are more preferable because they can increase the dissolution rate of exposed areas during development and improve sensitivity.
• compounds having two or more methylol groups or alkoxymethyl groups in the molecule are more preferred in terms of sensitivity and varnish stability, as well as the ability to prevent melting of the film during curing after pattern formation.
• Such compounds can be represented by the following general formulas (9) to (11).
• G represents a single bond or a monovalent to tetravalent organic group
• R 11 and R 12 each independently represent a hydrogen atom or a monovalent organic group
• o is an integer of 1 to 4
• p and q are each independently integers from 0 to 4.
• the two J's are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and may contain an oxygen atom or a fluorine atom
• R 13 to R 16 are each independently a hydrogen atom or a monovalent represents an organic group
• r and s are each independently an integer of 1 to 3
• p and q are each independently an integer of 0 to 3.
• R 17 and R 18 each independently represent a hydrogen atom or a monovalent organic group, and a plurality of R 18s have a ring structure and may be connected to each other.
• crosslinking agent examples include, but are not limited to, the following chemical formula (12). Moreover, these compounds can be used alone or in combination of two or more.
• the blending amount of component (e) is determined from the viewpoints of development time, permissible range of residual film rate in unexposed areas, and physical properties of the cured film. , preferably 1 part by mass to 50 parts by mass per 100 parts by mass of component (a) (base resin).
• the amount is more preferably 20 parts by mass or more, ie, 20 parts by mass to 50 parts by mass.
• the crosslinking agent (E) Polymer monomers may also be used.
• thermo acid generator that generates acid upon heating
• a thermal acid generator thermal latent acid generator
• the acid generated from the thermal acid generator is preferably a strong acid, and specifically, examples include p-toluenesulfonic acid, arylsulfonic acid such as benzenesulfonic acid, camphorsulfonic acid, Perfluoroalkylsulfonic acids such as trifluoromethanesulfonic acid and nonafluorobutanesulfonic acid, alkylsulfonic acids such as methanesulfonic acid, ethanesulfonic acid, butanesulfonic acid, and the like are preferred. These acids efficiently act as catalysts when the phenolic hydroxyl group-containing polyamide structure of the polybenzoxazole precursor undergoes a dehydration reaction and is cyclized.
• These acids are added to the first insulating film forming material as a thermal acid generator in the form of a salt such as an onium salt or a covalent bond form such as an imidosulfonate.
• onium salts examples include diaryliodonium salts such as diphenyliodonium salts, di(alkylaryl)iodonium salts such as di(t-butylphenyl)iodonium salts, trialkylsulfonium salts such as trimethylsulfonium salts, dimethyl Dialkylmonoarylsulfonium salts such as phenylsulfonium salts, diarylmonoalkyliodonium salts such as diphenylmethylsulfonium salts, and the like are preferred. These are preferred because the decomposition initiation temperature is in the range of 150°C to 250°C, and they are efficiently decomposed during the cyclization and dehydration reaction of the polybenzoxazole precursor at 280°C or lower.
• thermal acid generators in the form of onium salts include, for example, diaryliodonium salts, di(alkylaryl)iodonium salts, trialkyl sulfonic acids, camphorsulfonic acids, perfluoroalkylsulfonic acids, or alkylsulfonic acids.
• Sulfonium salts, dialkylmonoarylsulfonium salts, and diarylmonoalkyliodonium salts are preferred from the viewpoint of storage stability and developability.
• di(t-butylphenyl)iodonium salt of para-toluenesulfonic acid 1% weight loss temperature 180°C, 5% weight loss temperature 185°C
• di(t-butylphenyl) trifluoromethanesulfonic acid Iodonium salt 1% weight loss temperature 151°C, 5% weight loss temperature 173°C
• trimethylsulfonium salt of trifluoromethanesulfonic acid 1% weight loss temperature 255°C, 5% weight loss temperature 278°C
• diphenylmethylsulfonium salt of trifluoromethanesulfonic acid 1% weight loss temperature 154°C, 5% weight loss temperature 179°C
• examples of the imidosulfonate include phthalimide sulfonate and naphthoylimide sulfonate, with naphthoylimide sulfonate being preferred.
• Specific examples of naphthoylimide sulfonates include 1,8-naphthoylimide trifluoromethylsulfonate (1% weight loss temperature: 189°C, 5% weight loss temperature: 227°C), 2,3-naphthoylimide Preferred examples include trifluoromethylsulfonate (1% weight loss temperature: 185°C, 5% weight loss temperature: 216°C).
• R 21 is, for example, an aryl group such as a p-methylphenyl group or a phenyl group, an alkyl group such as a methyl group, an ethyl group, or an isopropyl group, or a perfluoroalkyl group such as a trifluoromethyl group or a nonafluorobutyl group. Examples include groups.
• examples of R 19 include a cyano group
• examples of R 20 include a methoxyphenyl group and a phenyl group.
• R 22 includes, for example, an alkyl group such as a methyl group, an ethyl group, and a propyl group, an aryl group such as a methylphenyl group and a phenyl group, and a perfluoroalkyl group such as a trifluoromethyl group and a nonafluorobutyl group. Can be mentioned.
• -HN-SO 2 -R 22 for example, 2,2,-bis(4-hydroxyphenyl)hexafluoropropane, 2,2,-bis(4-hydroxyphenyl)propane, di- (4-hydroxyphenyl)ether and the like.
• a salt formed from a strong acid and a base other than onium salts can also be used.
• strong acids include arylsulfonic acids such as p-toluenesulfonic acid and benzenesulfonic acid, perfluoroalkylsulfonic acids such as camphorsulfonic acid, trifluoromethanesulfonic acid, and nonafluorobutanesulfonic acid, and methanesulfonic acid.
• Acid, alkylsulfonic acids such as ethanesulfonic acid, butanesulfonic acid are preferred.
• Preferred examples of the base include pyridine, alkylpyridine such as 2,4,6-trimethylpyridine, N-alkylpyridine such as 2-chloro-N-methylpyridine, and halogenated-N-alkylpyridine. More specifically, p-toluenesulfonic acid pyridine salt (1% weight loss temperature 147°C, 5% weight loss temperature 190°C), p-toluenesulfonic acid L-aspartic acid dibenzyl ester salt (1% weight loss temperature 190°C), 2,4,6-trimethylpyridine salt of p-toluenesulfonic acid, 1,4-dimethylpyridine salt of p-toluenesulfonic acid, etc. have good storage stability and development. These are preferred from the viewpoint of performance. These also decompose during the cyclization and dehydration reaction of the polybenzoxazole precursor at 280° C. or lower, and can function as a catalyst.
• the blending amount of component (f) is preferably 0.1 parts by mass to 30 parts by mass, and preferably 0.2 parts by mass to 20 parts by mass, per 100 parts by mass of component (a) (base resin). is more preferable, and even more preferably 0.5 parts by weight to 10 parts by weight.
• the first insulating film forming material includes (1) a dissolution promoter, (2) a dissolution inhibitor, (3) an adhesion imparting agent, and (4) a surfactant.
• a dissolution promoter for a dissolution of a dissolution of a dissolution in a dissolution environment.
• the second insulating film forming material includes (A) a polyimide precursor as a thermosetting polyamide having a phenolic hydroxyl group in its molecule.
• the polyimide precursor may have a polymerizable unsaturated bond site.
• the second insulating film forming material may include a polybenzoxazole precursor having a phenolic hydroxyl group in its molecule, or a polyimide precursor having no phenolic hydroxyl group in its molecule.
• the second insulating film forming material contains at least one of a polybenzoxazole precursor having a phenolic hydroxyl group in its molecule and a polyimide precursor having no phenolic hydroxyl group in its molecule
• the proportion of the polyimide precursor that has a phenolic hydroxyl group in the molecule in the total of the polyimide precursor that has a phenolic hydroxyl group in the molecule, the polybenzoxazole precursor that has a phenolic hydroxyl group in the molecule, and the polyimide precursor that does not have a phenolic hydroxyl group in the molecule is , preferably 50% by mass or more and less than 100% by mass, more preferably 60% by mass to 90% by mass, even more preferably 65% by mass to 80% by mass.
• the second insulating film forming material does not need to contain a polybenzoxazole precursor having a phenolic hydroxyl group in its molecule, or it may not contain a polyimide precursor having no phenolic hydroxyl group in its molecule. Good too.
• the polyimide precursor is preferably at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide.
• Polyamic acid ester and polyamic acid amide are compounds in which at least some of the carboxy groups in polyamic acid have hydrogen atoms substituted with monovalent organic groups
• polyamic acid salts are compounds in which at least some of the carboxy groups in polyamic acid have been replaced with monovalent organic groups. It is a compound that forms a salt structure with a basic compound having a pH of 7 or higher.
• the polyimide precursor preferably contains a compound having a structural unit represented by the following general formula (1). Thereby, a semiconductor device including an insulating film exhibiting high reliability tends to be obtained.
• X represents a tetravalent organic group
• Y represents a divalent organic group
• R 6 and R 7 each independently represent a hydrogen atom or a monovalent organic group, and at least one of R 6 and R 7 may have a polymerizable unsaturated bond.
• the polyimide precursor may have a plurality of structural units represented by the above general formula (1), and X, Y, R 6 and R 7 in the plurality of structural units may be the same or different. You can leave it there. Note that the combination of R 6 and R 7 is not particularly limited as long as they are each independently a hydrogen atom or a monovalent organic group.
• R 6 and R 7 may be a hydrogen atom, and the rest may be monovalent organic groups described below, both may be the same or different monovalent organic groups, or both may be the same or different monovalent organic groups. may be a hydrogen atom.
• the combination of R 6 and R 7 of each structural unit may be the same or different. .
• the tetravalent organic group represented by X preferably has 4 to 25 carbon atoms, more preferably 5 to 13 carbon atoms, and even more preferably 6 to 12 carbon atoms. .
• the tetravalent organic group represented by X may contain an aromatic ring from the viewpoint of heat resistance. Examples of aromatic rings include aromatic hydrocarbon groups (for example, the number of carbon atoms constituting the aromatic ring is 6 to 20), aromatic heterocyclic groups (for example, the number of atoms constituting the heterocycle is 5 to 20), etc. It will be done.
• the tetravalent organic group represented by X is preferably an aromatic hydrocarbon group.
• aromatic hydrocarbon group examples include a benzene ring, a naphthalene ring, and a phenanthrene ring.
• each aromatic ring may have a substituent or may be unsubstituted.
• substituents on the aromatic ring include alkyl groups, fluorine atoms, halogenated alkyl groups, hydroxyl groups, and amino groups.
• the tetravalent organic group represented by X contains a benzene ring
• the tetravalent organic group represented by X preferably contains one to four benzene rings, and preferably contains one to three benzene rings.
• ether bond (-O-), sulfide bond (-S-), silylene bond (-Si(R A ) 2 -; two R A 's each independently represent a hydrogen atom, an alkyl group, or a phenyl group.
• siloxane bond (-O-(Si(R B ) 2 -O-) n ; two R B 's each independently represent a hydrogen atom, an alkyl group, or a phenyl group, and n is an integer of 1 or 2 or more ), or a composite linking group combining at least two of these linking groups.
• two benzene rings may be bonded at two locations by at least one of a single bond and a linking group, to form a five-membered ring or a six-membered ring containing a linking group between the two benzene rings.
