WO2022071329A1 - 樹脂組成物、半導体装置の製造方法、硬化物、半導体装置及びポリイミド前駆体の合成方法 - Google Patents
樹脂組成物、半導体装置の製造方法、硬化物、半導体装置及びポリイミド前駆体の合成方法 Download PDFInfo
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- WO2022071329A1 WO2022071329A1 PCT/JP2021/035672 JP2021035672W WO2022071329A1 WO 2022071329 A1 WO2022071329 A1 WO 2022071329A1 JP 2021035672 W JP2021035672 W JP 2021035672W WO 2022071329 A1 WO2022071329 A1 WO 2022071329A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
- C08F290/145—Polyamides; Polyesteramides; Polyimides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/022—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations
- C08F299/024—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polycondensates with side or terminal unsaturations the unsaturation being in acrylic or methacrylic groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
- C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/12—Unsaturated polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/24—Homopolymers or copolymers of amides or imides
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- H10P14/60—
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- H10W72/071—
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- H10W74/10—
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- H10W74/40—
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- H10W99/00—
Definitions
- the present disclosure relates to a resin composition, a method for manufacturing a semiconductor device, a cured product, a semiconductor device, and a method for synthesizing a polyimide precursor.
- Non-Patent Document 1 discloses an example of three-dimensional mounting of a semiconductor chip.
- Patent Document 1 discloses an example of a technique capable of lowering the bonding temperature by using a cyclic olefin resin.
- SoICTM System on Integrated Chips
- the heat resistance of the organic material is not sufficient, and the organic material is altered by being exposed to a high temperature at the time of C2W bonding. There is a risk that bonding defects may occur at the interface between the substrate and the insulating film.
- the present disclosure has been made in view of the above, and a resin composition capable of producing a semiconductor device having an insulating film having excellent heat resistance and suppressing the generation of voids at the bonding interface, and the above-mentioned resin composition were used. It is an object of the present invention to provide a semiconductor device provided with a method for manufacturing a semiconductor device, a cured product obtained by curing the above-mentioned resin composition, and an insulating film in which the generation of voids at a bonding interface is suppressed and the heat resistance is excellent. .. Furthermore, it is an object of the present disclosure to provide a method for synthesizing a polyimide precursor capable of synthesizing a polyimide precursor used for preparing the above-mentioned resin composition.
- a polyimide precursor which is at least one resin selected from the group consisting of (A) polyamic acid, polyamic acid ester, polyamic acid salt, and polyamic acid amide, and at least one of the polyimide resins, and (B) a solvent. And, including A resin composition for use in producing at least one of the first organic insulating film and the second organic insulating film in the method for manufacturing a semiconductor device including the following steps (1) to (5).
- Step (1) A first semiconductor substrate having the first substrate main body and the first organic insulating film and the first electrode provided on one surface of the first substrate main body is prepared.
- Step (2) A second semiconductor substrate having the second substrate main body, the second organic insulating film provided on one surface of the second substrate main body, and a plurality of second electrodes is prepared.
- Step (3) The second semiconductor substrate is individualized to obtain a plurality of semiconductor chips each having an organic insulating film portion corresponding to a part of the second organic insulating film and at least one second electrode. do.
- Step (4) The first organic insulating film of the first semiconductor substrate and the organic insulating film portion of the semiconductor chip are bonded to each other.
- Step (5) The first electrode of the first semiconductor substrate and the second electrode of the semiconductor chip are joined.
- a polyimide precursor which is at least one resin selected from the group consisting of (A) polyamic acid, polyamic acid ester, polyamic acid salt and polyamic acid amide, and at least one of the polyimide resins, and (B) solvent. And, including A resin composition for use in producing a cured product that is polished together with an electrode by a chemical mechanical polishing method.
- 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.
- E The resin composition according to ⁇ 3>, wherein the tetravalent organic group represented by X in the general formula (1) is a group represented by the following formula (E).
- C is a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (—O—), a sulfide bond (—S—), a phenylene group, and an ester bond (—O—).
- -C ( O)-)
- R independently represents an alkyl group, an alkoxy group, an alkyl halide group, a phenyl group or a halogen atom
- n independently represents an integer of 0 to 4, respectively.
- Sylylene bond (-Si ( RA ) 2- ;
- the two RAs independently represent a hydrogen atom, an alkyl group or a phenyl group), a siloxane bond (-O- (Si ( RB )). 2 - O-) n ;
- the two RBs independently represent a hydrogen atom, an alkyl group or a phenyl group, and n represents 1 or an integer of 2 or more) or a combination of at least two divalents. Represents the group of.
- the monovalent organic group in the R 6 and the R 7 is a group represented by the following general formula (2), an ethyl group, an isobutyl group or a t-butyl group.
- 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 content of the solvent (B) is any one of ⁇ 1> to ⁇ 6>, which is 1 part by mass to 10000 parts by mass with respect to 100 parts by mass of the total of the (A) polyimide precursor and the polyimide resin.
- the resin composition according to one.
- R 1 , R 2 , R 8 and R 10 are independently alkyl groups having 1 to 4 carbon atoms, and R 3 to R 7 and R 9 are independent of each other. In addition, it is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- s is an integer of 0 to 8
- t is an integer of 0 to 4
- r is an integer of 0 to 4
- u is an integer of 0 to 3.
- the resin composition according to any one of ⁇ 1> to ⁇ 11> which further contains (C) a photopolymerization initiator and (D) a polymerizable monomer.
- ⁇ 13> A negative type photosensitive resin composition or a positive type photosensitive resin composition, through holes for arranging a plurality of terminal electrodes in an organic insulating film provided on one surface of a substrate body by a photolithography method.
- the resin composition according to any one of ⁇ 1> to ⁇ 12> for use in providing a plurality of the above.
- ⁇ 14> The resin composition according to any one of ⁇ 1> to ⁇ 13>, wherein the cured product obtained by being cured has a tensile elastic modulus of 7.0 GPa or less at 25 ° C.
- ⁇ 15> The resin composition according to any one of ⁇ 1> to ⁇ 14>, wherein the cured product has a coefficient of thermal expansion of 150 ppm / K or less.
- the resin composition according to any one of ⁇ 1> to ⁇ 15> is used for producing at least one of the first organic insulating film and the second organic insulating film, and the following steps (1). )-A method for manufacturing a semiconductor device for manufacturing a semiconductor device through the process (5).
- Step (1) A first semiconductor substrate having a first substrate main body and the first organic insulating film and the first electrode provided on one surface of the first substrate main body is prepared.
- Step (2) A second semiconductor substrate having the second substrate main body, the second organic insulating film provided on one surface of the second substrate main body, and a plurality of second electrodes is prepared.
- Step (3) The second semiconductor substrate is individualized to obtain a plurality of semiconductor chips each having an organic insulating film portion corresponding to a part of the second organic insulating film and at least one second electrode. do.
- Step (4) The first organic insulating film of the first semiconductor substrate and the organic insulating film portion of the semiconductor chip are bonded to each other.
- Step (5) The first electrode of the first semiconductor substrate and the second electrode of the semiconductor chip are joined.
- the first organic insulating film and the organic insulating film portion are bonded together at a temperature at which the temperature difference between the semiconductor chip and the first semiconductor substrate is within 10 ° C.
- the thickness of the organic insulating film formed by joining the first organic insulating film and the organic insulating film portion is 0.1 ⁇ m or more in ⁇ 16> or ⁇ 17>.
- the step (1) includes a step of polishing the one side of the first semiconductor substrate, and the step (2) includes a step of polishing the one side of the second semiconductor substrate.
- the polishing rate of the first organic insulating film is 0.1 to 5 times the polishing rate of the first electrode, and the polishing rate of the second organic insulating film is the above.
- ⁇ 20> The method for manufacturing a semiconductor device according to any one of ⁇ 16> to ⁇ 19>, wherein the thickness of the second insulating film is larger than the thickness of the first insulating film.
- ⁇ 21> The method for manufacturing a semiconductor device according to any one of ⁇ 16> to ⁇ 19>, wherein the thickness of the second insulating film is smaller than the thickness of the first insulating film.
- ⁇ 22> A cured product obtained by curing the resin composition according to any one of ⁇ 1> to ⁇ 15>.
- ⁇ 23> A first semiconductor substrate having a first substrate main body, the first organic insulating film provided on one surface of the first substrate main body, and a first electrode.
- a semiconductor chip having a semiconductor chip substrate main body, an organic insulating film portion provided on one surface of the semiconductor chip substrate main body, and a second electrode.
- the first organic insulating film of the first semiconductor substrate and the organic insulating film portion of the semiconductor chip are bonded to the first electrode of the first semiconductor substrate and the first electrode of the semiconductor chip.
- the two electrodes are joined,
- Tetracarboxylic dianhydride and a diamine compound represented by H2NY-NH 2 ( in the formula, Y is a divalent organic group) are mixed with 3-methoxy-N, N.
- the step of reacting in dimethylpropanamide to obtain a polyamic acid solution and A step of allowing a dehydration condensing agent and a compound represented by R-OH (in the formula, R is a monovalent organic group) to act on the polyamic acid solution.
- a method for synthesizing a polyimide precursor comprises at least one selected from the group consisting of trifluoroacetic anhydride, N, N'-dicyclohexylcarbodiimide (DCC) and 1,3-diisopropylcarbodiimide (DIC), ⁇ 24.
- a resin composition capable of producing a semiconductor device having an insulating film excellent in heat resistance and suppressing the generation of voids at a bonding interface a method for manufacturing a semiconductor device using the above-mentioned resin composition, and the above-mentioned. It is possible to provide a semiconductor device provided with a cured product obtained by curing the resin composition of No. 1 and an insulating film having an insulating film excellent in heat resistance, in which the generation of voids at the bonding interface is suppressed. Furthermore, the present disclosure can provide a method for synthesizing a polyimide precursor capable of synthesizing a polyimide precursor used for preparing the above-mentioned resin composition.
- FIG. 1 is a cross-sectional view schematically showing an example of a semiconductor device manufactured by the method for manufacturing a semiconductor device according to an embodiment of the present invention.
- FIG. 2 is a diagram showing in order a method for manufacturing the semiconductor device shown in FIG.
- FIG. 3 is a diagram showing a joining method in the manufacturing method of the semiconductor device shown in FIG. 2 in more detail.
- FIG. 4 is a method for manufacturing the semiconductor device shown in FIG. 1, and is a diagram showing steps after the steps 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 of the present invention is applied to a Chip-to-Wafer (C2W).
- C2W Chip-to-Wafer
- a or B may include either A or B, and may include both.
- the term “process” includes, in addition to a process independent of other processes, the process as long as the purpose of the process is achieved even if it cannot be clearly distinguished from the other process. ..
- the numerical range indicated by using "-" includes the numerical values before and after "-" as the minimum value and the maximum value, respectively.
- the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in another stepwise description. ..
- each component may contain a plurality of applicable substances.
- the content or content of each component is the total content or content of the plurality of substances present in the composition unless otherwise specified. Means quantity.
- the term "layer” or “membrane” is used only in a part of the region, in addition to the case where the layer or the membrane is formed in the entire region when the region is observed. The case where it is formed is also included.
- the thickness of the layer or film is a value given as an arithmetic mean value obtained by measuring the thickness of five points of the target layer or film.
- the thickness of the layer or the film can be measured using a micrometer or the like. In the present disclosure, if the thickness of the layer or membrane can be directly measured, it is measured using a micrometer.
- the measurement may be performed by observing the cross section of the measurement target using an electron microscope.
- the "(meth) acrylic group” means "acrylic group” and "methacrylic group”.
- the number of carbon atoms in the functional group means the total number of carbon atoms including the number of carbon atoms of the substituent.
- the resin composition of the present disclosure comprises (A) a polyimide precursor which is at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt and polyamic acid amide, and at least one of the polyimide resins. , (B) For producing at least one insulating film of the first organic insulating film and the second organic insulating film in the method for manufacturing a semiconductor device including the following steps (1) to (5). It is a resin composition for use. Step (1) A first semiconductor substrate having the first substrate main body and the first organic insulating film and the first electrode provided on one surface of the first substrate main body is prepared.
- Step (2) A second semiconductor substrate having the second substrate main body, the second organic insulating film provided on one surface of the second substrate main body, and a plurality of second electrodes is prepared.
- Step (3) The second semiconductor substrate is individualized to obtain a plurality of semiconductor chips each having an organic insulating film portion corresponding to a part of the second organic insulating film and at least one second electrode.
- Step (4) The first organic insulating film of the first semiconductor substrate and the organic insulating film portion of the semiconductor chip are bonded to each other.
- Step (5) The first electrode of the first semiconductor substrate and the second electrode of the semiconductor chip are joined. Specific examples of each of the above-mentioned steps (1) to (5) will be described in the section of the method for manufacturing a semiconductor device described later.
- the insulating film which is a cured product obtained by curing a resin composition containing at least one of a polyimide precursor and a polyimide resin, has a lower elastic modulus and is softer than a molded product made of an inorganic material. Therefore, when foreign matter or the like is present on the surface of the first organic insulating film or the surface of the second organic insulating film when the first organic insulating film and the second organic insulating film, one of which is the insulating film, are bonded together. Even if the insulating film is present, the insulating film at the bonding interface is easily deformed, and foreign matter can be included in the insulating film without forming large voids in the insulating film.
- the cured product obtained by curing the resin composition containing at least one of the polyimide precursor and the polyimide resin is compared with the cured product obtained by curing the resin composition containing acrylic resin, epoxy resin and the like. Because of its high heat resistance, it tends to be suppressed from the occurrence of bonding failure at the interface between the substrate and the insulating film due to the deterioration of the resin in the manufacturing process of the semiconductor device. From the above points, the resin composition of the present disclosure is excellent in reliability in the manufacturing process of the semiconductor device and can realize a high yield.
- Modifications of the resin composition of the present disclosure include (A) a polyimide precursor which is at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt and polyamic acid amide, and a polyimide resin. It may be a resin composition containing at least one and (B) a solvent and used for producing a cured product to be polished by a chemical mechanical polishing (CMP) method together with an electrode.
- CMP chemical mechanical polishing
- the surface of the insulating film can be easily adjusted to a position slightly lower than the surface of the electrode, and preferably the height difference between the surface of the insulating film and the surface of the electrode can be easily adjusted to 1 nm to 300 nm. Therefore, the modified resin composition has excellent CMP adaptability.
- the 5% thermogravimetric reduction temperature of the cured product obtained by curing the resin composition of the present disclosure is preferably 200 ° C. or higher, more preferably 250 ° C. or higher, from the viewpoint of heat resistance of the cured product. Further, the upper limit of the 5% thermogravimetric reduction temperature of the cured product is not particularly limited, and may be, for example, 450 ° C. or lower.
- the 5% thermogravimetric reduction temperature of the cured product is measured as follows. First, the resin composition is heated at a predetermined curing temperature (for example, 150 ° C. to 375 ° C.) at which a curing reaction is possible under a nitrogen atmosphere for 1 hour or more to obtain a cured product. 10 mg of the obtained cured product was placed in a thermogravimetric measuring device (for example, TGA-50 manufactured by Shimadzu Corporation), and the temperature was raised from 25 ° C. to 500 ° C. at a rate of 10 ° C./min under a nitrogen atmosphere, and the weight was increased. The temperature at which the temperature is reduced by 5% from that before the temperature rise is defined as the 5% thermogravimetric reduction temperature.
- a predetermined curing temperature for example, 150 ° C. to 375 ° C.
- the glass transition temperature of the cured product obtained by curing the resin composition of the present disclosure is preferably 100 ° C. to 400 ° C., more preferably 150 ° C. to 350 ° C. from the viewpoint of bonding at a low temperature.
- the glass transition temperature of the cured product is measured as follows. First, the resin composition is heated in a nitrogen atmosphere for 2 hours at a predetermined curing temperature (for example, 150 ° C. to 375 ° C.) at which a curing reaction is possible to obtain a cured product. The obtained cured product is cut to prepare a rectangular body of 5 mm ⁇ 50 mm ⁇ 3 mm, and a dynamic viscoelasticity measuring device (for example, manufactured by TA Instrument, RSA-G2) is used with a tensile jig, and the frequency is 1 Hz. The dynamic viscoelasticity is measured in the temperature range of 50 ° C. to 350 ° C. under the condition of heating rate: 5 ° C./min.
- the glass transition temperature (Tg) is the temperature of the peak top portion in tan ⁇ obtained from the ratio of the storage elastic modulus and the loss elastic modulus obtained by the above method.
- a storage elastic modulus G1 at a temperature 100 ° C. lower than the glass transition temperature (Tg) of the cured product obtained by dynamic viscoelasticity measurement is preferably 0.001 to 0.02.
- the method for measuring the storage elastic modulus can be measured by the method described in the description of the method for measuring the glass transition temperature.
- the resin composition of the present disclosure may be a negative type photosensitive resin composition or a positive type photosensitive resin composition. Further, in the negative type photosensitive resin composition or the positive type photosensitive resin composition, a plurality of terminal electrodes are arranged on the first organic insulating film provided on one surface of the first substrate main body in the step (1). A plurality of through holes for arranging a plurality of terminal electrodes in the second organic insulating film provided on one surface of the second substrate main body in the step (2). It may be used for at least one of the provisions.