• -COOR 6 groups and -CONH- groups are preferably located at ortho positions
• -COOR 7 groups and -CO- groups are preferably located at ortho positions.
• tetravalent organic group represented by X include groups represented by the following formulas (A) to (F).
• a group represented by the following formula (E) is preferable from the viewpoint of obtaining an insulating film that has excellent flexibility and further suppresses the generation of voids at the bonding interface.
• a and B are each independently a single bond or a divalent group that is not conjugated with a benzene ring. However, both A and B cannot be a single bond.
• Divalent groups that are not conjugated with the benzene ring include methylene group, halogenated methylene group, halogenated methylmethylene group, carbonyl group, sulfonyl group, ether bond (-O-), sulfide bond (-S-), and silylene bond.
• a and B are each independently preferably a methylene group, a bis(trifluoromethyl)methylene group, a difluoromethylene group, an ether bond, a sulfide bond, etc., and an ether bond is more preferable.
• C preferably contains an ether bond, and is preferably an ether bond. Further, C may have a structure represented by the following formula (
• the alkylene group represented by C in formula (E) is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 5 carbon atoms, and an alkylene group having 1 to 5 carbon atoms. or 2 alkylene group is more preferable.
• alkylene group represented by C in formula (E) include linear alkylene groups such as methylene group, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, and hexamethylene group; methylmethylene group; Methylethylene group, ethylmethylene group, dimethylmethylene group, 1,1-dimethylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, ethylethylene group, 1-methyltetramethylene group, 2-methyltetramethylene group group, 1-ethyltrimethylene group, 2-ethyltrimethylene group, 1,1-dimethyltrimethylene group, 1,2-dimethyltrimethylene group, 2,2-dimethyltrimethylene group, 1-methylpentamethylene group, 2-methylpentamethylene group, 3-methylpentamethylene group, 1-ethyltetramethylene group, 2-ethyltetramethylene group, 1,1-dimethyltetramethylene group, 1,2-dimethyltramethylene group
• the halogenated alkylene group represented by C in formula (E) is preferably a halogenated alkylene group having 1 to 10 carbon atoms, more preferably a halogenated alkylene group having 1 to 5 carbon atoms. Preferably, a halogenated alkylene group having 1 to 3 carbon atoms is more preferable.
• at least one hydrogen atom contained in the alkylene group represented by C in formula (E) above is a fluorine atom, a chlorine atom, etc.
• Examples include alkylene groups substituted with halogen atoms. Among these, fluoromethylene group, difluoromethylene group, hexafluorodimethylmethylene group, etc. are preferred.
• the alkyl group represented by R A or R B included in the silylene bond or siloxane bond is preferably an alkyl group having 1 to 5 carbon atoms, and preferably an alkyl group having 1 to 3 carbon atoms. is more preferable, and even more preferably an alkyl group having 1 or 2 carbon atoms.
• Specific examples of the alkyl group represented by R A or R B include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, etc. Can be mentioned.
• tetravalent organic group represented by X may be groups represented by the following formulas (J) to (O).
• the tetravalent organic group represented by X may contain an alicyclic ring from the viewpoint of adjusting the coefficient of thermal expansion when a cured product is formed.
• the tetravalent organic group represented by Examples include ring structures that do not contain unsaturated bonds, such as a bicyclo[2.2.2]octane ring, and ring structures that contain unsaturated bonds, such as a cyclohexene ring. Also included are spiro ring structures containing these ring structures.
• an alkyl group such as a fluorine atom, a halogenated alkyl group, a hydroxyl group, or an amino group
• P a specific example of the case where the tetravalent organic group represented by X has a spiro ring structure is the following formula (P).
• the divalent organic group represented by Y preferably has 4 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 12 to 18 carbon atoms.
• the skeleton of the divalent organic group represented by Y may be the same as the skeleton of the tetravalent organic group represented by X, and the preferable skeleton of the divalent organic group represented by Y is It may be the same as the preferred skeleton of the tetravalent organic group represented by.
• the skeleton of the divalent organic group represented by Y is a tetravalent organic group represented by X, in which two bonding positions are substituted with atoms (e.g. hydrogen atoms) or functional groups (e.g.
• the divalent organic group represented by Y may be a divalent aliphatic group or a divalent aromatic group. From the viewpoint of heat resistance, the divalent organic group represented by Y is preferably a divalent aromatic group.
• divalent aromatic groups include divalent aromatic hydrocarbon groups (for example, the number of carbon atoms constituting the aromatic ring is 6 to 20), divalent aromatic heterocyclic groups (for example, the number of carbon atoms constituting the aromatic ring is 6 to 20), The number of atoms is 5 to 20), and divalent aromatic hydrocarbon groups are preferred.
• divalent aromatic group represented by Y include groups represented by the following formulas (G) to (H).
• a group represented by the following formula (H) is preferable from the viewpoint of obtaining an insulating film that has excellent flexibility and further suppresses the generation of voids at the bonding interface. is more preferably a group containing a single bond or an ether bond, and even more preferably a single bond or an ether bond.
• R each independently represents an alkyl group, an alkoxy group, a hydroxyl group, a halogenated alkyl group, a phenyl group, or a halogen atom
• n each independently represents 0 to 4. Represents an integer.
• two R A 's each independently represent a hydrogen atom, an alkyl group, or a phenyl group), a siloxane bond (-O- (Si(R B ) 2 -O-) n ;
• Two R B 's each independently represent a hydrogen atom, an alkyl group, or a phenyl group, and n represents an integer of 1 or 2 or more.) or at least these Represents a combination of two divalent groups.
• D may have a structure represented by the above formula (C1).
• a specific example of D in formula (H) is a single bond or the same as a specific example of C in formula (E).
• D in formula (H) is preferably a single bond, an ether bond, a group containing an ether bond and a phenylene group, a group containing an ether bond, a phenylene group, and an alkylene group, etc., each independently.
• the alkyl group represented by R in formulas (G) to (H) is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms. , more preferably an alkyl group having 1 or 2 carbon atoms.
• Specific examples of the alkyl group represented by R in formulas (G) to (H) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, Examples include t-butyl group.
• the alkoxy group represented by R in formulas (G) to (H) is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms. , more preferably an alkoxy group having 1 or 2 carbon atoms.
• Specific examples of the alkoxy group represented by R in formulas (G) to (H) include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, and s-butoxy group. , t-butoxy group and the like.
• the halogenated alkyl group represented by R in formulas (G) to (H) is preferably a halogenated alkyl group having 1 to 5 carbon atoms, and preferably a halogenated alkyl group having 1 to 3 carbon atoms. More preferably, it is a halogenated alkyl group having 1 or 2 carbon atoms.
• Specific examples of the halogenated alkyl group represented by R in formulas (G) to (H) include at least one hydrogen atom contained in the alkyl group represented by R in formulas (G) to (H). Examples include alkyl groups in which is substituted with a halogen atom such as a fluorine atom or a chlorine atom. Among these, fluoromethyl group, difluoromethyl group, trifluoromethyl group, etc. are preferred.
• n is each independently preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.
• divalent aliphatic group represented by Y examples include a linear or branched alkylene group, a cycloalkylene group, a divalent group having a polyalkylene oxide structure, and the like.
• the linear or branched alkylene group represented by Y is preferably an alkylene group having 1 to 20 carbon atoms, more preferably an alkylene group having 1 to 15 carbon atoms, and More preferably, the number is 1 to 10 alkylene groups.
• Specific examples of the alkylene group represented by Y include tetramethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group, 2-methylpentamethylene group. , 2-methylhexamethylene group, 2-methylheptamethylene group, 2-methyloctamethylene group, 2-methylnonamethylene group, 2-methyldecamethylene group, and the like.
• the cycloalkylene group represented by Y is preferably a cycloalkylene group having 3 to 10 carbon atoms, more preferably a cycloalkylene group having 3 to 6 carbon atoms.
• Specific examples of the cycloalkylene group represented by Y include a cyclopropylene group and a cyclohexylene group.
• the unit structure contained in the divalent group having a polyalkylene oxide structure represented by Y is preferably an alkylene oxide structure having 1 to 10 carbon atoms, more preferably an alkylene oxide structure having 1 to 8 carbon atoms, and An alkylene oxide structure of 1 to 4 is more preferred.
• a polyethylene oxide structure or a polypropylene oxide structure is preferable.
• the alkylene group in the alkylene oxide structure may be linear or branched.
• the number of unit structures in the polyalkylene oxide structure may be one, or two or more.
• the divalent organic group represented by Y may be a divalent group having a polysiloxane structure.
• a divalent group having a polysiloxane structure represented by Y a silicon atom in the polysiloxane structure is bonded to a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 18 carbon atoms. Examples include divalent groups having a polysiloxane structure.
• alkyl group having 1 to 20 carbon atoms bonded to the silicon atom in the polysiloxane structure include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n- Examples include octyl group, 2-ethylhexyl group, n-dodecyl group, and the like. Among these, methyl group is preferred.
• the aryl group having 6 to 18 carbon atoms bonded to the silicon atom in the polysiloxane structure may be unsubstituted or substituted with a substituent.
• substituent when the aryl group has a substituent include a halogen atom, an alkoxy group, and a hydroxy group.
• aryl group having 6 to 18 carbon atoms include phenyl group, naphthyl group, and benzyl group. Among these, phenyl group is preferred.
• the number of alkyl groups having 1 to 20 carbon atoms or aryl groups having 6 to 18 carbon atoms in the polysiloxane structure may be one type or two or more types.
• the silicon atom constituting the divalent group having a polysiloxane structure represented by Y is an NH group in general formula (1) via an alkylene group such as a methylene group or an ethylene group, or an arylene group such as a phenylene group. May be combined with
• the group represented by the formula (G) is preferably a group represented by the following formula (G'), and the group represented by the formula (H) is preferably a group represented by the following formula (H') or the formula (H'). ') or a group represented by the formula (H''') is preferable.
• R each independently represents an alkyl group, an alkoxy group, a halogenated alkyl group, a phenyl group, a hydroxyl group, or a halogen atom.
• R is preferably an alkyl group, more preferably a methyl group.
• the combination of the tetravalent organic group represented by X and the divalent organic group represented by Y in general formula (1) is not particularly limited.
• X is a group represented by formula (E)
• Y is a group represented by formula (H). Examples include combinations of groups.
• R 6 and R 7 each independently represent a hydrogen atom or a monovalent organic group.
• the monovalent organic group is preferably an aliphatic hydrocarbon group having 1 to 4 carbon atoms or an organic group having an unsaturated double bond, such as a group represented by the following general formula (2), an ethyl group, It is more preferably either an isobutyl group or a t-butyl group, and even more preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms or a group represented by the following general formula (2).
• the monovalent organic group contains an organic group having an unsaturated double bond, preferably a group represented by the following general formula (2), it has high i-line transmittance and is good even when cured at low temperatures of 400°C or less. It tends to form a cured product.
• the monovalent organic group includes an organic group having an unsaturated double bond, preferably a group represented by the following general formula (2), at least a portion of the unsaturated double bond moiety is removed by the compound (C). is detached.
• aliphatic hydrocarbon groups having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, etc. Among them, ethyl group, Isobutyl and t-butyl groups are preferred.
• R 8 to R 10 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and R x represents a divalent linking group.
• the aliphatic hydrocarbon group represented by R 8 to R 10 in general formula (2) has 1 to 3 carbon atoms, preferably 1 or 2 carbon atoms.