- the resin composition of the present disclosure is cured from the viewpoint of more preferably reducing bonding defects by including the foreign substances in the insulating film without further forming large voids when the foreign substances adhere to the bonding interface.
- the tensile elastic modulus of the cured product at 25 ° C. is preferably 7.0 GPa or less, more preferably 5.0 GPa or less, further preferably 3.0 GPa or less, and 2.0 GPa or less. It is particularly preferable, and it is even more preferable that it is 1.5 GPa or less.
- the cured product obtained by curing the resin composition of the present disclosure has a lower tensile elastic modulus than an inorganic material such as silicon dioxide (SiO 2 ). In the present disclosure, the tensile modulus is a value measured at 25 ° C. based on JIS K 7161 (1994).
- the storage elastic modulus at 300 ° C. may be 0.5 GPa to 0.001 GPa or 0.1 GPa to 0.01 GPa.
- the coefficient of thermal expansion of the cured product obtained by curing is preferably 150 ppm / K or less, more preferably 100 ppm / K or less, and further preferably 70 ppm / K or less. ..
- the coefficient of thermal expansion of the insulating film, which is a cured product, and the coefficient of thermal expansion of the electrodes are equal to or close to each other. Damage to the semiconductor device due to the difference in the coefficient of thermal expansion from the above can be suppressed.
- the coefficient of thermal expansion indicates the rate at which the length of the cured product expands due to temperature rise per temperature, and the amount of change in the length of the cured product from 100 ° C to 150 ° C is measured using a thermomechanical analyzer or the like. It can be calculated by doing.
- the resin composition of the present disclosure is (A) a polyimide precursor which is at least one resin selected from the group consisting of polyamic acid, polyamic acid ester, polyamic acid salt and polyamic acid amide, and at least one of polyimide resins (hereinafter , Also referred to as "(A) component").
- the component (A) is preferably at least one of a polyimide precursor and a polyimide resin capable of producing a cured product exhibiting high properties (for example, heat resistance), and has a polymerizable unsaturated bond as the polyimide precursor. It is more preferable to include a polyimide precursor.
- the component (A) contained in the resin composition is preferably a component that does not cause a problem in a polishing step, a bonding step, or the like.
- the polyimide precursor is a polyamic acid, a compound in which the hydrogen atom of at least a part of the carboxy group in the polyamic acid is replaced with a monovalent organic group, or a compound in which at least a part of the carboxy group in the polyamic acid has a pH of 7 or more. It means a compound corresponding to any of a basic compound and a polyamic acid salt which is a compound forming a salt structure.
- Examples of the compound in which at least a part of the hydrogen atom of the carboxy group in the polyamic acid is replaced with a monovalent organic group include a polyamic acid ester and a polyamic acid amide.
- the polyamic acid ester, polyamic acid amide and the like preferably have a polymerizable unsaturated bond.
- the component (A) contains a polyimide precursor
- the component (A) preferably contains a compound having a structural unit represented by the following general formula (1).
- X represents a tetravalent organic group and Y represents a divalent organic group.
- R 6 and R 7 each independently represent a hydrogen atom or a monovalent organic group.
- 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. May be.
- the combination of R 6 and R 7 is not particularly limited as long as they are independently hydrogen atoms or monovalent organic groups.
- R 6 and R 7 may both be hydrogen atoms, one may be a hydrogen atom and the other may be a monovalent organic group described later, and both may be the same or different monovalent organic groups. It may be.
- 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 further preferably 6 to 12 carbon atoms. ..
- the tetravalent organic group represented by X may contain an aromatic ring.
- the aromatic ring include an aromatic hydrocarbon group (for example, the number of carbon atoms constituting the aromatic ring is 6 to 20), an aromatic heterocyclic group (for example, the number of atoms constituting the heterocycle is 5 to 20), and the like. 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, a phenanthrene ring and the like.
- each aromatic ring may have a substituent or may be unsubstituted.
- substituent of the aromatic ring include an alkyl group, a fluorine atom, an alkyl halide group, a hydroxyl group, an amino group and the like.
- the tetravalent organic group represented by X contains a benzene ring
- the tetravalent organic group represented by X preferably contains 1 to 4 benzene rings, and preferably contains 1 to 3 benzene rings.
- each benzene ring may be linked by a single bond, or may be an alkylene group, a halogenated alkylene group, a carbonyl group, or a sulfonyl group.
- siloxane bond (-O- (Si (RB) 2 - O-) n ;
- the two RBs independently represent a hydrogen atom, an alkyl group or a phenyl group, where n is 1 or an integer of 2 or more. It may be bonded by a linking group such as), a composite linking group in which at least two of these linking groups are combined, or the like.
- the two benzene rings may be bonded at two points by at least one of a single bond and a linking group to form a 5-membered ring or a 6-membered ring containing a linking group between the two benzene rings.
- the -COOR 6 group and the -CONH- group are in the ortho position with each other, and the -COOR 7 group and the -CO- group are preferably in the ortho position with each other.
- tetravalent organic group represented by X include groups represented by the following formulas (A) to (F).
- the group represented by the following formula (E) is preferable, and the group represented by the following formula (E) is represented by C. Is more preferably a group containing an ether bond, and even more preferably an ether bond.
- the following formula (F) has a structure in which C in the following formula (E) is a single bond. The present disclosure is not limited to the following specific examples.
- a and B are each independently a divalent group that is not coupled to a single bond or benzene ring. However, both A and B are not single bonds. Divalent groups that are not conjugated to the benzene ring include methylene group, methylene halide group, methylmethylene halide group, carbonyl group, sulfonyl group, ether bond (-O-), sulfide bond (-S-), and silylene bond.
- (-Si ( RA ) 2- each of the two RAs independently represents a hydrogen atom, an alkyl group or a phenyl group
- a and B are independently preferable to have a methylene group, a bis (trifluoromethyl) methylene group, a difluoromethylene group, an ether bond, a sulfide bond and the like, and an ether bond is more preferable.
- C is a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (—O—), a sulfide bond (—S—), a phenylene group, and an ester bond (—O—).
- -C ( O)-)
- C (Si (RB) 2 - O-) n ;
- the two RBs 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.
- C preferably contains an ether bond, and is preferably an ether bond. Further, C may have a structure represented by the following formula (C1).
- the alkylene group represented by C in the 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 having 1 carbon atom. Alternatively, it is more preferably 2 alkylene groups.
- alkylene group represented by C in the formula (E) include a linear alkylene group such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, and a hexamethylene group; a 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,
- the halogenated alkylene group represented by C in the formula (E) is preferably a halogenated alkylene group having 1 to 10 carbon atoms, and more preferably a halogenated alkylene group having 1 to 5 carbon atoms. It is preferable that it is a halogenated alkylene group having 1 to 3 carbon atoms.
- the halogenated alkylene group represented by C in the formula (E) at least one hydrogen atom contained in the alkylene group represented by C in the above formula (E) is a fluorine atom, a chlorine atom or the like. Examples thereof include an alkylene group substituted with a halogen atom. Among these, a fluoromethylene group, a difluoromethylene group, a hexafluorodimethylmethylene group and the like are preferable.
- the alkyl group represented by RA or RB contained in the silylene bond or the 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 an alkyl group having 1 or 2 carbon atoms is further preferable.
- Specific examples of the alkyl group represented by RA or RB include a methyl group, an ethyl group, an n - propyl group, an isopropyl group, an n-butyl group, an isobutyl group, an s-butyl group, a t-butyl group and the like. Can be mentioned.
- tetravalent organic group represented by X may be groups represented by the following formulas (J) to (O).
- the divalent organic group represented by Y preferably has 4 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, and further preferably 12 to 18 carbon atoms. ..
- the skeleton of the divalent organic group represented by Y may be similar to the skeleton of the tetravalent organic group represented by X, and the preferred skeleton of the divalent organic group represented by Y is X. It may be the same as the preferable 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, and the two bonding positions are substituted with an atom (for example, a hydrogen atom) or a functional group (for example, an alkyl group). It may be a structure.
- 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.
- a divalent aromatic hydrocarbon group for example, the number of carbon atoms constituting the aromatic ring is 6 to 20
- a divalent aromatic heterocyclic group for example, forming a heterocycle
- the number of atoms is 5 to 20) and the like, and a divalent aromatic hydrocarbon group is preferable.
- divalent aromatic group represented by Y include groups represented by the following formulas (G) to (I).
- the group represented by the following formula (H) is preferable, and the group represented by the following formula (H) is represented by D from the viewpoint of obtaining an insulating film having excellent flexibility and more suppressed generation of voids at the bonding interface. Is more preferably a group containing an ether bond, and even more preferably an ether bond.
- R independently represents an alkyl group, an alkoxy group, an alkyl halide group, a phenyl group or a halogen atom
- n independently represents an integer of 0 to 4, respectively.
- D is a single bond, an alkylene group, a halogenated alkylene group, a carbonyl group, a sulfonyl group, an ether bond (—O—), a sulfide bond (—S—), a phenylene group, and an ester bond (—O—).
- D may have a structure represented by the above formula (C1).
- the specific example of D in the formula (H) is the same as the specific example of C in the formula (E).
- the D in the formula (H) is preferably 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, and the like.
- the alkyl group represented by R in the formulas (G) to (I) is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms. , It is more preferably an alkyl group having 1 or 2 carbon atoms.
- Specific examples of the alkyl group represented by R in the formulas (G) to (I) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group and an s-butyl group. Examples thereof include a t-butyl group.
- the alkoxy group represented by R in the formulas (G) to (I) is preferably an alkoxy group having 1 to 10 carbon atoms, and more preferably an alkoxy group having 1 to 5 carbon atoms. , It is more preferable that it is an alkoxy group having 1 or 2 carbon atoms.
- Specific examples of the alkoxy group represented by R in the formulas (G) to (I) include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group and an s-butoxy group. , T-butoxy group and the like.
- the alkyl halide group represented by R in the formulas (G) to (I) is preferably an alkyl halide group having 1 to 5 carbon atoms, and an alkyl halide group having 1 to 3 carbon atoms. It is more preferable that it is an alkyl halide group having 1 or 2 carbon atoms.
- the halogenated alkyl group represented by R in the formulas (G) to (I) at least one hydrogen atom contained in the alkyl group represented by R in the formulas (G) to (I).
- examples thereof include an alkyl group substituted with a halogen atom such as a fluorine atom and a chlorine atom.
- a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group and the like are preferable.
- n in the formulas (G) to (I) is preferably 0 to 2, more preferably 0 or 1, and even more preferably 0, respectively.
- 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 a divalent group having a polysiloxane structure. The basics of.
- 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 carbon. More preferably, it is an alkylene group having a number of 1 to 10.
- Specific examples of the alkylene group represented by Y include a tetramethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, a decamethylene group, an undecamethylene group, a dodecamethylene group, and a 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, and 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 alkylene oxide structure having 1 to 10 carbon atoms is preferable, the alkylene oxide structure having 1 to 8 carbon atoms is more preferable, and the alkylene oxide structure having 1 to 8 carbon atoms is more preferable.
- the alkylene oxide structure of 1 to 4 is more preferable.
- the polyethylene oxide structure or the polypropylene oxide structure is preferable as the polyalkylene oxide structure.
- the alkylene group in the alkylene oxide structure may be linear or branched.
- the unit structure in the polyalkylene oxide structure may be one kind or two or more kinds.
- 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 thereof include a divalent group having a polysiloxane structure.
- Specific examples of the alkyl group having 1 to 20 carbon atoms bonded to the silicon atom in the polysiloxane structure include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group and an n-.
- Examples thereof include an octyl group, a 2-ethylhexyl group and an n-dodecyl group. Among these, a methyl group is preferable.
- 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. Specific examples of the substituent when the aryl group has a substituent include a halogen atom, an alkoxy group, a hydroxy group and the like. Specific examples of the aryl group having 6 to 18 carbon atoms include a phenyl group, a naphthyl group, a benzyl group and the like.
- the alkyl group having 1 to 20 carbon atoms or the aryl group having 6 to 18 carbon atoms in the polysiloxane structure may be of one kind or two or more kinds.
- the silicon atom constituting the divalent group having a polysiloxane structure represented by Y is an NH group in the general formula (1) via an alkylene group such as a methylene group and an ethylene group and 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 the following formula (H') or the formula (H ". ) Is preferable, and the group represented by the formula (I) is preferably a group represented by the following formula (I').
- R independently represents an alkyl group, an alkoxy group, an alkyl halide group, a phenyl 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 the general formula (1) is not particularly limited.
- X is a group represented by the formula (E) and Y is represented by the formula (H).
- 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, and is a group represented by the following general formula (2), an ethyl group, or the like. It is more preferably either an isobutyl group or a t-butyl group, further preferably containing an aliphatic hydrocarbon group having 1 or 2 carbon atoms or a group represented by the following general formula (2), and the following general formula. It is particularly preferable to include the group represented by (2).
- the monovalent organic group contains an organic group having an unsaturated double bond, preferably a group represented by the following general formula (2), so that the i-ray transmittance is high and even when cured at a low temperature of 400 ° C. or lower. It tends to form a good cured product.
- the aliphatic hydrocarbon group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group and the like, and among them, an ethyl group and an ethyl group. Isobutyl groups 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 the 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 the like, and a methyl group is preferable.
- R 8 to R 10 in the general formula (2) a combination of R 8 and R 9 is a hydrogen atom, and R 10 is a hydrogen atom or a methyl group is preferable.
- R x in the 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 a linear or branched alkylene group.
- the number of carbon atoms in Rx is preferably 1 to 10, more preferably 2 to 5, and even more preferably 2 or 3.
- R 6 and R 7 are a group represented by the general formula (2), and both R 6 and R 7 are in the general formula (2). It is more preferable that it is a group represented.
- the component (A) contains a compound having a structural unit represented by the above-mentioned general formula (1), it is represented by the general formula (2) with respect to the total of R 6 and R 7 of all structural units contained in the compound.
- the ratio of R 6 and R 7 to be formed is preferably 60 mol% or more, more preferably 70 mol% or more, still 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 the general formula (2) is preferably a group represented by the following general formula (2').
- 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 in the general formula (2') 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 with respect to all the structural units. 70 mol% or more is more preferable, and 80 mol% or more is further preferable.
- the upper limit of the above-mentioned content rate is not particularly limited, and may be 100 mol%.
- the component (A) may be synthesized by using a tetracarboxylic acid 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 component (A) may be synthesized using tetracarboxylic dianhydride instead of tetracarboxylic dianhydride.
- tetracarboxylic acid dianhydride examples include pyromellitic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, and 3,3', 4,4'-biphenyltetracarboxylic acid dianhydride.
- diamine compound examples include 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2'-difluoro-4,4'-diaminobiphenyl, p-phenylenediamine, m-.
- diamine compound m-phenylenediamine, 4,4'-diaminodiphenyl ether and 1,3-bis (3-aminophenoxy) benzene are preferable.
- the diamine compound may be used alone or in combination of two or more.
- a compound having a structural unit represented by the general formula (1) and having at least one of R 6 and R 7 in the general formula (1) being a monovalent organic group is, for example, the following (a) or It can be obtained by the method of (b).
- (A) Tetracarboxylic acid dianhydride (preferably tetracarboxylic acid dianhydride represented by the following general formula (8)) and a compound represented by R-OH are reacted in an organic solvent to diester. After the derivative, the diester derivative and the diamine compound represented by H2NY-NH 2 are subjected to a condensation reaction.
- the tetracarboxylic dianhydride represented by the general formula (8), the diamine compound represented by H2NY — NH2 , and the compound represented by R—OH may be used alone. Often, two or more types may be combined. Examples of the above-mentioned organic solvent include N-methyl-2-pyrrolidone, ⁇ -butyrolactone, dimethoxyimidazolidinone, 3-methoxy-N, N-dimethylpropionamide and the like, among which 3-methoxy-N, N- Dimethylpropionamide is preferred.
- a polyimide precursor may be synthesized by allowing a dehydration condensing agent to act on a polyamic acid solution together with a compound represented by R-OH.
- the dehydration condensing 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 component (A) is obtained by reacting a tetracarboxylic acid dianhydride represented by the following general formula (8) with a compound represented by R-OH to form a diester derivative, and then thionyl chloride or the like. It can be obtained by reacting the chlorinating agent of the above to convert it into an acid chloride, and then reacting the diamine compound represented by H2NY-NH 2 with the acid chloride.
- the above-mentioned compound contained in the component (A) is prepared as a diester derivative by allowing a compound represented by R-OH to act on a tetracarboxylic acid dianhydride represented by the following general formula (8) to obtain a carbodiimide compound.
- the above-mentioned compound contained in the component (A) is a polyamic acid obtained by reacting a tetracarboxylic acid dianhydride represented by the following general formula (8) with a diamine compound represented by H2NY—NH 2 . Then, the polyamic acid is isoimided in the presence of a dehydration condensing agent such as trifluoroacetic anhydride, and then a compound represented by R-OH is allowed to act on the polyamic acid.