• Specific examples of the aliphatic hydrocarbon group represented by R 8 to R 10 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a methyl group is preferred.
• R 8 to R 10 in general formula (2) is preferably a combination in which R 8 and R 9 are hydrogen atoms, and R 10 is a hydrogen atom or a methyl group.
• R x in general formula (2) is a divalent linking group, preferably a hydrocarbon group having 1 to 10 carbon atoms.
• the hydrocarbon group having 1 to 10 carbon atoms include linear or branched alkylene groups.
• the number of carbon atoms in R x is preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 or 3.
• R 6 and R 7 may be a group represented by the above general formula (2), and both R 6 and R 7 may be a group represented by the above general formula (2). It may be a group represented by
• the general formula (2) is calculated based on the sum of R 6 and R 7 of all structural units contained in the compound.
• the ratio of R 6 and R 7 which are the groups represented by, is preferably 60 mol% or more, more preferably 70 mol% or more, and even more preferably 80 mol% or more.
• the upper limit is not particularly limited, and may be 100 mol%.
• the above-mentioned ratio may be 0 mol% or more and less than 60 mol%.
• the group represented by general formula (2) is preferably a group represented by general formula (2') below.
• R 8 to R 10 each independently represent a hydrogen atom or an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and q represents an integer of 1 to 10.
• q is an integer of 1 to 10, preferably an integer of 2 to 5, and more preferably 2 or 3.
• the content of the structural unit represented by the general formula (1) contained in the compound having the structural unit represented by the general formula (1) is preferably 60 mol% or more based on the total structural units, More preferably 70 mol% or more, and even more preferably 80 mol% or more.
• the upper limit of the above-mentioned content is not particularly limited, and may be 100 mol%.
• the polyimide precursor may be synthesized using a tetracarboxylic dianhydride and a diamine compound.
• X corresponds to a residue derived from a tetracarboxylic dianhydride
• Y corresponds to a residue derived from a diamine compound.
• the polyimide precursor may be synthesized using tetracarboxylic acid instead of tetracarboxylic dianhydride.
• tetracarboxylic dianhydride examples include pyromellitic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, and 3,3',4,4'-biphenyltetracarboxylic dianhydride.
• diamine compounds include 2,2'-dimethylbiphenyl-4,4'-diamine, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, and 2,2'-difluoro- 4,4'-diaminobiphenyl, p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 1,5-diaminonaphthalene, benzidine, 4,4'-diaminodiphenyl ether, 3,4 '-Diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 2,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3
• diamine compound 2,2'-dimethylbiphenyl-4,4'-diamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether and 1,3-bis(3-aminophenoxy)benzene are preferred.
• the diamine compounds may be used alone or in combination of two or more.
• a compound having a structural unit represented by general formula (1) and in which at least one of R 6 and R 7 in general formula (1) is a monovalent organic group is, for example, the following (a) or It can be obtained by the method (b).
• a diester is produced by reacting a tetracarboxylic dianhydride (preferably a tetracarboxylic dianhydride represented by the following general formula (8)) and a compound represented by R-OH in an organic solvent. After making the derivative, the diester derivative and a diamine compound represented by H 2 N--Y--NH 2 are subjected to a condensation reaction.
• Tetracarboxylic dianhydride and a diamine compound represented by H 2 N-Y-NH 2 are reacted in an organic solvent to obtain a polyamic acid solution, and the compound represented by R-OH is mixed into polyamide.
• the reaction is carried out in an organic solvent to introduce an ester group.
• Y in the diamine compound represented by H 2 N-Y-NH 2 is the same as Y in general formula (1), and specific examples and preferred examples are also the same.
• R in the compound represented by R-OH represents a monovalent organic group, and specific examples and preferred examples are the same as those for R 6 and R 7 in general formula (1).
• the tetracarboxylic dianhydride represented by the general formula (8), the diamine compound represented by H 2 N-Y-NH 2 and the compound represented by R-OH may each be used alone. Often, two or more types may be combined. Examples of the organic solvents mentioned above include N-methyl-2-pyrrolidone, ⁇ -butyrolactone, dimethoxyimidazolidinone, 3-methoxy-N,N-dimethylpropionamide, and among others, 3-methoxy-N,N- Dimethylpropionamide is preferred.
• a polyimide precursor may be synthesized by allowing a dehydration condensation agent to act on a polyamic acid solution together with a compound represented by R-OH.
• the dehydration condensation agent preferably contains at least one selected from the group consisting of trifluoroacetic anhydride, N,N'-dicyclohexylcarbodiimide (DCC), and 1,3-diisopropylcarbodiimide (DIC).
• DCC N,N'-dicyclohexylcarbodiimide
• DIC 1,3-diisopropylcarbodiimide
• the above-mentioned compound contained in the polyimide precursor is obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a compound represented by R-OH to form a diester derivative, and then converting it into a diester derivative. It can be obtained by converting it into an acid chloride by applying a chlorinating agent such as thionyl, and then reacting the acid chloride with a diamine compound represented by H 2 N-Y-NH 2 .
• the above-mentioned compound contained in the polyimide precursor is obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a compound represented by R-OH to form a diester derivative, and then converting it into a carbodiimide. It can be obtained by reacting a diamine compound represented by H 2 N-Y-NH 2 with a diester derivative in the presence of the compound.
• the above-mentioned compound contained in the polyimide precursor is obtained by reacting a tetracarboxylic dianhydride represented by the following general formula (8) with a diamine compound represented by H 2 N-Y-NH 2 It can be obtained by converting the polyamic acid into isoimidization in the presence of a dehydration condensation agent such as trifluoroacetic anhydride, and then reacting with a compound represented by R-OH. Alternatively, a compound represented by R-OH may be reacted on a portion of the tetracarboxylic dianhydride in advance to form a partially esterified tetracarboxylic dianhydride and a compound represented by H 2 N-Y-NH 2 . may be reacted with a diamine compound.
• X is the same as X in general formula (1), and specific examples and preferred examples are also the same.
• Compounds represented by R-OH used in the synthesis of the above-mentioned compounds contained in the polyimide precursor include compounds in which a hydroxy group is bonded to R x of the group represented by general formula (2); It may also be a compound in which a hydroxy group is bonded to the terminal methylene group of the group represented by formula (2').
• Specific examples of compounds represented by R-OH include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and methacryl.
• Examples include 2-hydroxypropyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, among others, 2-hydroxyethyl methacrylate and 2-hydroxybutyl acrylate. -Hydroxyethyl is preferred.
• the weight average molecular weight of the polyimide precursor (A) is preferably 10,000 to 200,000, more preferably 10,000 to 100,000.
• the weight average molecular weight of the polyimide precursor (A) can be determined in the same manner as for the polybenzoxazole precursor (a).
• the second insulating film-forming material may further contain dicarboxylic acid
• the (A) polyimide precursor contained in the second insulating film-forming material is such that some of the amino groups in the (A) polyimide precursor are It may have a structure formed by reacting with a carboxy group in a dicarboxylic acid.
• the dicarboxylic acid may be a dicarboxylic acid having a (meth)acrylic group, for example, a dicarboxylic acid represented by the following formula.
• the second insulating film forming material may contain a polyimide resin in addition to the polyimide precursor (A).
• a polyimide resin By combining a polyimide precursor and a polyimide resin, it is possible to suppress the production of volatiles due to dehydration cyclization during imide ring formation, and therefore it tends to be possible to suppress the generation of voids.
• the polyimide resin herein refers to a resin having an imide skeleton in all or part of the resin skeleton. It is preferable that the polyimide resin is soluble in a solvent in an insulating film forming material using a polyimide precursor.
• the polyimide resin is not particularly limited as long as it is a polymeric compound having a plurality of structural units containing imide bonds, and preferably includes, for example, a compound having a structural unit represented by the following general formula (X).
• X a compound having a structural unit represented by the following general formula (X).
• X represents a tetravalent organic group
• Y represents a divalent organic group.
• Preferred examples of substituents X and Y in general formula (X) are the same as preferred examples of substituents X and Y in general formula (1) described above.
• the proportion of the polyimide resin to the total of the polyimide precursor and the polyimide resin may be 15% to 50% by mass, or 10% to 20% by mass. There may be.
• the second insulating film forming material may include (A) a polyimide precursor and a resin other than the polyimide resin.
• Other resins include, from the viewpoint of heat resistance, the aforementioned polybenzoxazole precursors, novolac resins, acrylic resins, polyether nitrile resins, polyether sulfone resins, epoxy resins, polyethylene terephthalate resins, and polyethylene naphthalate resins. , polyvinyl chloride resin, etc.
• the other resins may be used alone or in combination of two or more.
• the content of the polyimide precursor (A) based on the total amount of resin components is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass. , more preferably 90% by mass to 100% by mass.
• the second insulating film forming material includes a (B) solvent (hereinafter also referred to as "component (B)").
• Component (B) preferably contains at least one selected from the group consisting of compounds represented by the following formulas (3) to (7).
• R 1 , R 2 , R 8 and R 10 are each independently an alkyl group having 1 to 4 carbon atoms
• R 3 to R 7 and R 9 are each independently an alkyl group having 1 to 4 carbon atoms.
• it is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
• s is an integer from 0 to 8
• t is an integer from 0 to 4
• r is an integer from 0 to 4
• u is an integer from 0 to 3.
• the alkyl group having 1 to 4 carbon atoms in R 2 is preferably a methyl group or an ethyl group.
• t is preferably 0, 1 or 2, more preferably 1.
• the alkyl group having 1 to 4 carbon atoms for R 3 is preferably a methyl group, ethyl group, propyl group or butyl group.
• the alkyl group having 1 to 4 carbon atoms for R 4 and R 5 is preferably a methyl group or an ethyl group.
• the alkyl group having 1 to 4 carbon atoms in R 6 to R 8 is preferably a methyl group or an ethyl group.
• r is preferably 0 or 1, more preferably 0.
• the alkyl group having 1 to 4 carbon atoms in R 9 and R 10 is preferably a methyl group or an ethyl group.
• u is preferably 0 or 1, more preferably 0.
• Component (B) may be, for example, at least one of the compounds represented by formulas (4), (5), (6), and (7), and may be a compound represented by formula (5) or It may also be a compound represented by formula (7).
• component (B) include the following compounds.
• the component (B) contained in the second insulating film forming material is not limited to the above-mentioned compounds, and may be other solvents.
• Component (B) may be an ester solvent, an ether solvent, a ketone solvent, a hydrocarbon solvent, an aromatic hydrocarbon solvent, a sulfoxide solvent, or the like.
• Solvents for esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, ⁇ -butyrolactone. , ⁇ -caprolactone, ⁇ -valerolactone, alkyl alkoxy acetates such as methyl alkoxy acetate, ethyl alkoxy acetate, butyl alkoxy acetate (e.g.
• 3-Alkoxypropionate alkyl esters such as methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate (e.g.
• 2-alkoxypropionate alkyl esters e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, Propyl 2-methoxypropionate, methyl 2-ethoxypropionate and ethyl 2-ethoxypropionate
• 2-alkoxy-2-methylpropionate such as methyl 2-methoxy-2-methylpropionate
• 2-ethoxy-2 - Ethyl 2-alkoxy-2-methylpropionate such as ethyl methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc.
• 2-alkoxypropionate alkyl esters e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, Prop
• Ether solvents include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene.
• Examples include glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and the like.
• Examples of the ketone solvent include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone (NMP).
• Examples of hydrocarbon solvents include limonene and the like.
• Examples of aromatic hydrocarbon solvents include toluene, xylene, anisole, and the like.
• Examples of solvents for sulfoxides include dimethyl sulfoxide and the like.
• Preferred examples of the solvent for component (B) include ⁇ -butyrolactone, cyclopentanone, and ethyl lactate.
• the content of NMP may be 1% by mass or less based on the total amount of the insulating film forming material. Often, the amount may be 3% by mass or less based on the total amount of the polyimide precursor (A).
• the content of the component (B) is preferably 1 part by mass to 10,000 parts by mass, and preferably 50 parts by mass to 10,000 parts by mass, based on 100 parts by mass of the polyimide precursor (A). It is more preferable that
• Component (B) is at least one solvent (1) selected from the group consisting of compounds represented by formulas (3) to (6), as well as ester solvents, ether solvents, and ketone solvents. , a hydrocarbon solvent, an aromatic hydrocarbon solvent, and a sulfoxide solvent. Further, the content of the solvent (1) may be 5% by mass to 100% by mass, or even 5% by mass to 50% by mass, based on the total of the solvent (1) and the solvent (2). good. The content of the solvent (1) may be 10 parts by mass to 1000 parts by mass, 10 parts by mass to 100 parts by mass, and 10 parts by mass based on 100 parts by mass of the polyimide precursor (A). Parts to 50 parts by mass may be used.
• solvent (1) selected from the group consisting of compounds represented by formulas (3) to (6), as well as ester solvents, ether solvents, and ketone solvents.
• the content of the solvent (1) may be 5% by mass to 100% by mass, or even 5% by mass to 50% by mass, based on the total
• the second insulating film forming material may contain the (C) compound.
• the compound (C) acts on the polymerizable unsaturated bond sites of the polyimide precursor (A) and promotes the elimination of the polymerizable unsaturated bond sites.
• Examples of the compound (C) include nitrogen-containing compounds.
• the nitrogen-containing compound may be a thermal base generator. The thermal base generator generates a base by heating, and this base promotes the elimination of unsaturated bond sites in the polyimide precursor (A).
• nitrogen-containing compounds include aniline diacetic acid, 2-(methylphenylamino)ethanol, 2-(ethylanilino)ethanol, N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N,N'-dimethyl Aniline, N-phenylethanolamine, 4-phenylmorpholine, 2,2'-(4-methylphenylimino)diethanol, 4-aminobenzamide, 2-aminobenzamide, nicotinamide, 4-amino-N-methylbenzamide, 4-aminoacetanilide, 4-aminoacetophenone, diazabicycloundecene, and salts thereof, among others, aniline diacetic acid, 4-aminobenzamide, nicotinamide, diazabicycloundecene, N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N,N'-dimethylaniline, N-phenylethanolamine,
• the nitrogen-containing compound preferably includes a compound represented by the following formula (17) or a compound represented by the following formula (18).
• R 31A to R 33A each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group, a monovalent aliphatic hydrocarbon group having a hydroxy group, or a monovalent aliphatic hydrocarbon group. is an aromatic group, and at least one (preferably one) of R 31A to R 33A is a monovalent aromatic group. Adjacent groups of R 31A to R 33A may form a ring structure. Examples of the ring structure formed include a 5-membered ring and a 6-membered ring which may have a substituent such as a methyl group or a phenyl group.
• the hydrogen atom of the monovalent aliphatic hydrocarbon group may be substituted with a functional group other than a hydroxy group.
• At least one (preferably one) of R 31A to R 33A is a monovalent aliphatic hydrocarbon group, a monovalent aliphatic hydrocarbon group having a hydroxy group, Alternatively, it is preferably a monovalent aromatic group.
• the monovalent aliphatic hydrocarbon groups R 31A to R 33A preferably have 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.
• the monovalent aliphatic hydrocarbon group is preferably a methyl group, an ethyl group, or the like.
• the monovalent aliphatic hydrocarbon group having a hydroxy group of R 31A to R 33A is one or more monovalent aliphatic hydrocarbon groups having a hydroxy group of R 31A to R 33A.
• a group having hydroxy groups bonded thereto is preferable, and a group having one to three hydroxy groups bonded is more preferable.
• Specific examples of the monovalent aliphatic hydrocarbon group having a hydroxy group include a methylol group, a hydroxyethyl group, and the like, with a hydroxyethyl group being preferred.
• Examples of the monovalent aromatic groups R 31A to R 33A in formulas (17) and (18) include monovalent aromatic hydrocarbon groups, monovalent aromatic heterocyclic groups, etc.
• An aromatic hydrocarbon group is preferred.
• the monovalent aromatic hydrocarbon group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms.
• Examples of the monovalent aromatic hydrocarbon group include a phenyl group and a naphthyl group.
• the monovalent aromatic groups R 31A to R 33A in formulas (17) and (18) may have a substituent.
• substituents include monovalent aliphatic hydrocarbon groups represented by R 31A to R 33A in formulas (17) and (18), and hydroxy groups represented by R 31A to R 33A in formulas (17) and (18) described above. The same groups as monovalent aliphatic hydrocarbon groups having groups can be mentioned.
• the content of the compound (C) is preferably 0.1 parts by mass to 20 parts by mass, and from the viewpoint of storage stability, 0.3 parts by mass to 100 parts by mass of the polyimide precursor (A). It is more preferably 15 parts by weight, and even more preferably 0.5 parts to 10 parts by weight.
• the second insulating film forming material contains (A) a polyimide precursor, and (B) a solvent, and optionally (C) a compound, (D) a photopolymerization initiator, (E) a polymerizable monomer, and (F ) a thermal polymerization initiator, (G) a polymerization inhibitor, an antioxidant, a coupling agent, a surfactant, a leveling agent, a rust preventive agent, etc., and other components and unavoidable impurities to the extent that they do not impair the effects of the present disclosure. May include. It is preferable that the second insulating film forming material further contains a component (D) and a component (E).
• the (C) compound is the (C) component
• the photopolymerization initiator is the (D) component
• the (E) polymerizable monomer is the (E) component
• the thermal polymerization initiator is the (F) component
• Polymerization inhibitor is also referred to as component (G).
• 80% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, or 100% by mass of the second insulating film forming material (A) polyimide precursor to (B) component, (A) polyimide precursor to (C) component, (A) polyimide precursor to (E) component, (A) polyimide precursor ⁇ (F) component, (A) polyimide precursor ⁇ (G) component, (A) polyimide precursor to (G) component and at least one selected from the group consisting of an antioxidant, a coupling agent, a surfactant, a leveling agent, and a rust preventive; It may consist of.
• an antioxidant a coupling agent, a surfactant, a leveling agent, and a rust preventive
• the second insulating film forming material preferably contains (D) a photopolymerization initiator. This makes it possible to reduce the number of steps for manufacturing electrodes among the steps for manufacturing a semiconductor device, and it is possible to reduce the cost of the entire process when manufacturing a semiconductor device.
• component (D) examples include benzophenone, N,N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N,N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy- 4'-dimethylaminobenzophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, 4,4'-bis(diethylamino)benzophenone, methyl o-benzoylbenzoate, 4-benzoyl- Benzophenone derivatives such as 4'-methyldiphenylketone, dibenzylketone, fluorenone; acetophenone, 2,2-diethoxyacetophenone, 3'-methylacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2- Acetophenone derivatives such as methylpropiophen
• the content of component (D) is determined based on 100 parts by mass of the polyimide precursor (A) from the viewpoint that photocrosslinking tends to be uniform in the film thickness direction. , is preferably 0.1 parts by weight to 20 parts by weight, more preferably 1 part to 15 parts by weight, and even more preferably 5 parts to 15 parts by weight.
• the second insulating film forming material may contain an antireflection agent that suppresses reflected light from the substrate direction from the viewpoint of improving photosensitivity.
• the second insulating film forming material preferably contains (E) a polymerizable monomer.
• Component (E) preferably has at least one group containing a polymerizable unsaturated double bond, and from the viewpoint of being suitably polymerizable in combination with a photopolymerization initiator, component (E) contains at least one (meth)acrylic group. It is more preferable to have one. From the viewpoint of improving crosslinking density and photosensitivity, it is preferable to have 2 to 6 groups, and more preferably 2 to 4 groups containing polymerizable unsaturated double bonds.
• the polymerizable monomers may be used alone or in combination of two or more.
• the polymerizable monomer having a (meth)acrylic group is not particularly limited, and examples thereof include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and tetraethylene glycol diacrylate.
• the polymerizable monomer other than the polymerizable monomer having a (meth)acrylic group is not particularly limited, and examples include styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, methylenebisacrylamide, N , N-dimethylacrylamide and N-methylolacrylamide.
• Component (E) is not limited to a compound having a group containing a polymerizable unsaturated double bond, and may be a compound having a polymerizable group other than an unsaturated double bond group (for example, an oxirane ring). .
• the content of component (E) is not particularly limited, and is 1 part by mass to 100 parts by mass with respect to 100 parts by mass of the polyimide precursor (A).
• the amount is preferably from 1 part by weight to 75 parts by weight, and even more preferably from 1 part by weight to 50 parts by weight.
• the second insulating film forming material preferably contains (F) a thermal polymerization initiator from the viewpoint of improving the physical properties of the cured product.
• component (F) include ketone peroxide such as methyl ethyl ketone peroxide, 1,1-di(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1,1-di(t-hexylperoxy) ) Peroxyketals such as cyclohexane, 1,1-di(t-butylperoxy)cyclohexane, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide hydroperoxides such as dicumyl peroxide, dialkyl peroxides such as di-t-butyl peroxide, diacyl peroxides such as dilauroyl peroxide and dibenzoyl peroxide, di(4-t-butylcyclohexyl) peroxydicarbonate, di(2- peroxydicarbonates
• the content of the (F) component may be 0.1 parts by mass to 20 parts by mass with respect to 100 parts by mass of the polyimide precursor, The amount may be 1 part by mass to 15 parts by mass, or 1 part by mass to 10 parts by mass.
• the second insulating film forming material may contain component (G) from the viewpoint of ensuring good storage stability.
• the polymerization inhibitor include radical polymerization inhibitors and radical polymerization inhibitors.
• component (G) examples include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, N-phenyl- Examples include 2-naphthylamine, cuperone, 2,5-torquinone, tannic acid, parabenzylaminophenol, nitrosamines, and hindered phenol compounds.
• the polymerization inhibitors may be used alone or in combination of two or more.
• the hindered phenol compound may have both the function of a polymerization inhibitor and the function of an antioxidant described below, or it may have either one of the functions.
• the hindered phenol compound is not particularly limited, and examples thereof include 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3-(3,5- di-t-butyl-4-hydroxyphenyl) propionate, isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,4'-methylenebis(2,6-di-t- butylphenol), 4,4'-thio-bis(3-methyl-6-t-butylphenol), 4,4'-butylidene-bis(3-methyl-6-t-butylphenol), triethylene glycol-bis[3 -(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2-
• the content of the (G) component is determined from the viewpoint of the storage stability of the insulating film forming material and the heat resistance of the resulting cured product.
• the amount is preferably 0.01 parts by mass to 30 parts by mass, more preferably 0.01 parts by mass to 10 parts by mass, and 0.05 parts by mass to 5 parts by mass, based on 100 parts by mass of the body. It is even more preferable.