- a dehydration condensing agent such as trifluoroacetic anhydride
- a compound represented by R-OH is allowed to act on a part of the tetracarboxylic acid dianhydride in advance to partially esterify the tetracarboxylic acid dianhydride and H2NY - NH2 . You may react with the diamine compound which is made.
- X is the same as the X in the general formula (1), and the specific example and the preferable example are also the same.
- Examples of the compound represented by R—OH used for the synthesis of the above-mentioned compound contained in the component (A) include a compound in which a hydroxy group is bonded to R x of the group represented by the general formula (2), and a general formula (A). It may be a compound in which a hydroxy group is bonded to a terminal methylene group of the group represented by 2').
- Specific examples of the compound represented by R-OH include methanol, ethanol, n-propanol, isopropanol, n-butanol, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, and acrylic.
- Examples thereof include 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl acrylate and the like. Among them, 2 hydroxyacrylate. -Hydroxyethyl and 2-hydroxyethyl acrylate are preferred.
- the molecular weight of the component (A) is not particularly limited, and for example, the weight average molecular weight is preferably 10,000 to 200,000, more preferably 10,000 to 100,000.
- the weight average molecular weight can be measured, for example, by a gel permeation chromatography method and can be determined by conversion using a standard polystyrene calibration curve.
- the resin composition of the present disclosure may further contain a dicarboxylic acid, and in the (A) polyimide precursor contained in the resin composition, a part of the amino group in the (A) polyimide precursor is a carboxy group in the dicarboxylic acid. It may have a structure formed by reacting with. For example, when synthesizing a polyimide precursor, a part of the amino group of the diamine compound may be reacted with the carboxy group of the dicarboxylic acid.
- the dicarboxylic acid may be a dicarboxylic acid having a (meth) acrylic group, and may be, for example, a dicarboxylic acid represented by the following formula.
- a methacrylic group derived from the dicarboxylic acid is added to the (A) polyimide precursor by reacting a part of the amino group of the diamine compound with the carboxy group of the dicarboxylic acid. Can be introduced.
- the resin composition of the present disclosure may contain a polyimide resin as a component (A), or may contain the above-mentioned polyimide precursor and the polyimide resin.
- the polyimide resin is not particularly limited as long as it is a polymer compound having a plurality of structural units containing an imide bond, and for example, it is preferable to include a compound having a structural unit represented by the following general formula (X). As a result, there is a tendency to obtain a semiconductor device having an insulating film showing high reliability.
- X represents a tetravalent organic group and Y represents a divalent organic group.
- Preferred examples of the substituents X and Y in the general formula (X) are the same as the preferred examples of the substituents X and Y in the above-mentioned general formula (1).
- the polyimide resin referred to here refers to a resin having an imide skeleton in all or part of the resin skeleton.
- the polyimide resin is preferably soluble in a solvent in a resin composition using a polyimide precursor.
- the ratio of the polyimide resin to the total of the polyimide precursor and the polyimide resin may be 15% by mass to 50% by mass, or 10% by mass to 20% by mass. May be.
- the resin composition of the present disclosure may contain a resin component other than the component (A).
- the resin composition of the present disclosure includes novolak resin, acrylic resin, polyether nitrile resin, polyether sulfone resin, epoxy resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polyvinyl chloride resin and the like. It may contain other resins. Other resins may be used alone or in combination of two or more.
- the content of the component (A) with respect to the total amount of the resin component is preferably 50% by mass to 100% by mass, more preferably 70% by mass to 100% by mass, and 90% by mass. It is more preferably% to 100% by mass.
- the resin composition of the present disclosure contains (B) a solvent (hereinafter, also referred to as “component (B)”).
- component (B) contains, for example, at least one selected from the group consisting of the compounds represented by the following formulas (3) to (7) from the viewpoint of reducing the reproductive toxicity and environmental load of the resin composition. Is preferable.
- R 1 , R 2 , R 8 and R 10 are independently alkyl groups having 1 to 4 carbon atoms, and R 3 to R 7 and R 9 are independent of each other. In addition, it is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- s is an integer of 0 to 8
- t is an integer of 0 to 4
- r is an integer of 0 to 4
- u is an integer of 0 to 3.
- the alkyl group having 1 to 4 carbon atoms of R2 is preferably a methyl group or an ethyl group.
- t is preferably 0, 1 or 2, and more preferably 1.
- the alkyl group having 1 to 4 carbon atoms of R3 is preferably a methyl group, an ethyl group, a propyl group or a butyl group.
- the alkyl group having 1 to 4 carbon atoms of R 4 and R 5 is preferably a methyl group or an ethyl group.
- the alkyl group having 1 to 4 carbon atoms of R 6 to R 8 is preferably a methyl group or an ethyl group.
- r is preferably 0 or 1, and more preferably 0.
- the alkyl group having 1 to 4 carbon atoms of R 9 and R 10 is preferably a methyl group or an ethyl group.
- u is preferably 0 or 1, more preferably 0.
- the component (B) may be, for example, at least one of the compounds represented by the formulas (4), (5), (6) and (7), and the compound represented by the formula (5) or It may be a compound represented by the formula (7).
- component (B) include the following compounds.
- the component (B) contained in the resin composition of the present disclosure is not limited to the above-mentioned compound, and may be another solvent.
- the component (B) may be a solvent for esters, a solvent for ethers, a solvent for ketones, a solvent for hydrocarbons, a solvent for aromatic hydrocarbons, a solvent for sulfoxides, and the like.
- Ester solvents 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, and ⁇ -butyrolactone.
- ⁇ -caprolactone, ⁇ -valerolactone methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate and other alkyl alkoxyacetates (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate and ethyl ethoxyacetate), 3-alkoxypropionate alkyl esters such as methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate and 3-ethoxypropionate).
- 3-alkoxypropionate alkyl esters such as methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate,
- 2-alkoxypropionate alkyl esters such as ethyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, etc.)
- Methyl 2-alkoxy-2-methylpropionate, 2-ethoxy-2 such as propyl 2-methoxypropionate, methyl 2-ethoxypropionate and ethyl 2-ethoxypropionate), methyl 2-methoxy-2-methylpropionate, etc.
- -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. Can be mentioned.
- 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, and propylene.
- examples thereof include glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.
- Examples of the solvent for the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone (NMP) and the like.
- Examples of the hydrocarbon solvent include limonene and the like.
- Examples of the solvent for aromatic hydrocarbons include toluene, xylene, anisole and the like.
- Examples of the solvent for sulfoxides include dimethyl sulfoxide and the like.
- Examples of the solvent for the component (B) include ⁇ -butyrolactone, cyclopentanone, ethyl lactate and the like.
- the content of NMP may be 1% by mass or less with respect to the total amount of the resin composition, and may be the total amount of the component (A). On the other hand, it may be 3% by mass or less.
- the content of the component (B) is preferably 1 part by mass to 10000 parts by mass, and 50 parts by mass to 10000 parts by mass with respect to 100 parts by mass of the component (A). Is more preferable.
- the component (B) is at least one solvent (1) selected from the group consisting of compounds represented by the formulas (3) to (6), as well as a solvent for esters, a solvent for ethers, and a solvent for ketones.
- At least one of the solvent (2) which is at least one selected from the group consisting of a solvent for hydrocarbons, a solvent for aromatic hydrocarbons, and a solvent for sulfoxides.
- the content of the solvent (1) may be 5% by mass to 100% by mass or 5% by mass to 50% by mass with respect to 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, or 10 parts by mass to 100 parts by mass with respect to 100 parts by mass of the component (A). It may be 50 parts by mass.
- the resin composition of the present disclosure preferably further contains (C) a photopolymerization initiator and (D) a polymerizable monomer (hereinafter, also referred to as (C) component and (D) component, respectively). Further, the resin composition of the present disclosure may further contain (E) a thermal polymerization initiator (hereinafter, also referred to as a component (E)).
- C photopolymerization initiator
- D polymerizable monomer
- E a thermal polymerization initiator
- the resin composition of the present disclosure preferably contains (C) a photopolymerization initiator.
- component (C) examples include benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Mihiler ketone), N, N'-tetraethyl-4,4'-diaminobenzophenone, 4-methoxy-.
- Benzoin derivatives such as methyl ether, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, ethyl benzoin, propyl benzoin; 1-phenyl-1,2-butandion-2- (O-methoxycarbonyl) oxime, 1-phenyl-1, 2-Phenyldione-2- (O-methoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, 1-phenyl-1,2-propanedione-2- ( O-benzoyl) oxime, 1,3-diphenylpropantrion-2- (O-ethoxycarbonyl) oxime, 1-phenyl-3-ethoxypropanetrion-2- (O-benzoyl) oxime, 1,2-octanedione, Oxym derivatives such as 1- [4- (phenylthio) pheny
- phosphine oxide derivatives examples thereof include phosphine oxide derivatives, Irgacure OXE03 (manufactured by BASF), Irgacure OXE04 (manufactured by BASF) and the like.
- the component (C) may be used alone or in combination of two or more.
- an oxime compound derivative is preferable from the viewpoint of high sensitivity, high reactivity, and no metal element.
- the content of the component (C) is 0. 1 part by mass to 20 parts by mass is preferable, 0.1 part by mass to 10 parts by mass is more preferable, and 0.1 part by mass to 6 parts by mass is further preferable.
- the resin composition of the present disclosure may contain an antireflection agent that suppresses reflected light from the substrate direction from the viewpoint of improving the photosensitive characteristics.
- the resin composition of the present disclosure preferably contains (D) a polymerizable monomer.
- the component (D) preferably has at least one group containing a polymerizable unsaturated double bond, and contains at least a (meth) acrylic group from the viewpoint that it can be suitably polymerized when used in combination with a photopolymerization initiator. It is more preferable to have one. From the viewpoint of improving the crosslink density and the photosensitivity, it is preferable to have 2 to 6 groups containing a polymerizable unsaturated double bond, and more preferably 2 to 4 groups.
- the polymerizable monomer may be used alone or in combination of two or more.
- the polymerizable monomer having a (meth) acrylic group is not particularly limited, and for example, 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 is, for example, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, methylenebisacrylamide, N. , N-dimethylacrylamide and N-methylolacrylamide.
- the component (D) is not limited to a compound having a group containing a polymerizable unsaturated double bond, and may be a compound having a polymerizable group (for example, an oxylan ring) other than the unsaturated double bond group. ..
- the content of the component (D) is not particularly limited, and may be 1 part by mass to 100 parts by mass with respect to 100 parts by mass of the component (A). It is preferably 1 part by mass to 75 parts by mass, more preferably 1 part by mass to 50 parts by mass.
- the resin composition of the present disclosure preferably contains (E) a thermal polymerization initiator from the viewpoint of improving the physical properties of the cured product.
- component (E) examples include a ketone peroxide such as methyl ethyl ketone peroxide, 1,1-di (t-hexyl peroxide) -3,3,5-trimethylcyclohexane, and 1,1-di (t-hexyl peroxide).
- a ketone peroxide such as methyl ethyl ketone peroxide, 1,1-di (t-hexyl peroxide) -3,3,5-trimethylcyclohexane, and 1,1-di (t-hexyl peroxide).
- Cyclohexane, peroxyketal such as 1,1-di (t-butylperoxy) cyclohexane, 1,1,3,3-tetramethylbutylhydroperoxide, cumenehydroperoxide, p-menthan hydroperoxide, diisopropylbenzenehydroperoxide Hydroperoxides such as, dicumyl peroxides, dialkyl peroxides such as di-t-butyl peroxides, diacyl peroxides such as dilauroyl peroxides and dibenzoyl peroxides, di (4-t-butylcyclohexyl) peroxydicarbonates, di (2-).
- peroxyketal such as 1,1-di (t-butylperoxy) cyclohexane, 1,1,3,3-tetramethylbutylhydroperoxide, cumenehydroperoxide, p-menthan hydroperoxide, diisopropylbenz
- Ethylhexyl) Peroxydicarbonate such as peroxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropylmonocarbonate, t-butylperoxybenzoate, 1,1,3,3- Examples thereof include peroxyesters such as tetramethylbutylperoxy-2-ethylhexanoate and bis (1-phenyl-1-methylethyl) peroxides.
- the thermal polymerization initiator may be used alone or in combination of two or more.
- the content of the component (E) may be 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the polyimide precursor. It may be 5 parts by mass to 15 parts by mass, or 5 parts by mass to 10 parts by mass.
- the resin composition of the present disclosure may contain (F) a polymerization inhibitor (hereinafter, also referred to as “component (F)”) from the viewpoint of ensuring good storage stability.
- a polymerization inhibitor hereinafter, also referred to as “component (F)”
- the polymerization inhibitor include a radical polymerization inhibitor, a radical polymerization inhibitor and the like.
- component (F) examples include p-methoxyphenol, diphenyl-p-benzoquinone, benzoquinone, hydroquinone, pyrogallol, phenothiazine, resorcinol, orthodinitrobenzene, paradinitrobenzene, metadinitrobenzene, phenanthraquinone, and N-phenyl-.
- Examples thereof include 2-naphthylamine, cuperon, 2,5-toluquinone, tannic acid, parabenzylaminophenol, nitrosoamines, hindered phenolic compounds and the like.
- the polymerization inhibitor may be used alone or in combination of two or more.
- the hindered phenolic compound may have both the function of a polymerization inhibitor and the function of an antioxidant described later, or may have either function.
- the hindered phenol-based compound is not particularly limited, and is, for example, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-butyl-hydroquinone, octadecyl-3- (3,5-).
- the content of the component (F) is 100 parts by mass of the component (A) from the viewpoint of storage stability of the resin composition and heat resistance of the obtained cured product.
- it is preferably 0.01 part by mass to 30 parts by mass, more preferably 0.01 part by mass to 10 parts by mass, and further preferably 0.05 part by mass to 5 parts by mass. ..
- the resin composition of the present disclosure may further contain an antioxidant, a coupling agent, a surfactant, a leveling agent, a rust inhibitor or a nitrogen-containing compound.
- the resin composition of the present disclosure may contain an antioxidant from the viewpoint of suppressing deterioration of adhesiveness by capturing oxygen radicals and peroxide radicals generated by high temperature storage, reflow treatment and the like. Since the resin composition of the present disclosure contains an antioxidant, it is possible to suppress the oxidation of the electrode during the insulation reliability test.
- antioxidants include the compound exemplified as the above-mentioned hindered phenolic compound, N, N'-bis [2- [2- (3,5-di-tert-butyl-4-hydroxyphenyl) ethyl.
- the content of the antioxidant is preferably 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the component (A), and 0. It is more preferably 1 part by mass to 10 parts by mass, and further preferably 0.1 part by mass to 5 parts by mass.
- the resin composition of the present disclosure may contain a coupling agent.
- the coupling agent reacts with the component (A) to crosslink, or the coupling agent itself polymerizes. Thereby, there is a tendency that the adhesiveness between the obtained cured product and the substrate can be further improved.
- the coupling agent are not particularly limited.
- the coupling agent 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3 -Methacryloxypropyldimethoxymethylsilane, 3-methacryloxypropyltrimethoxysilane, dimethoxymethyl-3-piperidinopropylsilane, diethoxy-3-glycidoxypropylmethylsilane, N- (3-diethoxymethylsilylpropyl) Succinimide, N- [3- (triethoxysilyl) propyl] phthalamide acid, benzophenone-3,3'-bis (N- [3-triethoxysilyl] propylamide) -4,4'-dicarboxylic acid, benzen
- the content of the coupling agent is preferably 0.1 part by mass to 20 parts by mass, preferably 0.3 parts by mass with respect to 100 parts by mass of the component (A). Up to 10 parts by mass is more preferable, and 1 part by mass to 10 parts by mass is further preferable.
- the resin composition of the present disclosure may contain at least one of a surfactant and a leveling agent.
- a surfactant and a leveling agent By containing at least one of a surfactant and a leveling agent in the resin composition, coatability (for example, suppression of striation (unevenness of film thickness)), improvement of adhesiveness, compatibility of compounds in the resin composition, etc. are improved. 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 surfactant and the leveling agent may be used alone or in combination of two or more.
- the total content of the surfactant and the leveling agent is 0.01 part by mass to 10 parts by mass with respect to 100 parts by mass of the component (A). It is preferably by mass, more preferably 0.05 parts to 5 parts by mass, and even more preferably 0.05 parts by mass to 3 parts by mass.
- the resin composition of the present disclosure may contain a rust inhibitor from the viewpoint of suppressing corrosion of metals such as copper and copper alloys and from the viewpoint of suppressing discoloration of the metal.
- a rust preventive agent include azole compounds and purine derivatives.
- azole compound examples include 1H-triazole, 5-methyl-1H-triazole, 5-ethyl-1H-triazole, 4,5-dimethyl-1H-triazole, 5-phenyl-1H-triazole, 4-t-.
- purine derivative examples include purine, adenine, guanine, hypoxanthine, xanthine, theobromine, caffeine, uric acid, isoguanine, 2,6-diaminopurine, 9-methyladenine, 2-hydroxyadenine, 2-methyladenine, and the like.
- the rust preventive agent may be used alone or in combination of two or more.