• the second insulating film forming material may further contain an antioxidant, a coupling agent, a surfactant, a leveling agent, or a rust preventive.
• the second insulating film forming material may contain an antioxidant from the viewpoint of suppressing deterioration of adhesive properties by capturing oxygen radicals and peroxide radicals generated during high-temperature storage, reflow treatment, etc. .
• an antioxidant By including the antioxidant in the second insulating film forming material, oxidation of the electrode during the insulation reliability test can be suppressed.
• antioxidants include the compounds exemplified as the aforementioned hindered phenol compounds, N,N'-bis[2-[2-(3,5-di-tert-butyl-4-hydroxyphenyl)ethyl] carbonyloxy]ethyl]oxamide, N,N'-bis-3-(3,5-di-tert-butyl-4'-hydroxyphenyl)propionylhexamethylenediamine, 1,3,5-tris(3-hydroxy- 4-tert-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,3,5-tris(4-t-butyl) -3-hydroxy-2,6-dimethylbenzyl)isocyanuric acid and the like.
• the antioxidants may be used alone or in combination of two or more.
• the content of the antioxidant is preferably 0.1 parts by mass to 20 parts by mass with respect to 100 parts by mass of (A) polyimide precursor. , more preferably 0.1 parts by mass to 10 parts by mass, and even more preferably 0.1 parts by mass to 5 parts by mass.
• the second insulating film forming material may include a coupling agent.
• the coupling agent reacts with (A) the polyimide precursor to crosslink, or the coupling agent itself polymerizes. This tends to further improve the adhesiveness between the obtained cured product and the substrate.
• Coupling agents include 3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, -Methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N-(3-diethoxymethylsilylpropyl) Succinimide, N-[3-(triethoxysilyl)propyl]phthalamic acid, benzophenone-3,3'-bis(N-[3-triethoxysilyl]propylamide)-4,4'-dicarboxylic acid, benzene-1
• the content of the coupling agent is preferably 0.1 parts by mass to 20 parts by mass, and 0.1 parts by mass to 20 parts by mass, based on 100 parts by mass of the polyimide precursor (A).
• the amount is more preferably 3 parts by weight to 10 parts by weight, and even more preferably 1 part to 10 parts by weight.
• the second insulating film forming material may include at least one of a surfactant and a leveling agent.
• a surfactant and a leveling agent When the insulating film forming material contains at least one of a surfactant and a leveling agent, it improves coating properties (for example, suppressing striae (unevenness in film thickness)), improves adhesion, and improves the compatibility of compounds in the insulating film forming material. etc. can be improved.
• surfactant or leveling agent examples include polyoxyethylene uralyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenol ether, and the like.
• the surfactants and leveling agents may be used alone or in combination of two or more.
• the second insulating film forming material contains at least one of a surfactant and a leveling agent
• the total content of the surfactant and the leveling agent is 0.01 mass parts with respect to 100 mass parts of (A) polyimide precursor.
• the amount is preferably from 10 parts to 10 parts by weight, more preferably from 0.05 parts to 5 parts by weight, even more preferably from 0.05 parts to 3 parts by weight.
• the second insulating film forming material may contain a rust preventive agent from the viewpoint of suppressing corrosion of metals such as copper and copper alloys, and from the viewpoint of suppressing discoloration of the metals.
• rust preventive agents include azole compounds and purine derivatives.
• azole compounds include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t- Butyl-5-phenyl-1H-triazole, 5-hydroxyphenyl-1H-triazole, phenyltriazole, p-ethoxyphenyltriazole, 5-phenyl-1-(2-dimethylaminoethyl)triazole, 5-benzyl-1H- Triazole, hydroxyphenyltriazole, 1,5-dimethyltriazole, 4,5-diethyl-1H-triazole, 1H-benzotriazole, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy- 3,5-bis( ⁇ , ⁇ -dimethylbenzyl)phenyl]-benzotriazole, 2-(3,5-di-t-butyl-2-hydroxyphenyl)
• purine derivatives include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, 1-methyladenine, N-methyladenine, N,N-dimethyladenine, 2-fluoroadenine, 9-(2-hydroxyethyl)adenine, guanine oxime, N-(2-hydroxyethyl)adenine, 8-aminoadenine, 6-Amino-8-phenyl-9H-purine, 1-ethyladenine, 6-ethylaminopurine, 1-benzyladenine, N-methylguanine, 7-(2-hydroxyethyl)guanine, N-(3-chlorophenyl) Examples include guanine, N-(3-ethylphenyl)guanine, 2-azaa
• the rust inhibitors may be used alone or in combination of two or more.
• the content of the rust preventive agent is preferably 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass of (A) polyimide precursor. , more preferably 0.1 parts by mass to 5 parts by mass, and even more preferably 0.5 parts by mass to 3 parts by mass.
• the content of the rust preventive agent is 0.1 parts by mass or more, when the second insulating film forming material is applied on the surface of the copper or copper alloy, discoloration of the surface of the copper or copper alloy is prevented. suppressed.
• the insulating film forming material of the present disclosure preferably has a glass transition temperature of 100° C. to 400° C., more preferably 150° C. to 350° C., when cured.
• the glass transition temperature of the cured product is measured as follows. First, an insulating film forming material is heated in a nitrogen atmosphere for 2 hours at a predetermined curing temperature (for example, 150° C. to 375° C.) that allows a curing reaction to occur, to obtain a cured product. The obtained cured product was cut to make a rectangular parallelepiped of 5 mm x 50 mm x 3 mm, and a dynamic viscoelasticity measuring device (for example, RSA-G2 manufactured by TA Instruments) was used with a tension jig at a frequency of 1 Hz. Dynamic viscoelasticity is measured in a temperature range of 50°C to 350°C under the conditions of heating rate: 5°C/min.
• the glass transition temperature (Tg) is defined as the temperature at the peak top of tan ⁇ , which is determined from the ratio of the storage modulus and loss modulus obtained by the above method.
• the insulating film forming material of the present disclosure may be a negative photosensitive insulating film forming material or a positive photosensitive insulating film forming material. Further, the negative photosensitive insulating film forming material or the positive photosensitive insulating film forming material is used for arranging a plurality of terminal electrodes on a first organic insulating film provided on one surface of the first substrate body, which will be described later. The method is used for at least one of providing a plurality of through holes for arranging a plurality of terminal electrodes in a second organic insulating film provided on one surface of the second substrate body. It's okay.
• the insulating film forming material of the present disclosure preferably has a coefficient of thermal expansion of 150 ppm/K or less, more preferably 100 ppm/K or less, even more preferably 70 ppm/K or less when cured. .
• the coefficient of thermal expansion of the insulating film, which is a cured product, and the coefficient of thermal expansion of the electrode are equal to or close to each other, so even if heat generation occurs during use of the semiconductor device, the insulating layer and the electrode Damage to the semiconductor device due to the difference in coefficient of thermal expansion between the two can be suppressed.
• the coefficient of thermal expansion indicates the rate at which the length of a cured product expands due to temperature rise, per temperature.
• the coefficient of thermal expansion can be calculated by measuring the amount of change in length of the cured product at 100° C. to 150° C. using a thermomechanical analyzer or the like.
• a semiconductor device of the present disclosure includes a first semiconductor substrate including a first substrate body, the first organic insulating film and a first electrode provided on one surface of the first substrate body, and a semiconductor chip substrate body. , a semiconductor chip having the second organic insulating film and a second electrode provided on one surface of the semiconductor chip substrate body, wherein the first organic insulating film and the second organic insulating film are bonded. However, the first electrode and the second electrode are bonded to each other, and at least one of the first organic insulating film and the second organic insulating film is a cured product of the insulating film forming material of the present disclosure.
• the insulating film since at least one of the first organic insulating film and the second organic insulating film (insulating film portion) is a cured product of the insulating film forming material of the present disclosure, the insulating film has excellent heat resistance.
• a semiconductor device is manufactured using the insulating film forming material of the present disclosure.
• the method for manufacturing a semiconductor device of the present disclosure includes a first semiconductor device having a first substrate body, a first electrode and a first organic insulating film provided on one surface of the first substrate body.
• a substrate is prepared, a semiconductor chip having a semiconductor chip substrate body, a second organic insulating film and a second electrode provided on one surface of the semiconductor chip substrate body is prepared, and the first electrode and the second electrode are provided on one surface of the semiconductor chip substrate body.
• 2 electrodes, and the first organic insulating film and the second organic insulating film are bonded together to form at least one of the first organic insulating film and the second organic insulating film.
• the disclosed insulating film forming material is used.
• FIG. 1 is a cross-sectional view schematically showing an example of a semiconductor device of the present disclosure.
• the semiconductor device 1 is an example of a semiconductor package, and includes a first semiconductor chip 10 (first semiconductor substrate), a second semiconductor chip 20 (semiconductor chip), a pillar part 30, and a rewiring layer 40. , a substrate 50, and a circuit board 60.
• the first semiconductor chip 10 is a semiconductor chip such as an LSI (Large Scale Integrated Circuit) chip or a CMOS (Complementary Metal Oxide Semiconductor) sensor, and has a three-dimensional mounting structure in which the second semiconductor chip 20 is mounted downward. There is.
• the second semiconductor chip 20 is a semiconductor chip such as an LSI or a memory, and is a chip component having a smaller area in plan view than the first semiconductor chip 10.
• the second semiconductor chip 20 is chip-to-chip (C2C) bonded to the back surface of the first semiconductor chip 10.
• the first semiconductor chip 10 and the second semiconductor chip 20 have their respective terminal electrodes and their surrounding insulating films firmly and finely bonded to each other by hybrid bonding, which will be described in detail later.
• the pillar part 30 is a connection part in which a plurality of pillars 31 made of metal such as copper (Cu) are sealed with resin 32.
• the plurality of pillars 31 are conductive members extending from the upper surface to the lower surface of the pillar section 30.
• the plurality of pillars 31 may have a cylindrical shape, for example, with a diameter of 3 ⁇ m or more and 20 ⁇ m or less (in one example, a diameter of 5 ⁇ m), and may be arranged such that the distance between the centers of each pillar 31 is 15 ⁇ m or less.
• the plurality of pillars 31 connect the lower terminal electrode of the first semiconductor chip 10 and the upper terminal electrode of the rewiring layer 40 by flip-chip connection.
• connection electrode can be formed in the semiconductor device 1 without using a technique called TMV (Through Mold Via) in which a hole is made in a mold and a solder connection is made.
• the pillar section 30 has, for example, the same thickness as the second semiconductor chip 20, and is arranged on the side of the second semiconductor chip 20 in the horizontal direction. Note that a plurality of solder balls may be arranged instead of the pillar portion 30, and the solder balls electrically connect the lower terminal electrode of the first semiconductor chip 10 and the upper terminal electrode of the rewiring layer 40. You may.
• the rewiring layer 40 is a wiring layer that has a terminal pitch conversion function, which is a function of a package substrate, and is formed by coating polyimide or polybenzoxazole on the lower insulating film of the second semiconductor chip 20 and the lower surface of the pillar section 30. This is a layer in which a rewiring pattern is formed using copper wiring or the like.
• the rewiring layer 40 is formed by turning the first semiconductor chip 10, the second semiconductor chip 20, etc. upside down (see (d) in FIG. 4).