- the content of the rust preventive is preferably 0.01 part by mass to 10 parts by mass with respect to 100 parts by mass of the component (A). It is more preferably 1 part by mass to 5 parts by mass, and further preferably 0.5 part by mass to 3 parts by mass.
- the content of the rust inhibitor is 0.1 part by mass or more, discoloration of the surface of copper or copper alloy is suppressed when the resin composition of the present disclosure is applied on the surface of copper or copper alloy. Will be done.
- the resin composition of the present disclosure may contain a nitrogen-containing compound from the viewpoint of promoting the imidization reaction of the component (A) to obtain a highly reliable cured product.
- nitrogen-containing compound examples include 2- (methylphenylamino) ethanol, 2- (ethylanilino) ethanol, N-phenyldiethanolamine, N-methylaniline, N-ethylaniline, N, N'-dimethylaniline, and N-.
- the nitrogen-containing compound may be used alone or in combination of two or more.
- the nitrogen-containing compound preferably contains a compound represented by the following formula (17).
- R 31A to R 33A are independently hydrogen atoms, monovalent aliphatic hydrocarbon groups, monovalent aliphatic hydrocarbon groups having a hydroxy group, or monovalent aromatic groups. Yes, at least one (preferably one) of R 31A to R 33A is a monovalent aromatic group.
- R 31A to R 33A may form a ring structure between adjacent groups. 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 and a phenyl group.
- the hydrogen atom of the monovalent aliphatic hydrocarbon group may be substituted with a functional group other than the 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, or a monovalent aromatic. It is preferably a family group.
- the monovalent aliphatic hydrocarbon group of R 31A to R 33A preferably has 1 to 10 carbon atoms, and 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 has one or more hydroxy groups bonded to the monovalent aliphatic hydrocarbon group of R 31A to R 33A . It is preferable that the group is a group, and it is more preferable that the group has one to three hydroxy groups bonded thereto. Specific examples of the monovalent aliphatic hydrocarbon group having a hydroxy group include a methylol group and a hydroxyethyl group, and among them, a hydroxyethyl group is preferable.
- Examples of the monovalent aromatic group of R 31A to R 33A of the formula (17) include a monovalent aromatic hydrocarbon group, a monovalent aromatic heterocyclic group and the like, and a monovalent aromatic hydrocarbon. Groups are preferred.
- the monovalent aromatic hydrocarbon group preferably has 6 to 12 carbon atoms, and 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 group of R 31A to R 33A of the formula (17) may have a substituent.
- a group similar to the group can be mentioned.
- the content of the nitrogen-containing compound is preferably 0.1 part by mass to 20 parts by mass with respect to 100 parts by mass of the component (A), and is stable in storage. From the viewpoint of sex, it is more preferably 0.3 parts by mass to 15 parts by mass, and further preferably 0.5 part by mass to 10 parts by mass.
- the resin composition of the present disclosure contains a component (A) and a component (B), and if necessary, a component (C) to a component (F), an antioxidant, a coupling agent, a surfactant, a leveling agent, and an anti-corrosion agent. It may contain a rust agent, a nitrogen-containing compound and the like, and may contain other components and unavoidable impurities as long as the effects of the present disclosure are not impaired. For example, 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 resin composition of the present disclosure.
- component and (B) component At least one selected from the group consisting of components (A) to (F) and antioxidants, coupling agents, surfactants, leveling agents, rust inhibitors and nitrogen-containing compounds. It may consist of.
- the semiconductor device of the present disclosure includes a first semiconductor substrate having a first substrate main body, the first organic insulating film and a first electrode provided on one surface of the first substrate main body, a semiconductor chip substrate main body, and the above.
- a semiconductor chip having an organic insulating film portion provided on one surface of a semiconductor chip substrate main body and a second electrode is provided, and the first organic insulating film of the first semiconductor substrate and the organic insulating film of the semiconductor chip are provided.
- the first electrode of the first semiconductor substrate and the second electrode of the semiconductor chip are joined to each other, and at least one of the first organic insulating film and the organic insulating film portion is present. It is a semiconductor device which is an insulating film obtained by curing the disclosed resin composition.
- the semiconductor device of the present disclosure Since at least one of the first organic insulating film and the organic insulating film portion is an insulating film obtained by curing the resin composition of the present disclosure, the semiconductor device of the present disclosure suppresses the generation of voids at the bonding interface of the insulating film. And has excellent heat resistance of the insulating film. Further, the semiconductor device of the present disclosure is manufactured through steps (1) to (5).
- a semiconductor device is manufactured using the resin composition of the present disclosure. Specifically, a semiconductor device can be manufactured by going through steps (1) to (5) using the resin composition of the present disclosure.
- the cured product of the present disclosure is obtained by curing the resin composition of the present disclosure.
- the cured product is used, for example, as an insulating film for a semiconductor device.
- FIG. 1 is a cross-sectional view schematically showing an example of the semiconductor device of the present disclosure.
- the semiconductor device 1 is an example of a semiconductor package, for example, a first semiconductor chip 10 (first semiconductor substrate), a second semiconductor chip 20 (semiconductor chip), a pillar portion 30, and a rewiring layer 40. , A substrate 50, and a circuit substrate 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 a 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 are finely bonded to each other by hybrid bonding, which will be described in detail later, so that the respective terminal electrodes and the insulating films around them are firmly and without displacement.
- the pillar portion 30 is a connecting portion in which a plurality of pillars 31 formed of a metal such as copper (Cu) are sealed with a resin 32.
- the plurality of pillars 31 are conductive members extending from the upper surface to the lower surface of the pillar portion 30.
- the plurality of pillars 31 may have a cylindrical shape having a diameter of 3 ⁇ m or more and 20 ⁇ m or less (in one example, a diameter of 5 ⁇ m), or may be arranged so that the distance between the centers of the pillars 31 is 15 ⁇ m or less.
- the plurality of pillars 31 flip-chip connect the lower terminal electrode of the first semiconductor chip 10 and the upper terminal electrode of the rewiring layer 40.
- the semiconductor device 1 can form a connection electrode without using a technique called TMV (Through mold via) in which a hole is made in a mold and soldered.
- the pillar portion 30 has, for example, a thickness similar to that of the second semiconductor chip 20, and is arranged on the lateral side of the second semiconductor chip 20 in the horizontal direction.
- a plurality of solder balls may be arranged in place 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 having a terminal pitch conversion function, which is a function of the package substrate, and is made of polyimide, copper wiring, or the like on the insulating film under the second semiconductor chip 20 and on the lower surface of the pillar portion 30. It is a layer in which a rewiring pattern is formed.
- the rewiring layer 40 is formed in a state where the first semiconductor chip 10, the second semiconductor chip 20, and the like are turned upside down (see (d) in FIG. 4).
- the rewiring layer 40 electrically connects the terminal electrode on the lower surface of the second semiconductor chip 20 and the terminal electrode of the first semiconductor chip 10 via the pillar portion 30 to the terminal electrode 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 substrate 50. If there is a large difference in the terminal pitch between the rewiring layer 40 and the substrate 50, an inorganic interposer or the like is used between the rewiring layer 40 and the substrate 50 to electrically connect the rewiring layer 40 and the substrate 50. You may make a connection.
- the circuit board 60 mounts the first semiconductor chip 10 and the second semiconductor chip 20 on it, and is electrically connected to the substrate 50 connected to the first semiconductor chip 10, the second semiconductor chip 20, the electronic component 51, and the like. It is a substrate having a plurality of through electrodes to be formed inside.
- the terminal electrodes of the first semiconductor chip 10 and the second semiconductor chip 20 are electrically connected to the terminal electrodes 61 provided on the back surface of the circuit board 60 by the plurality of through electrodes.
- FIG. 2 is a diagram showing in order 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. 2.
- FIG. 4 is a method for manufacturing the semiconductor device shown in FIG. 1, and is a diagram showing steps after the steps shown in FIG. 2 in order.
- the semiconductor device 1 can be manufactured, for example, through the following steps (a) to (n).
- B A step of preparing a second semiconductor substrate 200 corresponding to the second semiconductor chip 20.
- C A step of polishing the first semiconductor substrate 100.
- D A step of polishing the second semiconductor substrate 200.
- E A step of disassembling the second semiconductor substrate 200 and acquiring a plurality of semiconductor chips 205.
- F 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.
- (G) A step of bonding the insulating film 102 of the first semiconductor substrate 100 and the insulating film portions 202b of the plurality of semiconductor chips 205 to each other (see (b) in FIG. 3).
- (H) A step of joining the terminal electrode 103 of the first semiconductor substrate 100 and the terminal electrode 203 of each of the plurality of semiconductor chips 205 (see (c) in FIG. 3).
- (I) A step of forming a plurality of pillars 300 (corresponding to pillars 31) between a plurality of semiconductor chips 205 on the connection surface of the first semiconductor substrate 100.
- (J) A step of molding a resin 301 on a connection surface of a first semiconductor substrate 100 so as to cover the semiconductor chip 205 and the pillar 300 to obtain a semi-finished product M1.
- (K) A step of grinding and thinning the resin 301 side of the semi-finished product M1 molded in the step (j) to obtain the semi-finished product M2.
- (L) A step of forming a wiring layer 400 corresponding to the rewiring layer 40 on the semi-finished product M2 thinned in the step (k).
- (M) A step of cutting the semi-finished product M3 on which the wiring layer 400 is formed in the step (l) along the cutting line A so as to be each semiconductor device 1.
- (N) A step of inverting the semiconductor device 1a individualized in the step (m) and installing it on the substrate 50 and the circuit board 60 (see FIG. 1).
- step (1) corresponds to the above-mentioned steps (a) and (c)
- step (2) corresponds to the above-mentioned steps (b) and (d)
- step (3) corresponds to step (e)
- step (4) corresponds to step (g)
- step (5) corresponds to step (h).
- the resin composition of the present disclosure comprises a first organic insulating film and a second organic insulating in a method for manufacturing a semiconductor device including at least one step corresponding to the step (f) and the steps (i) to (n). It may be a resin composition for use in producing at least one insulating film of the film.
- the 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 in which an integrated circuit including a semiconductor element and wiring connecting them is formed.
- a plurality of terminal electrodes 103 made of copper, aluminum, or the like are designated on one surface 101a of the first substrate main body 101 made of silicon or the like.
- An insulating film 102 (first insulating film), which is a cured product obtained by curing the resin composition of the present disclosure while being provided at intervals, is provided.
- 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 and then the insulating film. 102 may be provided.
- a predetermined interval is provided between the plurality of terminal electrodes 103 in order to form the pillar 300 in a step 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.
- the step (b) is a step of preparing a second semiconductor substrate 200, which is a silicon substrate corresponding to a plurality of second semiconductor chips 20 and having an integrated circuit including semiconductor elements and wirings connecting them.
- a plurality of terminal electrodes 203 (a plurality of second electrodes) made of copper, aluminum, etc. are placed on one surface 201a of the second substrate main body 201 made of silicon or the like.
- an insulating film 202 (second insulating film) which is a cured product obtained by curing the resin composition of the present disclosure is provided.
- a plurality of terminal electrodes 203 may be provided after the insulating film 202 is provided on one surface 201a of the second substrate main body 201, or a plurality of terminal electrodes 203 may be provided on one surface 201a of the second substrate main body 201 and then the insulating film 202. May be provided.
- the insulating films 102 and 202 used in the steps (a) and (b) are not limited to the structure in which both the insulating films 102 and 202 are cured products obtained by curing the resin composition of the present disclosure, and at least one of the insulating films 102 and 202 is the present. It may be a cured product obtained by curing the disclosed resin composition.
- a resin composition containing an organic material such as polyimide, polyamideimide, benzocyclobutene (BCB), polybenzoxazole (PBO), and PBO precursor is cured without containing a polyimide precursor.
- a cured product made of polyimide can be mentioned.
- the tensile elastic 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, further preferably 3.0 GPa or less, and 2.0 GPa or less. The following is particularly preferable, and 1.5 GPa or less is even more 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. As a result, the processing time can be shortened in the subsequent polishing step while ensuring the uniformity of the film 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 from the viewpoint of facilitating the work in the step (c) and the step (d) and simplifying these steps. It is preferable that the polishing rate of the insulating film 202 satisfies at least one (preferably satisfying both) of 0.1 to 5 times the polishing rate of the terminal electrode 203. stomach.
- the polishing rate of the insulating film 102 or 202 is 200 nm / min or less (four times or less of the polishing rate of copper). It is more preferably 100 nm / min or less (twice or less of the polishing rate of copper), and even more preferably 50 nm / min or less (equal to or less than the polishing rate of copper).
- the insulating film is obtained by curing the resin composition.
- the method for producing the above-mentioned insulating film includes, for example, a step of applying ( ⁇ ) a resin composition on a substrate and drying it to form a resin film, and a step of heat-treating the resin film.
- ⁇ ) A step of forming a film with a certain film thickness on a film that has been subjected to a mold release treatment using a resin composition and then transferring the resin film to a substrate by a laminating method, and a resin film formed on the substrate after the transfer.
- Examples of the method for applying the resin composition include a spin coating method, an inkjet method, and a slit coating method.
- the rotation speed is 300 rpm (rotation per minute) to 3,500 rpm, preferably 500 rpm to 1,500 rpm, the acceleration is 500 rpm / sec to 15,000 rpm / sec, and the rotation time is 30 seconds to 300 seconds.
- the resin composition may be spin-coated.
- a drying step may be included after the resin composition is applied to a support, a film, or the like. Drying may be performed using a hot plate, an 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 twice or more. Thereby, a resin film obtained by forming the above-mentioned resin composition into a film can be obtained.
- the chemical discharge rate is 10 ⁇ L / sec to 400 ⁇ L / sec
- the chemical discharge portion height is 0.1 ⁇ m to 1.0 ⁇ m
- the stage speed (or the chemical discharge portion speed) is 1.0 mm / sec to 50.0 mm.
- the resin composition may be slit-coated at the above.
- 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 heating temperature is within the above range, it is possible to suitably produce an insulating film while suppressing damage to the substrate, device, 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 of the heat treatment may be in the atmosphere or in an inert atmosphere such as nitrogen, but a nitrogen atmosphere is preferable from the viewpoint of preventing oxidation of the resin film.
- Examples of the device used for the heat treatment include a quartz tube furnace, a hot plate, a rapid thermal annealing, a vertical diffusion furnace, an infrared curing furnace, an electron beam curing furnace, a microwave curing furnace, and the like.
- the insulating film 202 is provided on one surface 201a of the second substrate main body 201, and then a plurality of terminal electrodes 203 are provided.
- a step of heat-treating the pattern resin film may be used. Thereby, a cured pattern insulating film can be obtained.
- a step of applying a resin composition other than the resin composition of the present disclosure on the substrate for example, a step of applying a resin composition other than the resin composition of the present disclosure on the substrate.
- the process of forming a resin film by drying, and the resin composition of the present disclosure, which is a negative-type photosensitive resin composition or a positive-type photosensitive resin composition, is applied onto the resin film, and after drying, pattern exposure is performed and a developing solution is applied.
- a method including a step of developing to obtain a pattern resin film and a step of heat-treating the pattern resin film may be used. Thereby, a cured pattern insulating film can be obtained.
- the pattern exposure exposes a predetermined pattern through, for example, a photomask.
- the activated light beam to irradiate include i-ray, ultraviolet rays such as wide band, visible light, and radiation, and i-ray is preferable.
- a parallel exposure machine, a projection exposure machine, a stepper, a scanner exposure machine and the like can be used as the exposure apparatus.
- a patterned resin film which is a patterned resin film
- the resin composition of the present disclosure is a negative photosensitive resin composition
- the unexposed portion is removed with a developing solution.
- the organic solvent used as the negative type developer the good solvent of the photosensitive resin film can be used alone, or the good solvent and the poor solvent can be appropriately mixed and used as the developer.
- Good solvents include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, ⁇ -butyrolactone, ⁇ -acetyl- ⁇ -butyrolactone, Examples thereof include 3-methoxy-N, N-dimethylpropanamide, cyclopentanone, cyclohexanone and cycloheptanone.
- 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 developing solution.
- the solution used as the positive developer include tetramethylammonium hydroxide (TMAH) solution and sodium carbonate solution.
- At least one of the negative type developer and the positive type developer may contain a surfactant.
- the content of the surfactant is preferably 0.01 part by mass to 10 parts by mass, and more preferably 0.1 part by mass to 5 parts by mass with respect to 100 parts by mass of the developing solution.
- the development time can be, for example, twice the time required for the photosensitive resin film to be immersed in a developing solution and the resin film to be completely dissolved.
- the developing time may be adjusted according to the component (A) contained in the resin composition of the present disclosure, for example, preferably 10 seconds to 15 minutes, more preferably 10 seconds to 5 minutes, from the viewpoint of productivity. , 20 seconds to 5 minutes is more preferable.
- the pattern resin film after development may be washed with a rinsing solution.
- a rinsing solution distilled water, methanol, ethanol, isopropanol, toluene, xylene, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and the like may be used alone or appropriately mixed, or these may be used in a stepwise combination. May be.
- a photosensitive resin As an organic material constituting the insulating films 102 and 202 other than the cured product obtained by curing the resin composition of the present disclosure, a photosensitive resin, a thermosetting non-conductive film (NCF: NonConductive Film), or , Thermosetting resin may be used. This organic material may be an underfill material. Further, the organic material constituting the insulating films 102 and 202 may be a heat-resistant resin.