• the rewiring layer 40 electrically connects the terminal electrodes of the first semiconductor chip 10 via the terminal electrodes on the lower surface of the second semiconductor chip 20 and the pillar portion 30 to the terminal electrodes of the substrate 50.
• the terminal pitch of the substrate 50 is wider than the terminal pitch of the pillar 31 and the terminal pitch of the second semiconductor chip 20.
• various electronic components 51 may be mounted on the board 50.
• an inorganic interposer or the like may be used between the rewiring layer 40 and the substrate 50 to ensure electrical connection between the rewiring layer 40 and the substrate 50. You can also make a connection.
• the circuit board 60 has the first semiconductor chip 10 and the second semiconductor chip 20 mounted thereon, and is electrically connected to the board 50 which is connected to the first semiconductor chip 10, the second semiconductor chip 20, the electronic component 51, etc. This is a substrate that has a plurality of through electrodes inside.
• each terminal electrode of the first semiconductor chip 10 and the second semiconductor chip 20 is electrically connected to a terminal electrode 61 provided on the back surface of the circuit board 60 by a plurality of through electrodes.
• FIG. 2 is a diagram sequentially showing a method for manufacturing the semiconductor device shown in FIG.
• FIG. 3 is a diagram showing in more detail the bonding method (hybrid bonding) in the method for manufacturing the semiconductor device shown in FIG.
• FIG. 4 shows a method for manufacturing the semiconductor device shown in FIG. 1, and is a diagram showing the steps after the step shown in FIG. 2 in order.
• the semiconductor device 1 can be manufactured, for example, through the following steps (a) to (n).
• step (k) A process of grinding and thinning the resin 301 side of the semi-finished product M1 molded in step (j) to obtain a semi-finished product M2.
• step (l) A step of forming a wiring layer 400 corresponding to the rewiring layer 40 on the semi-finished product M2 thinned in step (k).
• step (m) A step of cutting the semi-finished product M3 on which the wiring layer 400 has been formed in step (l) along the cutting line A to form each semiconductor device 1.
• the insulating film forming material of the present disclosure provides a first organic insulating film and a second organic insulating film in a method for manufacturing a semiconductor device including at least one step corresponding to step (f) and steps (i) to (n). It may be an insulating film forming material for use in producing at least one of the insulating films.
• Step (a) is a step of preparing a first semiconductor substrate 100, which is a silicon substrate, corresponding to a plurality of first semiconductor chips 10 and on which an integrated circuit including semiconductor elements and wiring connecting them is formed.
• a plurality of terminal electrodes 103 made of copper, aluminum, etc. are placed on one surface 101a of the first substrate body 101 made of silicon or the like. are provided at predetermined intervals, and an insulating film 102 (first insulating film), which is a cured product of the insulating film forming material of the present disclosure, is provided in the spaced portion.
• a plurality of terminal electrodes 103 may be provided after the insulating film 102 is provided on one surface 101a of the first substrate main body 101, or a plurality of terminal electrodes 103 may be provided on one surface 101a of the first substrate main body 101.
• the insulating film 102 may be provided after that. Note that a predetermined interval is provided between the plurality of terminal electrodes 103 in order to form the pillar 300 in a process described later, and another terminal electrode (not shown) connected to the pillar 300 is provided between the plurality of terminal electrodes 103. It is formed.
• Step (b) is a step of preparing a second semiconductor substrate 200, which is a silicon substrate, on which an integrated circuit corresponding to a plurality of second semiconductor chips 20 and including semiconductor elements and wiring connecting them is formed.
• a plurality of terminal electrodes 203 a plurality of second An insulating film 202 (second insulating film, organic insulating region) which is a cured product of the insulating film forming material of the present disclosure is provided.
• the plurality of terminal electrodes 203 may be provided after the insulating film 202 is provided on the one surface 201a of the second substrate main body 201, or the plurality of terminal electrodes 203 may be provided on the one surface 201a of the second substrate main body 201. Alternatively, the insulating film 202 may be provided.
• one of the insulating films 102 and 202 used in step (a) and step (b) are both cured products of the insulating film forming material of the present disclosure
• one of the insulating films 102 and 202 is made of the insulating film forming material of the present disclosure.
• One may be a cured product and the other may be another cured product.
• Examples of other insulating film forming materials for forming the cured product include insulating film forming materials containing polyamideimide, benzocyclobutene (BCB), and the like.
• the tensile modulus of the insulating films 102 and 202 at 25° C. is preferably 7.0 GPa or less, more preferably 5.0 GPa or less, even more preferably 3.0 GPa or less, and 2.5 GPa or less. The following is particularly preferable.
• the coefficient of thermal expansion of the insulating films 102 and 202 is preferably 150 ppm/K or less, more preferably 100 ppm/K or less, and even more preferably 90 ppm/K or less.
• the thickness of the insulating films 102 and 202 is preferably 0.1 ⁇ m to 50 ⁇ m, more preferably 1 ⁇ m to 15 ⁇ m. This makes it possible to reduce the processing time in the subsequent polishing step while ensuring uniformity in the thickness of the insulating film.
• the polishing rate of the insulating film 102 is 0.1 to 5 times the polishing rate of the terminal electrode 103 in order to facilitate the work in steps (c) and (d) and to simplify these steps. It is preferable that the polishing rate of the insulating film 202 is 0.1 to 5 times the polishing rate of the terminal electrode 203 (preferably both). As an example, if the terminal electrode 103 or 203 is made of copper and the polishing rate of copper is 50 nm/min, the polishing rate of the insulating film 102 or 202 is 200 nm/min or less (4 times the polishing rate of copper or less). It is preferably 100 nm/min or less (twice or less the polishing rate of copper), and even more preferably 50 nm/min or less (equivalent to or less than the polishing rate of copper).
• the insulating film is obtained by curing an insulating film forming material.
• the method for producing the above-mentioned insulating film includes, for example, ( ⁇ ) a step of applying an insulating film forming material onto a substrate and drying it to form a resin film, and a step of heat-treating the resin film; ( ⁇ ) After forming a film with a constant thickness using an insulating film forming material on a film that has been subjected to mold release treatment, the process of transferring the resin film to the substrate by lamination method, and the process of forming the resin film on the substrate after transfer. Examples include a method including a step of heat-treating the resin film. From the viewpoint of flatness, the method ( ⁇ ) above is preferred.
• Examples of the method for applying the insulating film forming material include a spin coating method, an inkjet method, and a slit coating method.
• the rotation speed is 300 rpm (rotations per minute) to 3,500 rpm, preferably 500 rpm to 1,500 rpm, the acceleration is 500 rpm/second to 15,000 rpm/second, and the rotation time is 30 seconds to 300 seconds.
• the insulating film forming material may be spin coated under certain conditions.
• a drying step may be included after applying the insulating film forming material to the support, film, etc. Drying may be performed using a hot plate, oven, or the like.
• the drying temperature is preferably 75° C. to 130° C., and more preferably 90° C. to 120° C. from the viewpoint of improving the flatness of the insulating film.
• the drying time is preferably 30 seconds to 5 minutes. Drying may be performed two or more times. Thereby, it is possible to obtain a resin film in which the above-mentioned insulating film forming material is formed into a film shape.
• the chemical liquid discharge speed is 10 ⁇ L/sec to 400 ⁇ L/sec
• the chemical liquid discharge part height is 0.1 ⁇ m to 1.0 ⁇ m
• the stage speed (or chemical liquid discharge part speed) is 1.0 mm/sec to 50.0 mm. /second
• stage acceleration 10mm/second to 1000mm/second ultimate vacuum during vacuum drying 10Pa to 100Pa
• vacuum drying time 30 seconds to 600 seconds drying temperature 60°C to 150°C
• drying time 30 seconds to 300 seconds The insulating film forming material may be slit coated under certain conditions.
• the formed resin film may be heat-treated.
• the heating temperature is preferably 150°C to 450°C, more preferably 150°C to 350°C.
• the insulating film can be suitably produced while suppressing damage to the substrate, devices, etc. and realizing energy saving in the process.
• the heating time is preferably 5 hours or less, more preferably 30 minutes to 3 hours.
• the atmosphere for the heat treatment may be the air or an inert atmosphere such as nitrogen, but a nitrogen atmosphere is preferred from the viewpoint of preventing oxidation of the resin film.
• Devices used for heat treatment include quartz tube furnaces, hot plates, rapid thermal annealing, vertical diffusion furnaces, infrared curing furnaces, electron beam curing furnaces, microwave curing furnaces, and the like.
• the insulating film forming material of the present disclosure which is a negative photosensitive insulating film forming material or a positive photosensitive insulating film forming material
• the insulating film 202 is provided on one surface 201a of the second substrate main body 201, and then a plurality of
• a method including a step of obtaining a patterned resin film and a step of heat-treating the patterned resin film may be used. Thereby, a cured patterned insulating film can be obtained.
• an insulating film forming material other than the insulating film forming material of the present disclosure may be used on the substrate.
• a method may also be used that includes a step of subsequently performing pattern exposure and developing using a developer to obtain a patterned resin film, and a step of heat-treating the patterned resin film. Thereby, a cured patterned insulating film can be obtained.
• a predetermined pattern is exposed through a photomask.
• the active light to be irradiated includes i-line, broadband ultraviolet rays, visible light, radiation, etc., and i-line is preferable.
• the exposure device a parallel exposure device, a projection exposure device, a stepper, a scanner exposure device, etc. can be used.
• a patterned resin film which is a patterned resin film
• the insulating film forming material of the present disclosure is a negative photosensitive insulating film forming material
• the unexposed portions are removed with a developer.
• the organic solvent used as the negative developing solution can be used alone as a good solvent for the photosensitive resin film, or in an appropriate mixture of a good solvent and a poor solvent.
• Good solvents include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide, ⁇ -butyrolactone, ⁇ -acetyl- ⁇ -butyrolactone, Examples include 3-methoxy-N,N-dimethylpropanamide, cyclopentanone, cyclohexanone, and cycloheptanone.
• Examples of the poor solvent include toluene, xylene, methanol, ethanol, isopropanol, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, water, and the like.
• the exposed portion is removed with a developer.
• the solution used as a positive developer include a tetramethylammonium hydroxide (TMAH) solution and a sodium carbonate solution.
• At least one of the negative developer and the positive developer may contain a surfactant.
• the content of the surfactant is preferably 0.01 parts by mass to 10 parts by mass, more preferably 0.1 parts by mass to 5 parts by mass, based on 100 parts by mass of the developer.
• the development time can be, for example, twice the time required for the photosensitive resin film to be completely dissolved after being immersed in the developer.
• the development time may be adjusted depending on the thermosetting polyamide having a phenolic hydroxyl group in the molecule contained in the insulating film forming material of the present disclosure, for example, it is preferably 10 seconds to 15 minutes, and 10 seconds to 5 minutes. is more preferable, and from the viewpoint of productivity, 20 seconds to 5 minutes is even more preferable.
• the patterned resin film after development may be washed with a rinsing liquid.
• a rinsing liquid distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, etc. may be used alone or in an appropriate mixture, or they may be used in a stepwise combination. You can.
• thermosetting non-conductive film NCF
• thermosetting A synthetic resin may also be used as an organic material constituting the insulating films 102 and 202 other than the cured product of the insulating film forming material of the present disclosure.
• This organic material may be an underfill material.
• the organic material forming the insulating films 102 and 202 may be a heat-resistant resin.
• Step (c) is a step of polishing the first semiconductor substrate 100.
• step (c) as shown in FIG. 3(a), chemical treatment is applied so that each surface 103a of the terminal electrode 103 is at the same position or slightly higher (protrudes) from the surface 102a of the insulating film 102.
• One surface 101a side which is the surface of the first semiconductor substrate 100, is polished using a mechanical polishing method (CMP method).
• CMP method mechanical polishing method
• the first semiconductor substrate 100 may be polished by CMP under the condition that the terminal electrode 103 made of copper or the like is selectively etched deeply.
• each surface 103a of the terminal electrode 103 may be polished using a CMP method so as to match the surface 102a of the insulating film 102.
• the polishing method is not limited to the CMP method, and back grinding or the like may be employed.
• mechanical polishing may be performed using a polishing device such as a surface planer.
• each surface 103a of the terminal electrode 103 is located at a slightly higher position than the surface 102a of the insulating film 102 (that is, the thickness of the terminal electrode 103, which is the first electrode, is greater than the thickness of the insulating film 102, which is the first insulating film), (if the thickness is also thick), the difference in height between each surface 103a and the surface 102a (difference in thickness between the terminal electrode 103 and the insulating film 102) may be 1 nm to 150 nm, or even 1 nm to 80 nm. good.
• the difference in height between the insulating film (surface 102a, etc.) and the electrode (surface 103a, etc.) is determined when five points on a measurement target such as a wafer are measured using an atomic force microscope (AFM). It refers to the arithmetic mean.
• Step (d) is a step of polishing the second semiconductor substrate 200.
• step (d) as shown in FIG. 3(a), each surface 203a of the terminal electrode 203 is placed at the same position or slightly higher (protrudes) from the surface 202a of the insulating film 202.
• One surface 201a side which is the surface of the second semiconductor substrate 200, is polished using the CMP method.
• the second semiconductor substrate 200 is polished by CMP under conditions that selectively and deeply shave the terminal electrodes 203 made of copper or the like, for example.
• each surface 203a of the terminal electrode 203 may be polished by a CMP method so as to match the surface 202a of the insulating film 202.
• the polishing method is not limited to the CMP method, and back grinding or the like may be used.
• the difference in height between each surface 203a and the surface 202a may be 1 nm to 150 nm, or even 1 nm to 80 nm. good.
• polishing may be performed so that the thickness of the insulating film 102 and the thickness of the insulating film 202 are the same, but for example, the thickness of the insulating film 202 may be the same as the thickness of the insulating film 102. It may be polished to be larger than the diameter. On the other hand, polishing may be performed so that the thickness of the insulating film 202 is smaller than the thickness of the insulating film 102. If the thickness of the insulating film 202 is greater than the thickness of the insulating film 102, the insulating film 202 will contain most of the foreign matter that adheres to the bonding interface when the second semiconductor substrate 200 is diced or when chips are mounted. This makes it possible to further reduce bonding defects.
• step (c) and step (d) may be performed, and it is preferable to perform both step (c) and step (d).
• Step (e) is a step of dividing the second semiconductor substrate 200 into pieces to obtain a plurality of semiconductor chips 205.
• the second semiconductor substrate 200 is diced into a plurality of semiconductor chips 205 by cutting means such as dicing.
• the insulating film 202 may be coated with a protective material or the like, and then it may be diced.
• the insulating film 202 of the second semiconductor substrate 200 is divided into insulating film portions 202b corresponding to each semiconductor chip 205. Examples of the dicing method for dividing the second semiconductor substrate 200 into pieces include plasma dicing, stealth dicing, laser dicing, and the like.
• the second semiconductor substrate 200 during dicing for example, an organic film that can be removed with water, TMAH, etc., or a thin film such as a carbon film that can be removed with plasma or the like may be provided.
• a large-area second semiconductor substrate 200 is prepared and then separated into pieces to obtain a plurality of semiconductor chips 205; however, the method for preparing the semiconductor chips 205 is not limited to this.
• the semiconductor chip 205 includes a semiconductor chip substrate body, and a second organic insulating film and a second electrode provided on one surface of the semiconductor chip substrate body.
• Step (f) is a step of aligning the terminal electrodes 203 of each of the plurality of semiconductor chips 205 with respect to the terminal electrodes 103 of the first semiconductor substrate 100.
• step (f) as shown in FIG. 2C, each semiconductor chip 205 is placed so that the terminal electrode 203 of each semiconductor chip 205 faces the corresponding plurality of terminal electrodes 103 of the first semiconductor substrate 100.
• Perform alignment for this alignment, an alignment mark or the like may be provided on the first semiconductor substrate 100.
• Step (g) is a step of bonding the insulating film 102 of the first semiconductor substrate 100 and each insulating film portion 202b of the plurality of semiconductor chips 205 to each other.
• step (g) after removing organic substances, metal oxides, etc. attached to the surface of each semiconductor chip 205, the semiconductor chips 205 are aligned with respect to the first semiconductor substrate 100, as shown in FIG. 2(c).
• the insulating film portions 202b of each of the plurality of semiconductor chips 205 are bonded to the insulating film 102 of the first semiconductor substrate 100 as hybrid bonding (see FIG. 3(b)).
• the insulating film portions of the plurality of semiconductor chips 205 and the insulating film 102 of the first semiconductor substrate 100 may be uniformly heated before bonding.
• the insulating film 102 and the insulating film portion 202b are more easily bonded than the terminal electrodes 103 and 203 due to the difference between the coefficient of thermal expansion of the insulating film 102 and the insulating film portion 202b and that of the terminal electrodes 103 and 203. It also expands.
• the first semiconductor substrate 100 may be polished in step (c) so that the height of the insulating film 102 becomes equal to or higher than the height of the terminal electrode 103 due to thermal expansion due to heating, and the insulating film portion 202b is polished.
• the second semiconductor substrate 200 may be polished in step (d) so that the height is approximately equal to or higher than the height of the terminal electrode 203.
• the temperature difference between the semiconductor chip 205 and the first semiconductor substrate 100 during bonding is preferably within 10° C., for example.
• the insulating film 102 and the insulating film portion 202b are bonded to form an insulating bonding portion S1, and the plurality of semiconductor chips 205 are mechanically firmly attached to the first semiconductor substrate 100. can be attached to.
• the bonding is performed by heating at a highly uniform temperature, it is difficult for positional deviations to occur at the bonding location, and highly accurate bonding can be performed.
• the terminal electrodes 103 of the first semiconductor substrate 100 and the terminal electrodes 203 of the semiconductor chip 205 are separated from each other and are not connected (however, they are aligned).
• the semiconductor chip 205 may be bonded to the first semiconductor substrate 100 by other bonding methods, for example, by room temperature bonding or the like.
• the total thickness of the organic insulating film which is the insulating bonding portion where the insulating film 102 and the insulating film portion 202b are bonded, is not particularly limited, and may be, for example, 0.1 ⁇ m or more, from the viewpoint of suppressing the influence of foreign substances. From the viewpoint of device design, the thickness may be 1 ⁇ m to 20 ⁇ m, preferably 1 ⁇ m to 5 ⁇ m.
• Step (h) is a step of bonding the terminal electrode 103 of the first semiconductor substrate 100 and the terminal electrode 203 of each of the plurality of semiconductor chips 205.
• step (h) as shown in FIG. 2(d), after the bonding in step (g) is completed, heat H, pressure, or both are applied to bond the terminals of the first semiconductor substrate 100 as hybrid bonding.
• the electrode 103 and each terminal electrode 203 of the plurality of semiconductor chips 205 are bonded (see FIG. 3C).
• the annealing temperature in step (g) is preferably 150°C or more and 400°C or less, more preferably 200°C or more and 300°C or less.
• the terminal electrode 103 and the corresponding terminal electrode 203 are bonded to form an electrode bonding portion S2, and the terminal electrode 103 and the terminal electrode 203 are mechanically and electrically strongly bonded.
• the electrode bonding in step (h) may be performed after the bonding in step (g), or may be performed simultaneously with the bonding in step (g).
• the plurality of semiconductor chips 205 are electrically and mechanically installed at predetermined positions on the first semiconductor substrate 100 with high precision.
• a product reliability test (connection test, etc.) may be performed at the semi-finished product stage shown in FIG. 2(d), and only non-defective products may be used in subsequent steps.
• a method for manufacturing an example of a semiconductor device using such a semi-finished product will be described with reference to FIG.
• Step (i) is a step of forming a plurality of pillars 300 on the connection surface 100a of the first semiconductor substrate 100 and between the plurality of semiconductor chips 205.
• step (i) as shown in FIG. 4A, a large number of pillars 300 made of copper, for example, are formed between a plurality of semiconductor chips 205.
• Pillar 300 can be formed from copper plating, conductive paste, copper pins, or the like. The pillar 300 is formed such that one end is connected to a terminal electrode of the first semiconductor substrate 100 that is not connected to the terminal electrode 203 of the semiconductor chip 205, and the other end extends upward.
• the pillar 300 has a diameter of 10 ⁇ m or more and 100 ⁇ m or less, and a height of 10 ⁇ m or more and 1000 ⁇ m or less, for example. Note that, for example, one or more and 10,000 or less pillars 300 may be provided between the pair of semiconductor chips 205.
• Step (j) is a step of molding resin 301 on the connection surface 100a of the first semiconductor substrate 100 so as to cover the plurality of semiconductor chips 205 and the plurality of pillars 300.
• step (j) as shown in FIG. 4B, epoxy resin or the like is molded to completely cover the plurality of semiconductor chips 205 and the plurality of pillars 300.
• the molding method include compression molding, transfer molding, and a method of laminating film-like epoxy films.
• a curing treatment may be performed after molding the epoxy resin or the like.
• step (i) and step (j) are performed almost simultaneously, that is, when the pillar 300 is also formed at the same time as resin molding, the pillar is formed using imprint, which is fine transfer, and conductive paste or electrolytic plating. may be formed.
• step (k) the semi-finished product M1, which is molded in step (j) and includes the resin 301, a plurality of pillars 300, and a plurality of semiconductor chips 205, is ground from the resin 301 side to obtain a semi-finished product M2. It is a process.
• step (k) as shown in FIG. 4(c), the resin-molded first semiconductor substrate 100 and the like are thinned by polishing the upper part of the semi-finished product M1 with a grinder, etc., to form a semi-finished product M2. .
• step (k) By polishing in step (k), the thickness of the semiconductor chip 205, the pillar 300, and the resin 301 is reduced to, for example, about several tens of ⁇ m, and the semiconductor chip 205 has a shape corresponding to the second semiconductor chip 20, and the pillar 300 and the resin 301 are thinned. 301 has a shape corresponding to the pillar portion 30.
• Step (l) is a step of forming a wiring layer 400 corresponding to the rewiring layer 40 on the semi-finished product M2 thinned in step (k).
• step (l) as shown in FIG. 4(d), a rewiring pattern is formed using polyimide or polybenzoxazole, copper wiring, etc. on the second semiconductor chip 20 and pillar portion 30 of the ground semi-finished product M2. Form.
• a semi-finished product M3 having a wiring structure in which the terminal pitch of the second semiconductor chip 20 and the pillar portion 30 is widened is formed.
• Step (m) is a step of cutting the semi-finished product M3 on which the wiring layer 400 was formed in step (l) along the cutting line A to form each semiconductor device 1.