- the step (c) is a step of polishing the first semiconductor substrate 100.
- the CMP is such that each surface 103a of the terminal electrode 103 is at an equivalent position or a slightly higher (protruding) position with respect to the surface 102a of the insulating film 102.
- the one side 101a which is the surface of the first semiconductor substrate 100, is polished by the method.
- the first semiconductor substrate 100 can be polished by the CMP method under the condition that the terminal electrode 103 made of copper or the like is selectively deeply ground.
- each surface 103a of the terminal electrode 103 may be polished by the CMP method so as to coincide with the surface 102a of the insulating film 102.
- the polishing method is not limited to the CMP method, and a back grind or the like may be adopted.
- the height difference between each surface 103a and the surface 102a may be 1 nm to 150 nm and 1 nm to 15 nm. It may be.
- the step (d) is a step of polishing the second semiconductor substrate 200.
- each surface 203a of the terminal electrode 203 is at the same position or slightly higher (protruding) position with respect to the surface 202a of the insulating film 202.
- the one side 201a which is the surface of the second semiconductor substrate 200, is polished using the CMP method.
- the second semiconductor substrate 200 is polished by the CMP method under the condition that the terminal electrode 203 made of copper or the like is selectively deeply ground.
- each surface 203a of the terminal electrode 203 may be polished by the CMP method so as to coincide with the surface 202a of the insulating film 202.
- the polishing method is not limited to the CMP method, and a back grind or the like may be adopted.
- the height difference between each surface 203a and the surface 202a may be 1 nm to 50 nm and 1 nm to 15 nm. It may be.
- the insulating film 102 may be polished so that the thickness of the insulating film 102 and the thickness of the insulating film 202 are the same.
- the thickness of the insulating film 202 is the thickness of the insulating film 102. It may be polished to be larger than the halfbeak.
- the thickness of the insulating film 202 may be polished to be smaller than the thickness of the insulating film 102.
- the insulating film 202 contains most of the foreign matter adhering to the bonding interface when the second semiconductor substrate 200 is fragmented or when the chip is mounted. It is possible to further reduce joint defects.
- the thickness of the insulating film 202 is smaller than the thickness of the insulating film 102, the height of the mounted semiconductor chip 205, that is, the semiconductor device 1 can be reduced.
- the step (e) is a step of disassembling the second semiconductor substrate 200 and acquiring a plurality of semiconductor chips 205.
- the second semiconductor substrate 200 is separated 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 individualized.
- the insulating film 202 of the second semiconductor substrate 200 is divided into the insulating film portion 202b corresponding to each semiconductor chip 205.
- Examples of the dicing method for individualizing the second semiconductor substrate 200 include plasma dicing, stealth dicing, laser dicing and the like.
- a thin film such as an organic film that can be removed by water, TMAH or the like, or a carbon film that can be removed by plasma or the like may be provided.
- the 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.
- the terminal electrodes 203 of the semiconductor chips 205 face each of the corresponding terminal electrodes 103 of the first semiconductor substrate 100.
- Perform alignment For this alignment, an alliance mark or the like may be provided on the first semiconductor substrate 100.
- the step (g) is a step of bonding the insulating film 102 of the first semiconductor substrate 100 and the insulating film portions 202b of the plurality of semiconductor chips 205 to each other.
- the semiconductor chip 205 is aligned with the first semiconductor substrate 100 as shown in FIG. 2 (c).
- the insulating film portion 202b of each of the plurality of semiconductor chips 205 is bonded to the insulating film 102 of the first semiconductor substrate 100 (see (b) in FIG. 3).
- the insulating film portion of the plurality of semiconductor chips 205 and the insulating film 102 of the first semiconductor substrate 100 may be uniformly heated before joining.
- the insulating film 102 and the insulating film portion 202b are separated from 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 the coefficient of thermal expansion of the terminal electrodes 103 and 203.
- 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 may be polished.
- the second semiconductor substrate 200 may be polished in the step (d) so that the height is 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 at the time of joining is preferably, for example, 10 ° C. or less.
- 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 strong against the first semiconductor substrate 100. Can be attached to.
- the heat bonding is performed at a highly uniform temperature, it is difficult for positional deviation or the like to occur at the bonding location, and high-precision bonding can be performed.
- the terminal electrode 103 of the first semiconductor substrate 100 and the terminal electrode 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 another bonding method, for example, room temperature bonding or the like.
- the thickness of the organic insulating film which is the insulating bonding portion to which 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, to suppress the influence of foreign substances and to design the device. From the viewpoint of the above, it may be 1 ⁇ m to 20 ⁇ m, preferably 1 ⁇ m to 5 ⁇ m.
- the step (h) is a step of joining the terminal electrode 103 of the first semiconductor substrate 100 and the terminal electrode 203 of each of the plurality of semiconductor chips 205.
- the step (h) as shown in (d) of FIG. 2, when the bonding of the step (g) is completed, heat H, pressure, or both are applied to 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 joined (see (c) in FIG. 3).
- the annealing temperature in the step (g) is preferably 150 ° C. or higher and 400 ° C. or lower, and more preferably 200 ° C.
- the electrode bonding in the step (h) may be performed after the bonding in the step (g), or may be performed at the same time as the bonding in the step (g).
- a plurality of semiconductor chips 205 are electrically and mechanically installed at predetermined positions on the first semiconductor substrate 100 with high accuracy.
- 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 the subsequent steps. Subsequently, a manufacturing method of an example of a semiconductor device using such a semi-finished product will be described with reference to FIG.
- the step (i) is a step of forming a plurality of pillars 300 between the plurality of semiconductor chips 205 on the connection surface 100a of the first semiconductor substrate 100.
- a large number of pillars 300 made of copper, for example, are formed between the plurality of semiconductor chips 205.
- the pillar 300 can be formed from copper plating, a conductor paste, a copper pin, or the like.
- the pillar 300 is formed so that one end is connected to a terminal electrode of the 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, for example, 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. It should be noted that, for example, one or more and 10,000 or less pillars 300 may be provided between the pair of semiconductor chips 205.
- the step (j) is a step of molding the 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.
- an epoxy resin or the like is molded to cover the plurality of semiconductor chips 205 and the plurality of pillars 300 as a whole.
- the molding method include a compression mold, a transfer mold, a method of laminating a film-shaped epoxy film, and the like.
- the semi-finished product M1 filled with the resin is formed.
- the curing treatment may be performed after molding the epoxy resin or the like.
- the step (i) and the step (j) are performed substantially at the same time, that is, when the pillar 300 is also formed at the timing of resin molding, the pillar is formed by using imprint which is a fine transfer and conductive paste or electrolytic plating. It may be formed.
- Step (k) In the step (k), the semi-finished product M1 composed of the resin 301 molded in the step (j), the plurality of pillars 300, and the plurality of semiconductor chips 205 is ground from the resin 301 side to be thinned, and the semi-finished product M2 is obtained. It is a process.
- the resin-molded first semiconductor substrate 100 or the like is thinned by polishing the upper part of the semi-finished product M1 with a grander or the like to obtain the semi-finished product M2. ..
- 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 are formed.
- the shape of 301 corresponds to the pillar portion 30.
- the step (l) is a step of forming the wiring layer 400 corresponding to the rewiring layer 40 on the semi-finished product M2 thinned in the step (k).
- a rewiring pattern is formed on the second semiconductor chip 20 and the pillar portion 30 of the ground semi-finished product M2 with polyimide, copper wiring or the like.
- a semi-finished product M3 having a wiring structure in which the terminal pitches of the second semiconductor chip 20 and the pillar portion 30 are widened is formed.
- the step (m) is a step of cutting the semi-finished product M3 on which the wiring layer 400 is formed in the step (l) along the cutting line A so as to become each semiconductor device 1.
- the semiconductor device substrate is cut along the cutting line A so as to become each semiconductor device 1 by dicing or the like.
- the semiconductor device 1a individualized in the step (m) is inverted and installed on the substrate 50 and the circuit board 60, and a plurality of the semiconductor devices 1 shown in FIG. 1 are acquired.
- the insulating film 102 of the first semiconductor substrate 100 and the insulating film 202 of the second semiconductor substrate 200 cure the resin composition of the present disclosure. It is a cured product. Since the cured product obtained by curing the resin composition of the present disclosure has a lower elastic coefficient than an inorganic material such as silicon dioxide, a second semiconductor substrate can be obtained by using the resin composition for producing an insulating film for hybrid bonding. Even if foreign matter generated by dicing when the 200 is separated into the semiconductor chip 205 adheres to the insulating film, the insulating film around the foreign matter is easily deformed and the foreign matter is insulated without forming a large void in the insulating film.
- the insulating film makes it possible to suppress the influence of foreign matter. Therefore, according to the manufacturing method according to the present embodiment, it is possible to reduce bonding defects while performing fine bonding between the first semiconductor substrate 100 and the semiconductor chip 205.
- the resin composition of the present disclosure contains a material having a low elastic modulus or has a resin composition having high toughness, damage to the semiconductor device 1 manufactured by the above manufacturing method can be more reliably suppressed. Can be done.
- the present invention is not limited to the above embodiment.
- the step (i) of forming the pillar 300 in the step 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 and the like are performed.
- the step (j) of molding the resin 301 on the connection surface of the first semiconductor substrate 100 is first performed, and then the step (k) of grinding the resin 301 to a predetermined thickness to make it thinner.
- the step (i) for forming the pillar 300 may be performed. In this case, the work of scraping the pillar 300 and the like can be reduced, and the material cost can be reduced because the scraped portion of the pillar 300 becomes unnecessary.
- the semiconductor wafer 410 (first electrode) having the substrate main body 411 (first substrate main body), the insulating film 412 (first insulating film) provided on one surface of the substrate main body 411, and a plurality of terminal electrodes 413 (first electrode).
- (1 semiconductor substrate) is prepared, and the substrate main body 421 (second substrate main body), the insulating film portion 422 (second insulating film) provided on one surface of the substrate main body 421, and a plurality of terminal electrodes 423 (second electrode) are prepared.
- a semiconductor substrate (second semiconductor substrate) before fragmentation of a plurality of semiconductor chips 420 having the above is prepared. Then, one side of the semiconductor wafer 410 and one side of the second semiconductor substrate before being fragmented into the semiconductor chip 420 are polished by the CMP method or the like in the same manner as in the above steps (c) and (d). .. After that, the same fragmentation process as in step (e) is performed on the second semiconductor substrate to acquire a plurality of semiconductor chips 420.
- the terminal electrode 423 of the semiconductor chip 420 is aligned with the terminal electrode 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 to each other (step (g)), and the terminal electrode 413 of the semiconductor wafer 410 and the terminal electrode 423 of the semiconductor chip 420 are bonded to each other. (Step (h)), the semi-finished product shown in FIG. 5 (b) is acquired.
- the insulating film 412 and the insulating film portion 422 are joined to form the insulating bonding portion S3, and the semiconductor chip 420 is mechanically firmly and highly accurately attached to the semiconductor wafer 410.
- the terminal electrode 413 and the corresponding terminal electrode 423 are bonded to each other to form an electrode bonding portion S4, and the terminal electrode 413 and the terminal electrode 423 are mechanically and electrically firmly bonded to each other.
- the semiconductor device 401 is acquired by joining the plurality of semiconductor chips 420 to the semiconductor wafer 410, which is a semiconductor wafer, in the same manner.
- the plurality of semiconductor chips 420 may be bonded to the semiconductor wafer 410 one by one by hybrid bonding, but may be collectively bonded to the semiconductor wafer 410 by hybrid bonding.
- the insulating film 412 of the semiconductor wafer 410 and the insulating film portion 422 of the semiconductor chip 420 has the resin composition of the present disclosure, as in the method of manufacturing the semiconductor device 1 described above. It is an insulating film that is a cured product obtained by curing an object. Therefore, even if foreign matter generated by dicing during dicing into the semiconductor chip 420 adheres to the insulating film, the insulating film around the foreign matter is easily deformed, and the foreign matter is removed without forming a large void in the insulating film. It can be included in the insulating film. That is, the insulating film makes it possible to suppress the influence of foreign matter. Therefore, even in the above-mentioned manufacturing method according to C2W, it is possible to reduce bonding defects while finely bonding the semiconductor wafer 410 and the semiconductor chip 420, as in the case of C2C.
- an inorganic material may be contained in a part of the insulating film 102 of the semiconductor substrate 110, the insulating film 202 of the semiconductor chip 205, and the like within the range in which the effect of the present invention is exhibited.
- the weight average molecular weight of A1 was determined by standard polystyrene conversion using a gel permeation chromatography (GPC) method.
- THF tetrahydrofuran
- DMF dimethylformamide
- the esterification rate of A2 was calculated by performing NMR measurement under the above-mentioned conditions.
- the esterification rate was 70 mol% and the proportion of unreacted carboxy groups was 30 mol%.
- the esterification rate of A3 was calculated by performing NMR measurement under the above-mentioned conditions.
- the esterification rate was 72 mol% and the proportion of unreacted carboxy groups was 28 mol%.
- the esterification rate of A4 was calculated by performing NMR measurement under the above-mentioned conditions.
- the esterification rate was 70 mol% and the proportion of unreacted carboxy groups was 30 mol%.
- the obtained reaction solution was added to 3 liters of ethyl alcohol to form a precipitate composed of a crude polymer.
- the produced crude polymer was filtered off and dissolved in 1 liter of tetrahydrofuran to obtain a crude polymer solution.
- the obtained crude polymer solution was added dropwise to water to precipitate the polymer, and the obtained precipitate was filtered off and then vacuum dried to obtain a polyimide precursor A6 which is a powdery polymer.
- the weight average molecular weight of A6 was 24,000.
- the esterification rate of A6 was calculated by performing NMR measurement under the above-mentioned conditions.
- the esterification rate was 100 mol%.
- Synthesis Example 7 (Synthesis of A7)
- the polyimide precursor was synthesized by the same method except that ODPA 155 g was changed to 147 g of 3,3'-4.4'-biphenyltetracarboxylic dianhydride, and the polyimide precursor A7 was obtained. Obtained. The weight average molecular weight of A7 was 28,000.
- the esterification rate of A7 was calculated by performing NMR measurement under the above-mentioned conditions.
- the esterification rate was approximately 100 mol%.
- Example 1 to 8, Comparative Example 1 (Preparation of resin composition)
- the resin compositions of Examples 1 to 8 and Comparative Example 1 were prepared as follows with the components and blending amounts shown in Table 1.
- the unit of the blending amount of each component in Table 1 is a mass part. Further, the blanks in Table 1 mean that the corresponding component is not blended.
- a mixture of each component was kneaded overnight in a general solvent-resistant container at room temperature, and then pressure filtration was performed using a 0.2 ⁇ m pore filter. The following evaluation was performed using the obtained resin composition.
- a cured film was formed as follows, and then the storage elastic modulus was measured.
- the photosensitive resin composition was spin-coated on a Si substrate, heated and dried on a hot plate at the temperature (° C.) and time (seconds, s in Table 1) under the drying conditions for film formation in Table 1, and after curing.
- a photosensitive resin film was formed so as to have a thickness of about 10 ⁇ m.
- the obtained photosensitive resin film was exposed to a wide band (BB) using a mask aligner MA-8 (manufactured by Susu Microtech) at the exposure amounts shown in Table 1.
- the exposed resin film was treated with cyclopentanone (corresponding to Dev1 in Table 1) for Examples 1 to 4, 7 and 8 and a 2.38% TMAH aqueous solution (for Dev2 in Table 1) for Comparative Example 1.
- the coater developer ACT8 manufactured by Tokyo Electron Limited was used to develop for the time shown in Table 1 to obtain a strip-shaped pattern resin film having a width of 10 mm.
- the obtained pattern resin film was cured using a vertical diffusion furnace ⁇ -TF at the temperature and time shown in Table 1 under a nitrogen atmosphere to obtain a patterned cured product having a film thickness of 10 ⁇ m.
- the obtained pattern cured product was immersed in a 4.9 mass% hydrofluoric acid aqueous solution, and the 10 mm wide pattern cured product was peeled off from the Si substrate.
- test frequency 1Hz, temperature rise rate 5 ° C / min, measurement mode: tension, under N2 atmosphere, measurement range -50 ° C to 400 ° C, chuck distance 10 mm, sample width The storage elastic modulus and the loss elastic modulus of the pattern cured product peeled off from the Si substrate were measured under the condition of 2.0 mm.
- the loss tangent was obtained from the obtained storage elastic modulus and loss elastic modulus, and the peak of the loss tangent was defined as Tg (glass transition temperature).
- G2 / G1 was determined from the storage elastic modulus at a temperature 100 ° C. lower than Tg (G1 in Table 2) and the storage elastic modulus at a temperature 100 ° C. higher than Tg (G2 in Table 2). The results are shown in Table 2.
- the G2 / G1 in Table 2 is preferably 0.3 or less, more preferably 0.1 or less, and even more preferably 0.05 or less.
- the resin compositions of Examples 1 to 8 and Comparative Example 1 were spin-coated on an 8-inch Si wafer using a coating device spin coater, and a drying step was performed to form a resin film.
- the resin composition was a photosensitive resin composition
- a mask capable of producing a circular resin film having a diameter of 180 mm was placed on the obtained resin film, and light having a wavelength of 365 nm was irradiated with a predetermined exposure amount. Then, it was developed with cyclopentanone or 2.38% TMAH for a predetermined time, and 10 mm of the resin film on the Si wafer was removed from the outer circumference to prepare a patterned resin film.
- the edge portion of the resin film after spin coating is edge-rinsed with cyclopentanone to remove about 10 mm of the outer peripheral portion of the wafer, and a circular resin film having a diameter of about 180 mm.
- the resin film was heated in a nitrogen atmosphere at the temperature shown in Table 3 for a predetermined time using a clean oven to obtain a cured film having a film thickness of 2 ⁇ m to 8 ⁇ m after curing.
- the obtained cured film was polished by a CMP step to obtain a polished cured film having a surface roughness Ra of 0.5 nm to 3 nm in 10 ⁇ m 2 as measured by using an AFM (atomic force microscope). ..
- a part of the washed polished hardened film is separated into 5 mm squares with a blade dicer (DISCO DFD-6362) to form a chip with resin.
- DISCO DFD-6362 blade dicer
- Got The obtained chip with resin was pressure-bonded to the polished cured film with a flip chip bonder at a predetermined pressure and the bonding temperature shown in Table 3 for 15 seconds to prepare a cured film with a chip.
- Each resin composition was evaluated as described below for each of five chips pressure-bonded to the polished cured film.
- SAT Ultrasonic Deep Scratch Inspection: Scanning Acoustic Tomography
- the adhesive strength between the SiO 2 as an insulating layer or the cured film was measured using a share tester. Adhesive strength was evaluated using the following criteria. The results are shown in Table 3. -Evaluation criteria for adhesive strength- A: The average share strength of the five chips is 1 Mpa or more. B: The average share strength of the five chips is 1 Mpa or less. C: Adhesive strength is low and measurement is not possible. If the adhesive strength was 1 MPa or more, the steps after the production of the cured film with chips could be carried out without any problem.
- thermocompression bonding When the copper terminal is hybrid-bonded together with the insulating layer, the bonding is generally performed by applying pressure at a temperature of 200 ° C. to 400 ° C. due to the problem of reliability of the copper terminal.
- the insulating layer is a cured film of the insulating resin, there is a possibility that voids or the like may be generated due to the volatile components generated by the thermal decomposition of the insulating resin during bonding. Therefore, the above-mentioned cured film with a chip was subjected to thermocompression bonding at a higher temperature to evaluate whether voids and the like were generated and whether the adhesive strength was lowered.
- thermocompression bonding A carbon sheet for absorbing steps is placed on the above-mentioned cured film with a tip, and a crimping device (made by EVG) is used to create a pressure area of 8 inch size at 300 ° C for 4 hours under the conditions of a predetermined vacuum degree. A load of 7200 N was applied and crimping was performed. Then, the presence or absence of voids after thermocompression bonding and the adhesive strength between the cured films were evaluated by the same method as described above. The evaluation criteria for the presence or absence of voids and the adhesive strength are as follows. The results are shown in Table 3.
- thermocompression bonding- A Of the five chips, no more than two chips have voids observed. B: Of the five chips, more than two have voids observed. C: One or more chips are peeled off when measuring SAT. -Evaluation criteria for adhesive strength after thermocompression bonding- A +: The fracture mode of at least 3 of the 5 chips is the cohesive fracture of the Si portion. A: The average share strength of the five chips is 5 MPa or more. B: The average share strength of the five chips is less than 5 MPa. C: Adhesive strength is low and measurement is not possible.
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Abstract
Description
さらに、本開示は、前述の樹脂組成物の調製に用いるポリイミド前駆体を合成可能であるポリイミド前駆体の合成方法を提供することを目的とする。
<1> (A)ポリアミド酸、ポリアミド酸エステル、ポリアミド酸塩及びポリアミド酸アミドからなる群より選択される少なくとも1種の樹脂であるポリイミド前駆体、並びにポリイミド樹脂の少なくとも一方と、(B)溶剤と、を含み、
以下の工程(1)~工程(5)を含む半導体装置の製造方法での第1有機絶縁膜及び第2有機絶縁膜の少なくとも一方の有機絶縁膜の作製に用いるための樹脂組成物。
工程(1) 第1基板本体と、前記第1基板本体の一面に設けられた前記第1有機絶縁膜及び第1電極とを有する第1半導体基板を準備する。
工程(2) 第2基板本体と、前記第2基板本体の一面に設けられた前記第2有機絶縁膜及び複数の第2電極とを有する第2半導体基板を準備する。
工程(3) 前記第2半導体基板を個片化し、前記第2有機絶縁膜の一部に対応する有機絶縁膜部分と少なくとも1つの前記第2電極とをそれぞれが備えた複数の半導体チップを取得する。
工程(4) 前記第1半導体基板の前記第1有機絶縁膜と前記半導体チップの前記有機絶縁膜部分とを互いに貼り合わせる。
工程(5) 前記第1半導体基板の前記第1電極と前記半導体チップの前記第2電極とを接合する。
<2> (A)ポリアミド酸、ポリアミド酸エステル、ポリアミド酸塩及びポリアミド酸アミドからなる群より選択される少なくとも1種の樹脂であるポリイミド前駆体、並びにポリイミド樹脂の少なくとも一方と、(B)溶剤と、を含み、
電極と共に化学機械研磨法により研磨される硬化物の作製に用いるための樹脂組成物。
<3> 前記(A)ポリイミド前駆体は、下記一般式(1)で表される構造単位を有する化合物を含む<1>又は<2>に記載の樹脂組成物。
<4> 前記一般式(1)中、前記Xで表される4価の有機基は、下記式(E)で表される基である<3>に記載の樹脂組成物。
<5> 前記一般式(1)中、前記Yで表される2価の有機基は、下記式(H)で表される基である<3>又は<4>に記載の樹脂組成物。
<6> 前記一般式(1)中、前記R6及び前記R7における前記1価の有機基は、下記一般式(2)で表される基、エチル基、イソブチル基又はt-ブチル基のいずれかである<3>~<5>のいずれか1つに記載の樹脂組成物。
<7> 前記(B)溶剤の含有量は、前記(A)ポリイミド前駆体及びポリイミド樹脂の合計100質量部に対して1質量部~10000質量部である<1>~<6>のいずれか1つに記載の樹脂組成物。
<8> 前記(B)溶剤は下記式(3)~式(6)で表される化合物からなる群より選択される少なくとも一種を含む<1>~<7>のいずれか1つに記載の樹脂組成物。
<9> 前記樹脂組成物を硬化してなる硬化物の5%熱重量減少温度が200℃以上である<1>~<8>のいずれか1つに記載の樹脂組成物。
<10> 前記樹脂組成物を硬化してなる硬化物のガラス転移温度が100℃~400℃である<1>~<9>のいずれか1つに記載の樹脂組成物。
<11> 前記樹脂組成物を硬化してなる硬化物について、動的粘弾性測定で求めた前記硬化物のガラス転移温度(Tg)よりも100℃低い温度での貯蔵弾性率G1に対する前記動的粘弾性測定で求めた前記硬化物のガラス転移温度(Tg)よりも100℃高い温度での貯蔵弾性率G2の比率であるG2/G1は、0.001~0.02である<1>~<10>のいずれか1つに記載の樹脂組成物。
<12> (C)光重合開始剤及び(D)重合性モノマーをさらに含む<1>~<11>のいずれか1つに記載の樹脂組成物。
<13> ネガ型感光性樹脂組成物又はポジ型感光性樹脂組成物であり、フォトリソグラフィ工法により、基板本体の一面上に設けられた有機絶縁膜に複数の端子電極を配置するための貫通孔を複数設けることに用いるための<1>~<12>のいずれか1つに記載の樹脂組成物。
<14> 硬化してなる硬化物の25℃での引張弾性率が7.0GPa以下である<1>~<13>のいずれか1つに記載の樹脂組成物。
<15> 硬化してなる硬化物の熱膨張率が150ppm/K以下である<1>~<14>のいずれか1つに記載の樹脂組成物。
<16> <1>~<15>のいずれか1つに記載の樹脂組成物を第1有機絶縁膜及び第2有機絶縁膜の少なくとも一方の有機絶縁膜の作製に用い、以下の工程(1)~工程(5)を経て半導体装置を製造する半導体装置の製造方法。
工程(1) 第1基板本体と、前記第1基板本体の一面に設けられ前記第1有機絶縁膜及び第1電極とを有する第1半導体基板を準備する。
工程(2) 第2基板本体と、前記第2基板本体の一面に設けられた前記第2有機絶縁膜及び複数の第2電極とを有する第2半導体基板を準備する。
工程(3) 前記第2半導体基板を個片化し、前記第2有機絶縁膜の一部に対応する有機絶縁膜部分と少なくとも1つの前記第2電極とをそれぞれが備えた複数の半導体チップを取得する。
工程(4) 前記第1半導体基板の前記第1有機絶縁膜と前記半導体チップの前記有機絶縁膜部分とを互いに貼り合わせる。
工程(5) 前記第1半導体基板の前記第1電極と前記半導体チップの前記第2電極とを接合する。
<17> 前記工程(4)において、前記半導体チップと前記第1半導体基板との温度差が10℃以内となる温度で前記第1有機絶縁膜と前記有機絶縁膜部分とを貼り合わせる<16>に記載の半導体装置の製造方法。
<18> 製造された半導体装置において、前記第1有機絶縁膜と前記有機絶縁膜部分との接合により形成された有機絶縁膜の厚さが0.1μm以上である<16>又は<17>に記載の半導体装置の製造方法。
<19> 前記工程(1)が前記第1半導体基板の前記一面側を研磨する工程を含むこと、及び、前記工程(2)が前記第2半導体基板の前記一面側を研磨する工程を含むことの少なくとも一方を満たし、前記第1有機絶縁膜の研磨レートは、前記第1電極の研磨レートの0.1倍~5倍であること、及び、前記第2有機絶縁膜の研磨レートは、前記第2電極の研磨レートの0.1倍~5倍であることの少なくとも一方を満たす<16>~<18>のいずれか1つに記載の半導体装置の製造方法。
<20> 前記第2絶縁膜の厚さは、前記第1絶縁膜の厚さよりも大きい<16>~<19>のいずれか1つに記載の半導体装置の製造方法。
<21> 前記第2絶縁膜の厚さは、前記第1絶縁膜の厚さよりも小さい<16>~<19>のいずれか1つに記載の半導体装置の製造方法。
<22> <1>~<15>のいずれか1つに記載の樹脂組成物を硬化してなる硬化物。
<23> 第1基板本体と、前記第1基板本体の一面に設けられた前記第1有機絶縁膜及び第1電極とを有する第1半導体基板と、
半導体チップ基板本体と、前記半導体チップ基板本体の一面に設けられた有機絶縁膜部分及び第2電極とを有する半導体チップと、
を備え、前記第1半導体基板の前記第1有機絶縁膜と、前記半導体チップの前記有機絶縁膜部分と、が接合し、前記第1半導体基板の前記第1電極と、前記半導体チップの前記第2電極と、が接合し、
前記第1有機絶縁膜及び前記有機絶縁膜部分の少なくとも一方が<1>~<15>のいずれか1つに記載の樹脂組成物を硬化してなる有機絶縁膜である半導体装置。
<24> テトラカルボン酸二無水物と、H2N-Y-NH2で表されるジアミン化合物(式中、Yは2価の有機基である。)と、を3-メトキシ-N,N-ジメチルプロパンアミド中にて反応させポリアミド酸溶液を得る工程と、
前記ポリアミド酸溶液に脱水縮合剤及びR-OHで表される化合物(式中、Rは1価の有機基である。)を作用させる工程と、
を含む、ポリイミド前駆体の合成方法。
<25> 前記脱水縮合剤は、トリフルオロ酢酸無水物、N,N’-ジシクロヘキシルカルボジイミド(DCC)及び1,3-ジイソプロピルカルボジイミド(DIC)からなる群より選択される少なくとも1種を含む、<24>に記載のポリイミド前駆体の合成方法。
さらに、本開示は、前述の樹脂組成物の調製に用いるポリイミド前駆体を合成可能であるポリイミド前駆体の合成方法を提供することができる。
本開示において「工程」との語には、他の工程から独立した工程に加え、他の工程と明確に区別できない場合であってもその工程の目的が達成されれば、当該工程も含まれる。
本開示において「~」を用いて示された数値範囲には、「~」の前後に記載される数値がそれぞれ最小値及び最大値として含まれる。
本開示中に段階的に記載されている数値範囲において、一つの数値範囲で記載された上限値又は下限値は、他の段階的な記載の数値範囲の上限値又は下限値に置き換えてもよい。また、本開示中に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてもよい。
本開示において、各成分には、該当する物質が複数種含まれていてもよい。組成物中に各成分に該当する物質が複数種存在する場合、各成分の含有率又は含有量は、特に断らない限り、組成物中に存在する当該複数種の物質の合計の含有率又は含有量を意味する。