• step (m) as shown in FIG. 4(d), the semiconductor device substrate is cut along cutting lines A by dicing or the like to form each semiconductor device 1.
• step (n) the semiconductor devices 1a that were individualized in step (m) are reversed and placed on the substrate 50 and the circuit board 60 to obtain a plurality of semiconductor devices 1 shown in FIG.
• the insulating film 102 of the first semiconductor substrate 100 and the insulating film 202 of the second semiconductor substrate 200 are made of a cured product of the insulating film forming material of the present disclosure. It is. Since the cured product of the insulating film forming material of the present disclosure has high heat resistance, deterioration of the insulating film due to heating such as bonding is suppressed, and occurrence of peeling, deterioration, etc. of the insulating film is suppressed. Moreover, since the bonding temperature can be lowered by using the insulating film forming material of the present disclosure, the occurrence of defects such as deterioration of the insulating film is further reduced.
• the present disclosure is not limited to the above embodiment.
• the step (i) of forming the pillar 300 in the steps shown in FIG. 4, after the step (i) of forming the pillar 300, the step (j) of molding the resin 301 and the step (k) of grinding and thinning the resin 301 etc. were carried out in order, but the step (j) of molding the resin 301 on the connection surface of the first semiconductor substrate 100 was first performed, and then the step (k) of thinning the resin 301 by grinding it to a predetermined thickness.
• the step (i) of forming the pillar 300 may be performed. In this case, the work of cutting the pillar 300, etc. can be reduced, and since the portion of the pillar 300 to be cut is not necessary, the material cost can be reduced.
• a semiconductor wafer 410 has a substrate body 411 (first substrate body), an insulating film 412 (first insulating film) provided on one surface of the substrate body 411, and a plurality of terminal electrodes 413 (first electrodes).
• first semiconductor substrate a substrate body 421 (second substrate body), an insulating film portion 422 (second insulating film) provided on one surface of the substrate body 421, and a plurality of terminal electrodes 423 (first semiconductor substrate).
• a semiconductor substrate (second semiconductor substrate) before being diced into pieces of a plurality of semiconductor chips 420 having two electrodes) is prepared. Then, one surface side of the semiconductor wafer 410 and one surface side of the second semiconductor substrate before being singulated into semiconductor chips 420 are subjected to the CMP process in the same manner as in the above steps (c) and (d). Polish by etc. Thereafter, the second semiconductor substrate is subjected to the same singulation process as in step (e) to obtain a plurality of semiconductor chips 420.
• the terminal electrodes 423 of the semiconductor chip 420 are aligned with the terminal electrodes 413 of the semiconductor wafer 410 (step (f)). Then, the insulating film 412 of the semiconductor wafer 410 and the insulating film portion 422 of the semiconductor chip 420 are bonded together (step (g)), and the terminal electrodes 413 of the semiconductor wafer 410 and the terminal electrodes 423 of the semiconductor chip 420 are bonded. (step (h)) to obtain a semi-finished product shown in FIG. 5(b).
• the insulating film portion 412 and the insulating film portion 422 become an insulating bonding portion S3, and the semiconductor chip 420 is mechanically firmly attached to the semiconductor wafer 410 with high precision.
• the terminal electrode 413 and the corresponding terminal electrode 423 are joined to form an electrode joint portion S4, and the terminal electrode 413 and the terminal electrode 423 are mechanically and electrically firmly joined.
• a semiconductor device 401 is obtained by bonding a plurality of semiconductor chips 420 to a semiconductor wafer 410 in the same manner.
• the plurality of semiconductor chips 420 may be bonded to the semiconductor wafer 410 one by one by hybrid bonding, or may be bonded to the semiconductor wafer 410 all together by hybrid bonding.
• the manufacturing method related to C2W described above can perform fine bonding between semiconductor wafer 410 and semiconductor chip 420 while reducing bonding defects.
• an inorganic material may be included in a part of the insulating film 102 of the semiconductor substrate 100, the insulating film 202 of the semiconductor chip 205, etc., within the range where the effects of the present disclosure are achieved.
• thermosetting polyamide A1 having a phenolic hydroxyl group in the molecule (Synthesis of thermosetting polyamide A1 having a phenolic hydroxyl group in the molecule)
• 15.48 g of 4,4'-diphenyl ether dicarboxylic acid and 90 g of N-methyl-2-pyrrolidone were charged, and after cooling the flask to 5°C, 12.64 g of thionyl chloride was added dropwise and reacted for 30 minutes to obtain a solution of 4,4'-diphenyl ether dicarboxylic acid chloride.
• Polymer A1 polybenzoxazole precursor
• thermosetting polyamide A2 having a phenolic hydroxyl group in the molecule (Synthesis of thermosetting polyamide A2 having a phenolic hydroxyl group in the molecule) Into a 0.2 liter flask equipped with a stirrer and a thermometer, 60 g of N-methyl-2-pyrrolidone was charged, and 13.92 g of 2,2'-bis(3-amino-4-hydroxyphenyl)hexafluoropropane was added. and stirred to dissolve.
• the weight average molecular weight of Polymer A3 determined by GPC standard polystyrene conversion was 20,000. Furthermore, the esterification rate was calculated from the NMR results using the measurement conditions described below. The esterification rate of Polymer A3 was 70%, and the proportion of unreacted carboxyl groups was 30 mol%. (Measurement condition) Measuring equipment: Bruker Biospin AV400M Magnetic field strength: 400MHz Reference material: Tetramethylsilane (TMS) Solvent: dimethyl sulfoxide (DMSO)
• polyimide precursor A5 that does not contain phenolic hydroxyl groups in the molecule
• DMAP 4,4'-diaminodiphenyl ether
• MPD m-phenylenediamine
• Polyimide precursor A6 (Synthesis of polyimide precursor A6 that does not contain phenolic hydroxyl groups in the molecule) Polyimide precursor A6 was obtained by performing the same operation except that DMAP was changed to 3.89 g of ODA in the synthesis of polyimide precursor A3 (hereinafter referred to as polymer A6).
• the weight average molecular weight of Polymer A6 was 21,000.
• the esterification rate of Polymer A6 was calculated by performing NMR measurement under the conditions described above. The esterification rate was 70 mol%, and the proportion of unreacted carboxyl groups was 30 mol%.
• polyimide precursor A7 (Synthesis of polyimide precursor A7 containing no phenolic hydroxyl group in the molecule) Same procedure except that ODPA was changed to 6.71 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) and DMAP was changed to 3.89 g of ODA in the synthesis of polyimide precursor A3.
• Polyimide precursor A7 was obtained (hereinafter referred to as polymer A7).
• the weight average molecular weight of Polymer A7 was 20,000.
• the esterification rate of Polymer A7 was calculated by performing NMR measurement under the conditions described above. The esterification rate was 60 mol%, and the proportion of unreacted carboxyl groups was 40 mol%.
• GPC gel permeation chromatography
• Example 1 to 6 Comparative Examples 1 to 2
• Insulating film forming materials of Examples 1 to 6 and Comparative Examples 1 to 2 were prepared as follows using the components and blending amounts shown in Table 1. The unit of the amount of each component in Table 1 is parts by mass. In addition, a blank column in Table 1 means that the corresponding component is not blended.
• the mixture of each component was kneaded overnight at room temperature (25°C) in a general solvent-resistant container, and then filtered under pressure using a 0.2 ⁇ m pore filter. Ta. The following evaluations were performed using the obtained insulating film forming material.
• ⁇ Polyimide precursor or polybenzoxazole derivative The above-mentioned polymers A1 to A7 ⁇ Solvent B1: 3-methoxy-N,N-dimethylpropanamide B2: ⁇ -butyrolactone B3: Dimethyl sulfoxide ⁇ Polymerizable monomer C1: 2,2-bis(3,5-bis(hydroxylmethyl)-4-hydroxyphenyl) )-1,1,1,3,3,3-hexafluoropropane (TML-BPAF) C2: Tetraethylene glycol dimethacrylate (TEGDMA) C3: Tricyclodecane dimethanol diacrylate (A-DCP) ⁇ Rust inhibitor D1: Benzotriazole (BT) ⁇ Polymerization initiator E1: The following compound (TPPA428)
• E2 8-Methoxypyrene-1,3,6-trisulfonic acid trisodium salt (MPTS)
• E3 Bis(1-phenyl-1-methylethyl) peroxide (PercumylD)
• E4 1-phenyl-1,2-propanedione-2-(o-ethoxycarbonyl)oxime (PDO)
• E5 4,4'-bis(diethylamino)benzophenone (EMK)
• Cured films were formed using the insulating film forming materials of Examples 1 to 6 and Comparative Examples 1 to 2 as follows, and then the glass transition points were measured. First, an insulating film forming material was spin-coated onto a Si substrate, heated and dried on a hot plate at 95°C for 120 seconds, and then further dried at 105°C for 120 seconds, resulting in a resin film with a thickness of about 10 ⁇ m after drying. was formed. The obtained resin film was cured at 350° C. for 2 hours in a nitrogen atmosphere using a vertical diffusion furnace ⁇ -TF to obtain a cured product with a film thickness of 10 ⁇ m.
• the obtained cured product was immersed in a 4.9% by mass hydrofluoric acid aqueous solution to peel the cured product from the Si substrate.
• the cured film after peeling was shaped using a razor into a sample length of 15 mm and sample width of 4 mm.
• TMA7100 model manufactured by Hitachi High-Tech Science Co., Ltd.
• the sample elongates (expands) in the temperature range of 50°C to 350°C using a tensile jig with an initial sample length of 10 mm, heating rate: 5°C/min, and a load of 10 g.
• the glass transition temperature (Tg) was defined as the temperature at the starting point of the change determined by the tangential method at a point in the curve obtained by the above method where there was a sudden change in the expansion coefficient.
• the insulating film forming materials of Examples 1 to 6 and Comparative Examples 1 to 2 were spin-coated onto an 8-inch Si wafer using a spin coater coating device, and dried by heating at 95° C. for 120 seconds on a hot plate. The resin film was further dried at 105° C. for 120 seconds to form a resin film having a thickness of about 10 ⁇ m after drying.
• the obtained resin films were subjected to broadband (BB) exposure at an exposure dose of 600 mJ/cm 2 using Mask Aligner MA-8 (manufactured by SUSS Microtech).
• the exposed resin film was developed with cyclopentanone using a developing machine AD1200 (manufactured by Mikasa Co., Ltd.) such that the total development time was 20 seconds.
• the obtained resin film was cured at 350° C. for 2 hours in a nitrogen atmosphere using a vertical diffusion furnace ⁇ -TF to obtain a cured film.
• a part of the obtained cured film was diced into 5 mm square pieces using a blade dicer (DISCO DFD-6362) to obtain resin-coated chips.
• the obtained resin-coated chips were pressed onto the cured film using a thermocompression bonding machine (manufactured by Showa Denko Materials Co., Ltd.) at a predetermined pressure and the bonding temperature shown in Table 1 for 15 seconds to produce a cured film with chips.
• a thermocompression bonding machine manufactured by Showa Denko Materials Co., Ltd.
• the below-mentioned evaluation was performed on five chips that were pressure-bonded to the cured film.
• Chips bonded using a thermocompression bonding machine were judged to be defective if they fell off when force was applied with tweezers.
• -Evaluation criteria for joining results A: Two or less chips out of five chips were observed to have poor bonding. B: More than two chips out of five chips were observed to have poor bonding.

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