本開示において「層」又は「膜」との語には、当該層又は膜が存在する領域を観察したときに、当該領域の全体に形成されている場合に加え、当該領域の一部にのみ形成されている場合も含まれる。
本開示において、層又は膜の厚さは、対象となる層又は膜の5点の厚さを測定し、その算術平均値として与えられる値とする。
層又は膜の厚さは、マイクロメーター等を用いて測定することができる。本開示において、層又は膜の厚さを直接測定可能な場合には、マイクロメーターを用いて測定する。一方、1つの層の厚さ又は複数の層の総厚さを測定する場合には、電子顕微鏡を用いて、測定対象の断面を観察することで測定してもよい。
本開示において「(メタ)アクリル基」とは、「アクリル基」及び「メタクリル基」を意味する。
本開示において官能基が置換基を有する場合、官能基中の炭素数は、置換基の炭素数も含んだ全体の炭素数を意味する。
本開示において実施形態を図面を参照して説明する場合、当該実施形態の構成は図面に示された構成に限定されない。また、各図における部材の大きさは概念的なものであり、部材間の大きさの相対的な関係はこれに限定されない。
本開示の樹脂組成物は、(A)ポリアミド酸、ポリアミド酸エステル、ポリアミド酸塩及びポリアミド酸アミドからなる群より選択される少なくとも1種の樹脂であるポリイミド前駆体、並びにポリイミド樹脂の少なくとも一方と、(B)溶剤と、を含み、以下の工程(1)~工程(5)を含む半導体装置の製造方法での第1有機絶縁膜及び第2有機絶縁膜の少なくとも一方の絶縁膜の作製に用いるための樹脂組成物である。
工程(1) 第1基板本体と、前記第1基板本体の一面に設けられた前記第1有機絶縁膜及び第1電極とを有する第1半導体基板を準備する。
工程(2) 第2基板本体と、前記第2基板本体の一面に設けられた前記第2有機絶縁膜及び複数の第2電極とを有する第2半導体基板を準備する。
工程(3) 前記第2半導体基板を個片化し、前記第2有機絶縁膜の一部に対応する有機絶縁膜部分と少なくとも1つの前記第2電極とをそれぞれが備えた複数の半導体チップを取得する工程と、
工程(4) 前記第1半導体基板の前記第1有機絶縁膜と前記半導体チップの前記有機絶縁膜部分とを互いに貼り合わせる。
工程(5) 前記第1半導体基板の前記第1電極と前記半導体チップの前記第2電極とを接合する。
前述の各工程(1)~工程(5)については、後述の半導体装置の製造方法の項目にて具体例を説明する。
変形例の樹脂組成物では、銅等の金属からなる電極と、当該樹脂組成物を硬化して得られた硬化物である絶縁膜とをCMP法により研磨する際、電極の厚さ及び絶縁膜の厚さを好適に調整しやすい。例えば、絶縁膜の表面が電極の表面に対して少し低い位置に調整しやすく、好ましくは、絶縁膜の表面と電極の表面との高さの差を、1nm~300nmに調整しやすい。そのため、変形例の樹脂組成物は優れたCMP適応性を有する。
本開示において、貯蔵弾性率の測定方法は、ガラス転移温度の測定方法の説明にて記載した方法で測定することができる。
本開示において、引張弾性率は、JIS K 7161(1994)に基づいて25℃にて測定される値である。
本開示の樹脂組成物は(A)ポリアミド酸、ポリアミド酸エステル、ポリアミド酸塩及びポリアミド酸アミドからなる群より選択される少なくとも1種の樹脂であるポリイミド前駆体、並びにポリイミド樹脂の少なくとも一方(以下、「(A)成分」とも称する。)を含む。(A)成分は、高い特性(例えば、耐熱性)を示す硬化物が製造可能となるポリイミド前駆体及びポリイミド樹脂の少なくとも一方であることが好ましく、ポリイミド前駆体として重合性の不飽和結合を有するポリイミド前駆体を含むことがより好ましい。樹脂組成物に含まれる(A)成分は、研磨工程、ボンディング工程等において不具合を起こさない成分であることが好ましい。
本開示において、ポリイミド前駆体は、ポリアミド酸、ポリアミド酸における少なくとも一部のカルボキシ基の水素原子が1価の有機基に置換された化合物、又はポリアミド酸における少なくとも一部のカルボキシ基がpH7以上の塩基性化合物と塩構造を形成している化合物であるポリアミド酸塩のいずれかに該当する化合物を意味する。
ポリアミド酸における少なくとも一部のカルボキシ基の水素原子が1価の有機基に置換された化合物としては、ポリアミド酸エステル、ポリアミド酸アミド等が挙げられる。
ポリアミド酸エステル、ポリアミド酸アミド等は、重合性の不飽和結合を有することが好ましい。
ポリイミド前駆体は、上記一般式(1)で表される構造単位を複数有していてもよく、複数の構造単位におけるX、Y、R6及びR7はそれぞれ同じであってもよく、異なっていてもよい。
なお、R6及びR7は、それぞれ独立に水素原子、又は1価の有機基であればその組み合わせは特に限定されない。例えば、R6及びR7は、いずれも水素原子であってもよく、一方が水素原子かつ他方が後述する1価の有機基であってもよく、いずれも同じ又は互いに異なる1価の有機基であってもよい。前述のようにポリイミド前駆体が上記一般式(1)で表される構造単位を複数有する場合、各構造単位のR6及びR7の組み合わせはそれぞれ同じであってもよく、異なっていてもよい。
Xで表される4価の有機基は、芳香環を含んでもよい。芳香環としては、芳香族炭化水素基(例えば、芳香環を構成する炭素数は6~20)、芳香族複素環式基(例えば、複素環を構成する原子数は5~20)等が挙げられる。Xで表される4価の有機基は、芳香族炭化水素基であることが好ましい。芳香族炭化水素基としては、ベンゼン環、ナフタレン環、フェナントレン環等が挙げられる。
Xで表される4価の有機基が芳香環を含む場合、各芳香環は、置換基を有していてもよいし、無置換であってもよい。芳香環の置換基としては、アルキル基、フッ素原子、ハロゲン化アルキル基、水酸基、アミノ基等が挙げられる。
Xで表される4価の有機基がベンゼン環を含む場合、Xで表される4価の有機基は1つ~4つのベンゼン環を含むことが好ましく、1つ~3つのベンゼン環を含むことがより好ましく、1つ又は2つのベンゼン環を含むことがさらに好ましい。
Xで表される4価の有機基が2つ以上のベンゼン環を含む場合、各ベンゼン環は、単結合により連結されていてもよいし、アルキレン基、ハロゲン化アルキレン基、カルボニル基、スルホニル基、エーテル結合(-O-)、スルフィド結合(-S-)、シリレン結合(-Si(RA)2-;2つのRAは、それぞれ独立に、水素原子、アルキル基又はフェニル基を表す。)、シロキサン結合(-O-(Si(RB)2-O-)n;2つのRBは、それぞれ独立に、水素原子、アルキル基又はフェニル基を表し、nは1又は2以上の整数を表す。)等の連結基、これら連結基を少なくとも2つ組み合わせた複合連結基などにより結合されていてもよい。また、2つのベンゼン環が単結合及び連結基の少なくとも一方により2箇所で結合されて、2つのベンゼン環の間に連結基を含む5員環又は6員環が形成されていてもよい。
なお、本開示は下記具体例に限定されるものではない。
また、Cは、下記式(C1)で表される構造であってもよい。
式(E)におけるCで表されるアルキレン基の具体例としては、メチレン基、エチレン基、トリメチレン基、テトラメチレン基、ペンタメチレン基、ヘキサメチレン基等の直鎖状アルキレン基;メチルメチレン基、メチルエチレン基、エチルメチレン基、ジメチルメチレン基、1,1-ジメチルエチレン基、1-メチルトリメチレン基、2-メチルトリメチレン基、エチルエチレン基、1-メチルテトラメチレン基、2-メチルテトラメチレン基、1-エチルトリメチレン基、2-エチルトリメチレン基、1,1-ジメチルトリメチレン基、1,2-ジメチルトリメチレン基、2,2-ジメチルトリメチレン基、1-メチルペンタメチレン基、2-メチルペンタメチレン基、3-メチルペンタメチレン基、1-エチルテトラメチレン基、2-エチルテトラメチレン基、1,1-ジメチルテトラメチレン基、1,2-ジメチルテトラメチレン基、2,2-ジメチルテトラメチレン基、1,3-ジメチルテトラメチレン基、2,3-ジメチルテトラメチレン基、1,4-ジメチルテトラメチレン基等の分岐鎖状アルキレン基;などが挙げられる。これらの中でも、メチレン基が好ましい。
式(E)におけるCで表されるハロゲン化アルキレン基の具体例としては、上述の式(E)におけるCで表されるアルキレン基に含まれる少なくとも1つの水素原子がフッ素原子、塩素原子等のハロゲン原子で置換されたアルキレン基が挙げられる。これらの中でも、フルオロメチレン基、ジフルオロメチレン基、ヘキサフルオロジメチルメチレン基等が好ましい。
Yで表される2価の有機基の骨格は、Xで表される4価の有機基の骨格と同様であってもよく、Yで表される2価の有機基の好ましい骨格は、Xで表される4価の有機基の好ましい骨格と同様であってもよい。Yで表される2価の有機基の骨格は、Xで表される4価の有機基にて、2つの結合位置が原子(例えば水素原子)又は官能基(例えばアルキル基)に置換された構造であってもよい。
Yで表される2価の有機基は、2価の脂肪族基であってもよく、2価の芳香族基であってもよい。耐熱性の観点から、Yで表される2価の有機基は、2価の芳香族基であることが好ましい。2価の芳香族基としては、2価の芳香族炭化水素基(例えば、芳香環を構成する炭素数は6~20)、2価の芳香族複素環式基(例えば、複素環を構成する原子数は5~20)等が挙げられ、2価の芳香族炭化水素基が好ましい。
式(H)において、Dは、単結合、アルキレン基、ハロゲン化アルキレン基、カルボニル基、スルホニル基、エーテル結合(-O-)、スルフィド結合(-S-)、フェニレン基、エステル結合(-O-C(=O)-)、シリレン結合(-Si(RA)2-;2つのRAは、それぞれ独立に、水素原子、アルキル基又はフェニル基を表す。)、シロキサン結合(-O-(Si(RB)2-O-)n;2つのRBは、それぞれ独立に、水素原子、アルキル基又はフェニル基を表し、nは1又は2以上の整数を表す。)又はこれらを少なくとも2つ組み合わせた2価の基を表す。また、Dは、上記式(C1)で表される構造であってもよい。式(H)におけるDの具体例は、式(E)におけるCの具体例と同様である。
式(H)におけるDとしては、エーテル結合、エーテル結合とフェニレン基とを含む基、エーテル結合とフェニレン基とアルキレン基とを含む基等であることが好ましい。
式(G)~式(I)におけるRで表されるアルキル基の具体例としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、s-ブチル基、t-ブチル基等が挙げられる。
式(G)~式(I)におけるRで表されるアルコキシ基の具体例としては、メトキシ基、エトキシ基、n-プロポキシ基、イソプロポキシ基、n-ブトキシ基、イソブトキシ基、s-ブトキシ基、t-ブトキシ基等が挙げられる。
式(G)~式(I)におけるRで表されるハロゲン化アルキル基の具体例としては、式(G)~式(I)におけるRで表されるアルキル基に含まれる少なくとも1つの水素原子がフッ素原子、塩素原子等のハロゲン原子で置換されたアルキル基が挙げられる。これらの中でも、フルオロメチル基、ジフルオロメチル基、トリフルオロメチル基等が好ましい。
Yで表されるアルキレン基の具体例としては、テトラメチレン基、ヘキサメチレン基、ヘプタメチレン基、オクタメチレン基、ノナメチレン基、デカメチレン基、ウンデカメチレン基、ドデカメチレン基、2-メチルペンタメチレン基、2-メチルヘキサメチレン基、2-メチルヘプタメチレン基、2-メチルオクタメチレン基、2-メチルノナメチレン基、2-メチルデカメチレン基等が挙げられる。
Yで表されるシクロアルキレン基の具体例としては、シクロプロピレン基、シクロヘキシレン基等が挙げられる。
ポリシロキサン構造中のケイ素原子と結合する炭素数1~20のアルキル基の具体例としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、t-ブチル基、n-オクチル基、2-エチルヘキシル基、n-ドデシル基等が挙げられる。これらの中でも、メチル基が好ましい。
ポリシロキサン構造中のケイ素原子と結合する炭素数6~18のアリール基は、無置換でも置換基で置換されていてもよい。アリール基が置換基を有する場合の置換基の具体例としては、ハロゲン原子、アルコキシ基、ヒドロキシ基等が挙げられる。炭素数6~18のアリール基の具体例としては、フェニル基、ナフチル基、ベンジル基等が挙げられる。これらの中でも、フェニル基が好ましい。
ポリシロキサン構造中の炭素数1~20のアルキル基又は炭素数6~18のアリール基は、1種類でもよく、2種類以上であってもよい。
Yで表されるポリシロキサン構造を有する2価の基を構成するケイ素原子は、メチレン基、エチレン基等のアルキレン基、フェニレン基等のアリーレン基などを介して一般式(1)中のNH基と結合していてもよい。
炭素数1~4の脂肪族炭化水素基の具体例としては、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、t-ブチル基等が挙げられ、中でも、エチル基、イソブチル基及びt-ブチル基が好ましい。
Rxにおける炭素数は、1つ~10つが好ましく、2つ~5つがより好ましく、2つ又は3つがさらに好ましい。
なお、前述の割合は、0モル%以上60モル%未満であってもよい。
テトラカルボン酸二無水物は、1種を単独で用いても2種以上を併用してもよい。
ジアミン化合物は、1種を単独で用いても2種以上を併用してもよい。
(a) テトラカルボン酸二無水物(好ましくは、下記一般式(8)で表されるテトラカルボン酸二無水物)とR-OHで表される化合物とを、有機溶剤中にて反応させジエステル誘導体とした後、ジエステル誘導体とH2N-Y-NH2で表されるジアミン化合物とを縮合反応させる。
(b) テトラカルボン酸二無水物とH2N-Y-NH2で表されるジアミン化合物とを有機溶剤中にて反応させポリアミド酸溶液を得て、R-OHで表される化合物をポリアミド酸溶液に加え、有機溶剤中で反応させエステル基を導入する。
ここで、H2N-Y-NH2で表されるジアミン化合物におけるYは、一般式(1)におけるYと同様であり、具体例及び好ましい例も同様である。また、R-OHで表される化合物におけるRは、1価の有機基を表し、具体例及び好ましい例は、一般式(1)におけるR6及びR7の場合と同様である。
一般式(8)で表されるテトラカルボン酸二無水物、H2N-Y-NH2で表されるジアミン化合物及びR-OHで表される化合物は、各々、1種単独で用いてもよく、2種以上を組み合わせてもよい。
前述の有機溶媒としては、N-メチル-2-ピロリドン、γ-ブチロラクトン、ジメトキシイミダゾリジノン、3-メトキシ-N,N-ジメチルプロピオンアミド等が挙げられ、中でも、3-メトキシ-N,N-ジメチルプロピオンアミドが好ましい。
R-OHで表される化合物とともに脱水縮合剤をポリアミド酸溶液に作用させてポリイミド前駆体を合成してもよい。脱水縮合剤は、トリフルオロ酢酸無水物、N,N’-ジシクロヘキシルカルボジイミド(DCC)及び1,3-ジイソプロピルカルボジイミド(DIC)からなる群より選択される少なくとも1種を含むことが好ましい。
(A)成分に含まれる前述の化合物は、下記一般式(8)で表されるテトラカルボン酸二無水物にR-OHで表される化合物を作用させてジエステル誘導体とした後、カルボジイミド化合物の存在下でH2N-Y-NH2で表されるジアミン化合物とジエステル誘導体とを反応させることで得ることができる。
(A)成分に含まれる前述の化合物は、下記一般式(8)で表されるテトラカルボン酸二無水物とH2N-Y-NH2で表されるジアミン化合物とを反応させてポリアミド酸とした後、トリフルオロ酢酸無水物等の脱水縮合剤の存在下でポリアミド酸をイソイミド化し、次いでR-OHで表される化合物を作用させて得ることができる。あるいは、テトラカルボン酸二無水物の一部に予めR-OHで表される化合物を作用させて、部分的にエステル化されたテトラカルボン酸二無水物とH2N-Y-NH2で表されるジアミン化合物とを反応させてもよい。
重量平均分子量は、例えば、ゲルパーミエーションクロマトグラフィー法によって測定することができ、標準ポリスチレン検量線を用いて換算することによって求めることができる。
ジカルボン酸は、(メタ)アクリル基を有するジカルボン酸であってもよく、例えば、以下の式で表されるジカルボン酸であってもよい。このとき、(A)ポリイミド前駆体を合成する際に、ジアミン化合物のアミノ基の一部とジカルボン酸のカルボキシ基とを反応させることで、(A)ポリイミド前駆体にジカルボン酸由来のメタクリル基を導入することができる。
本開示の樹脂組成物は(B)溶剤(以下、「(B)成分」とも称する。)を含む。(B)成分は、例えば、樹脂組成物の生殖毒性及び環境負荷を低減させる観点から、下記式(3)~式(7)で表される化合物からなる群より選択される少なくとも一種を含むことが好ましい。
式(4)において、R2の炭素数1~4のアルキル基としては、好ましくはメチル基又はエチル基である。tは好ましくは0、1又は2であり、より好ましくは1である。
式(5)において、R3の炭素数1~4のアルキル基としては、好ましくはメチル基、エチル基、プロピル基又はブチル基である。R4及びR5の炭素数1~4のアルキル基としては、好ましくはメチル基又はエチル基である。
式(6)において、R6~R8の炭素数1~4のアルキル基としては、好ましくはメチル基又はエチル基である。rは好ましくは0又は1であり、より好ましくは0である。
式(7)において、R9及びR10の炭素数1~4のアルキル基としては、好ましくはメチル基又はエチル基である。uは好ましくは0又は1であり、より好ましくは0である。
ケトン類の溶剤として、メチルエチルケトン、シクロヘキサノン、シクロペンタノン、2-ヘプタノン、3-ヘプタノン、N-メチル-2-ピロリドン(NMP)等が挙げられる。
炭化水素類の溶剤としては、リモネン等が挙げられる。
芳香族炭化水素類の溶剤として、トルエン、キシレン、アニソール等が挙げられる。
スルホキシド類の溶剤として、ジメチルスルホキシド等が挙げられる。
また、溶剤(1)の含有率は、溶剤(1)及び溶剤(2)の合計に対して、5質量%~100質量%であってもよく、5質量%~50質量%であってもよい。
溶剤(1)の含有量は、(A)成分100質量部に対して、10質量部~1000質量部であってもよく、10質量部~100質量部であってもよく、10質量部~50質量部であってもよい。
本開示の樹脂組成物は、(C)光重合開始剤を含むことが好ましい。これにより、半導体装置を作製する工程の中で電極を作製する工程数を低減することができ、半導体装置を作製する際のプロセス全体のコストを低減する事ができる。
(C)成分は、1種単独で用いてもよく、2種以上を組み合わせてもよい。
これらの中でも、金属元素を含まず、且つ反応性が高く高感度の観点からオキシム化合物誘導体が好ましい。
本開示の樹脂組成物は、(D)重合性モノマーを含むことが好ましい。(D)成分は、重合性の不飽和二重結合を含む基を少なくとも1つ有することが好ましく、光重合開始剤との併用によって好適に重合可能である観点から、(メタ)アクリル基を少なくとも1つ有することがより好ましい。架橋密度の向上及び光感度の向上の観点から、重合性の不飽和二重結合を含む基を、2つ~6つ有することが好ましく、2つ~4つ有することがより好ましい。
重合性モノマーは、1種単独で用いてもよく、2種以上を組み合わせてもよい。
本開示の樹脂組成物は、硬化物の物性を向上させる観点から、(E)熱重合開始剤を含むことが好ましい。
本開示の樹脂組成物は、良好な保存安定性を確保する観点から、(F)重合禁止剤(以下、「(F)成分」とも称する。)を含んでいてもよい。重合禁止剤としては、ラジカル重合禁止剤、ラジカル重合抑制剤等が挙げられる。
これらの中でもN,N’-ヘキサン-1,6-ジイルビス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオンアミド]が好ましい。
本開示の樹脂組成物は、高温保存、リフロー処理等で発生する酸素ラジカル及び過酸化物ラジカルを捕捉することで、接着性の低下を抑制できる観点から、酸化防止剤を含んでいてもよい。本開示の樹脂組成物が酸化防止剤を含むことで、絶縁信頼性試験時の電極の酸化を抑制することができる。
酸化防止剤は、1種単独で用いてもよく、2種以上を組み合わせてもよい。
本開示の樹脂組成物は、カップリング剤を含んでもよい。カップリング剤は、加熱処理において、(A)成分と反応して架橋する、又はカップリング剤自体が重合する。これにより、得られる硬化物と基板との接着性をより向上させることができる傾向にある。
カップリング剤は、1種単独で用いてもよく、2種以上を組み合わせてもよい。
本開示の樹脂組成物は、界面活性剤及びレベリング剤の少なくとも一方を含んでもよい。樹脂組成物が界面活性剤及びレベリング剤の少なくとも一方を含むことにより、塗布性(例えばストリエーション(膜厚のムラ)の抑制)、接着性の改善、樹脂組成物中の化合物の相溶性等を向上させることができる。
本開示の樹脂組成物は、銅、銅合金等の金属の腐食を抑制する観点、及び、当該金属の変色を抑制する観点から、防錆剤を含んでもよい。防錆剤としては、アゾール化合物、プリン誘導体等が挙げられる。
1価の芳香族炭化水素基としては、フェニル基、ナフチル基等が挙げられる。
本開示の樹脂組成物の、例えば、80質量%以上、90質量%以上、95質量%以上、98質量%以上又は100質量%が、
(A)成分及び(B)成分、
(A)成分~(C)成分、
(A)成分~(E)成分、
(A)成分~(F)成分、
(A)成分~(F)成分並びに酸化防止剤、カップリング剤、界面活性剤、レベリング剤、防錆剤及び含窒素化合物からなる群より選択される少なくともいずれか1つ、
からなっていてもよい。
本開示の半導体装置は、第1基板本体と、前記第1基板本体の一面に設けられた前記第1有機絶縁膜及び第1電極とを有する第1半導体基板と、半導体チップ基板本体と、前記半導体チップ基板本体の一面に設けられた有機絶縁膜部分及び第2電極とを有する半導体チップと、を備え、前記第1半導体基板の前記第1有機絶縁膜と、前記半導体チップの前記有機絶縁膜部分と、が接合し、前記第1半導体基板の前記第1電極と、前記半導体チップの前記第2電極と、が接合し、前記第1有機絶縁膜及び前記有機絶縁膜部分の少なくとも一方が本開示の樹脂組成物を硬化してなる絶縁膜である半導体装置である。
本開示の半導体装置は、第1有機絶縁膜及び有機絶縁膜部分の少なくとも一方が本開示の樹脂組成物を硬化してなる絶縁膜であるため、絶縁膜の接合界面での空隙の発生が抑制され、絶縁膜の耐熱性に優れる。また、本開示の半導体装置は、工程(1)~工程(5)を経て製造される。
本開示の半導体装置の製造方法では、本開示の樹脂組成物を用いて半導体装置を製造する。具体的には、本開示の樹脂組成物を用いて工程(1)~工程(5)を経ることで半導体装置を製造することができる。
本開示の硬化物は、本開示の樹脂組成物を硬化してなる。硬化物は、例えば、半導体装置の絶縁膜に用いられる。
図1は、本開示の半導体装置の一例を模式的に示す断面図である。図1に示すように、半導体装置1は、例えば半導体パッケージの一例であり、第1半導体チップ10(第1半導体基板)、第2半導体チップ20(半導体チップ)、ピラー部30、再配線層40、基板50、及び、回路基板60を備えている。
次に、半導体装置1の製造方法の一例について、図2~図4を参照して、説明する。図2は、図1に示す半導体装置を製造するための方法を順に示す図である。図3は、図2に示す半導体装置の製造方法における接合方法(ハイブリッドボンディング)をより詳細に示す図である。図4は、図1に示す半導体装置を製造するための方法であり、図2に示す工程の後の工程を順に示す図である。
(a)第1半導体チップ10に対応する第1半導体基板100を準備する工程。
(b)第2半導体チップ20に対応する第2半導体基板200を準備する工程。
(c)第1半導体基板100を研磨する工程。
(d)第2半導体基板200を研磨する工程。
(e)第2半導体基板200を個片化し、複数の半導体チップ205を取得する工程。
(f)第1半導体基板100の端子電極103に対して複数の半導体チップ205それぞれの端子電極203の位置合わせを行う工程。
(g)第1半導体基板100の絶縁膜102と複数の半導体チップ205の各絶縁膜部分202bとを互いに貼り合わせる工程(図3の(b)参照)。
(h)第1半導体基板100の端子電極103と複数の半導体チップ205それぞれの端子電極203とを接合する工程(図3の(c)参照)。
(i)第1半導体基板100の接続面上であって複数の半導体チップ205の間に複数のピラー300(ピラー31に対応)を形成する工程。
(j)半導体チップ205とピラー300とを覆うように、第1半導体基板100の接続面上に樹脂301をモールドして半製品M1を取得する工程。
(k)工程(j)でモールドがされた半製品M1の樹脂301側を研削して薄化し、半製品M2を取得する工程。
(l)工程(k)で薄化された半製品M2に再配線層40に対応する配線層400を形成する工程。
(m)工程(l)で配線層400が形成された半製品M3を各半導体装置1となるように切断線Aに沿って切断する工程。
(n)工程(m)で個体化された半導体装置1aを反転して基板50及び回路基板60上に設置する工程(図1参照)。
工程(a)は、複数の第1半導体チップ10に対応し、半導体素子及びそれらを接続する配線等からなる集積回路が形成されたシリコン基板である第1半導体基板100を準備する工程である。工程(a)では、図2の(a)に示すように、シリコン等からなる第1基板本体101の一面101aに、銅、アルミニウム等からなる複数の端子電極103(第1電極)を所定の間隔で設けると共に本開示の樹脂組成物を硬化してなる硬化物である絶縁膜102(第1絶縁膜)を設ける。絶縁膜102を第1基板本体101の一面101a上に設けてから、複数の端子電極103を設けてもよいし、複数の端子電極103を第1基板本体101の一面101aに設けてから絶縁膜102を設けてもよい。なお、複数の端子電極103の間には、後述する工程でピラー300を形成するため、所定の間隔が設けられており、その間にはピラー300に接続される別の端子電極(不図示)が形成されている。
い。一例として、端子電極103又は203が銅からなり、銅の研磨レートが50nm/minの場合、絶縁膜102又は202の研磨レートは、200nm/min以下(銅の研磨レートの4倍以下)であることが好ましく、100nm/min以下(銅の研磨レートの2倍以下)であることがより好ましく、50nm/min以下(銅の研磨レートの同等以下)であることがさらに好ましい。
乾燥は、2回以上行ってもよい。これにより、上述の樹脂組成物を膜状に形成した樹脂膜を得ることができる。
加熱処理の雰囲気は大気中であっても、窒素等の不活性雰囲気中であってもよいが、樹脂膜の酸化を防ぐことができる観点から、窒素雰囲気下が好ましい。
照射する活性光線は、i線、広帯域等の紫外線、可視光線、放射線などが挙げられ、i線であることが好ましい。露光装置としては、平行露光機、投影露光機、ステッパ、スキャナ露光機等を用いることができる。
ネガ型の現像液として用いる有機溶剤は、現像液としては、感光性樹脂膜の良溶媒を単独で、又は良溶媒と貧溶媒とを適宜混合して用いることができる。
良溶媒としては、N-メチル-2-ピロリドン、N-アセチル-2-ピロリドン、N,N-ジメチルアセトアミド、N,N-ジメチルホルムアミド、ジメチルスルホキシド、γ-ブチロラクトン、α-アセチル-γ-ブチロラクトン、3-メトキシ-N、N-ジメチルプロパンアミド、シクロペンタノン、シクロヘキサノン、シクロヘプタノン等が挙げられる。
貧溶媒としては、トルエン、キシレン、メタノール、エタノール、イソプロパノール、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテル、水等が挙げられる。
ポジ型の現像液として用いる溶液としては水酸化テトラメチルアンモニウム(TMAH)溶液、炭酸ナトリウム溶液等が挙げられる。
現像時間は、本開示の樹脂組成物に含まれる(A)成分に応じて調節してもよく、例えば、10秒間~15分間が好ましく、10秒間~5分間がより好ましく、生産性の観点から、20秒間~5分間がさらに好ましい。
リンス液としては、蒸留水、メタノール、エタノール、イソプロパノール、トルエン、キシレン、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテル等を単独又は適宜混合して用いてもよく、またこれらを段階的に組み合わせて用いてもよい。
工程(c)は、第1半導体基板100を研磨する工程である。工程(c)では、図3の(a)に示すように、端子電極103の各表面103aが絶縁膜102の表面102aに対して同等の位置か少し高い(突き出た)位置となるようにCMP法を用いて第1半導体基板100の表面である一面101a側を研磨する。工程(c)では、例えば、銅等からなる端子電極103を選択的に深く削る条件でCMP法によって第1半導体基板100を研磨することもできる。工程(c)において、端子電極103の各表面103aが絶縁膜102の表面102aと一致するようにCMP法で研磨してもよい。研磨方法はCMP法に限定されず、バックグラインド等を採用してもよい。
端子電極103の各表面103aが絶縁膜102の表面102aに対して少し高い位置である場合、各表面103aと表面102aとの高さの差は、1nm~150nmであってもよく、1nm~15nmであってもよい。
端子電極203の各表面203aが絶縁膜202の表面202aに対して少し高い位置である場合、各表面203aと表面202aとの高さの差は、1nm~50nmであってもよく、1nm~15nmであってもよい。
工程(e)は、第2半導体基板200を個片化し、複数の半導体チップ205を取得する工程である。工程(e)では、図2の(b)に示すように、第2半導体基板200をダイシング等の切断手段により複数の半導体チップ205に個片化する。第2半導体基板200をダイシングする際に絶縁膜202に保護材等を被覆して、それから個片化してもよい。工程(e)により、第2半導体基板200の絶縁膜202は、各半導体チップ205に対応する絶縁膜部分202bへと分割される。第2半導体基板200を個片化するダイシング方法としては、プラズマダイシング、ステルスダイシング、レーザーダイシング等が挙げられる。ダイシングの際の第2半導体基板200の表面保護材としては、例えば、水、TMAH等で除去可能な有機膜、又は、プラズマ等で除去可能な炭素膜などの薄膜を設けてもよい。
工程(f)は、第1半導体基板100の端子電極103に対して複数の半導体チップ205それぞれの端子電極203の位置合わせを行う工程である。工程(f)では、図2の(c)に示すように、各半導体チップ205の端子電極203が第1半導体基板100の対応する複数の端子電極103に対向するように、各半導体チップ205の位置合わせを行う。この位置合わせ用に、第1半導体基板100上にアライアメントマーク等を設けてもよい。
工程(g)は、第1半導体基板100の絶縁膜102と複数の半導体チップ205の各絶縁膜部分202bとを互いに貼り合わせる工程である。工程(g)では、各半導体チップ205の表面に付着した有機物、金属酸化物等を除去した後、図2の(c)に示すように、第1半導体基板100に対する半導体チップ205の位置合わせを行い、その後、ハイブリッドボンディングとして複数の半導体チップ205それぞれの絶縁膜部分202bを第1半導体基板100の絶縁膜102に接合する(図3の(b)参照)。この際、複数の半導体チップ205の絶縁膜部分と第1半導体基板100の絶縁膜102とを均一に加熱してから接合を行ってもよい。加熱しながら接合を行うことで絶縁膜102及び絶縁膜部分202bの熱膨張率と端子電極103、203の熱膨張率との差により、絶縁膜102及び絶縁膜部分202bが端子電極103、203よりも膨張する。加熱による熱膨張により、絶縁膜102の高さが端子電極103の高さと同程度以上となるように、工程(c)にて第1半導体基板100を研磨してもよく、絶縁膜部分202bの高さが端子電極203の高さと同程度以上となるように、工程(d)にて第2半導体基板200を研磨してもよい。接合の際の半導体チップ205と第1半導体基板100との温度差は、例えば10℃以下が好ましい。このような均一性の高い温度での加熱接合により、絶縁膜102と絶縁膜部分202bが接合された絶縁接合部分S1となり、複数の半導体チップ205が第1半導体基板100に対して機械的に強固に取り付けられる。また、均一性の高い温度での加熱接合であることから、接合箇所における位置ズレ等が生じ難く、高精度な接合を行うことができる。この取り付けの段階では、第1半導体基板100の端子電極103と半導体チップ205の端子電極203とは互いに離間しており、接続されていない(但し位置合わせはされている)。半導体チップ205の第1半導体基板100への貼り合わせは、他の接合方法によって行ってもよく、例えば常温接合等で接合してもよい。
工程(h)は、第1半導体基板100の端子電極103と複数の半導体チップ205それぞれの端子電極203とを接合する工程である。工程(h)では、図2の(d)に示すように、工程(g)の貼り合わせが終了すると、熱H、圧力又はその両方を付与して、ハイブリッドボンディングとして第1半導体基板100の端子電極103と複数の半導体チップ205の各端子電極203とを接合する(図3の(c)参照)。端子電極103及び203が銅から構成されている場合、工程(g)でのアニーリング温度は、150℃以上400℃以下であることが好ましく、200℃以上300℃以下であることがより好ましい。このような接合処理により、端子電極103とそれに対応する端子電極203とが接合された電極接合部分S2となり、端子電極103と端子電極203とが機械的且つ電気的に強固に接合される。なお、工程(h)の電極接合は、工程(g)の貼り合わせ後に行われてもよく、工程(g)の貼り合わせと同時に行われてもよい。
工程(i)は、第1半導体基板100の接続面100a上であって複数の半導体チップ205の間に複数のピラー300を形成する工程である。工程(i)では、図4の(a)に示すように、複数の半導体チップ205の間に、例えば銅製の多数のピラー300を形成する。ピラー300は、銅めっき、導電体ペースト、銅ピン等から形成することができる。ピラー300は、一端が第1半導体基板100の端子電極のうち半導体チップ205の端子電極203に接続されていない端子電極に接続されるように形成され、他端が上方に向かって延在する。ピラー300は、例えば、直径10μm以上100μm以下であり、また、高さ10μm以上1000μm以下である。なお、一対の半導体チップ205の間には、例えば1個以上10000個以下のピラー300が設けられてもよい。
工程(j)は、複数の半導体チップ205と複数のピラー300とを覆うように、第1半導体基板100の接続面100a上に樹脂301をモールドする工程である。工程(j)では、図4の(b)に示すように、エポキシ樹脂等をモールドして、複数の半導体チップ205と複数のピラー300とを全体的に覆う。モールド方法としては、例えば、コンプレッションモールド、トランスファモールド、フィルム状のエポキシフィルムをラミネートする方法等が挙げられる。この樹脂モールドにより、複数のピラー300の間及びピラー300と半導体チップ205との間が樹脂301によって充填される。
これにより、樹脂が充填された半製品M1が形成される。なお、エポキシ樹脂等をモールドした後に硬化処理を行ってもよい。また、工程(i)と工程(j)とを略同時に行う場合、すなわち樹脂モールドするタイミングでピラー300も形成する場合、微細転写であるインプリントと導電性ペースト若しくは電解めっきとを用いてピラーを形成してもよい。
工程(k)は、工程(j)でモールドがされた樹脂301、複数のピラー300及び複数の半導体チップ205からなる半製品M1を樹脂301側から研削して薄化し、半製品M2を取得する工程である。工程(k)では、図4の(c)に示すように、半製品M1の上方をグランダー等で研磨することにより、樹脂モールドされた第1半導体基板100等を薄化し、半製品M2とする。工程(k)での研磨により、半導体チップ205、ピラー300及び樹脂301の厚さは例えば数10μm程度に薄化され、半導体チップ205は第2半導体チップ20に対応する形状となり、ピラー300及び樹脂301は、ピラー部30に対応する形状となる。
工程(l)は、工程(k)で薄化された半製品M2に再配線層40に対応する配線層400を形成する工程である。工程(l)では、図4の(d)に示すように、研削された半製品M2の第2半導体チップ20及びピラー部30の上にポリイミド、銅配線等で再配線パターンを形成する。これにより、第2半導体チップ20及びピラー部30の端子ピッチを広げた配線構造を有する半製品M3が形成される。
工程(m)は、工程(l)で配線層400が形成された半製品M3を各半導体装置1となるように切断線Aに沿って切断する工程である。工程(m)では、図4の(d)に示すように、ダイシング等によって、各半導体装置1となるように、半導体装置基板を切断線Aに沿って切断する。その後、工程(n)では、工程(m)で個別化された半導体装置1aを反転して基板50及び回路基板60上に設置し、図1に示す半導体装置1を複数取得する。
3,3’,4,4’‐ジフェニルエーテルテトラカルボン酸二無水物(ODPA)7.07gと2,2’-ジメチルビフェニル-4,4’-ジアミン(DMAP)4.12gとをN-メチル-2-ピロリドン(NMP)30gに溶解させた。得られた溶液を30℃で4時間、その後室温下で一晩撹拌し、ポリアミド酸を得た。そこに室温にてトリフルオロ酢酸無水物9.45gを加えたのち、メタクリル酸2-ヒドロキシエチル(HEMA)7.08gを加え、45℃で10時間撹拌した。この反応液を蒸留水に滴下し、沈殿物をろ別して集め、減圧乾燥することによってポリイミド前駆体A1を得た。
ゲルパーミエーションクロマトグラフィー(GPC)法を用いて、標準ポリスチレン換算により、A1の重量平均分子量を求めた。A1の重量平均分子量は20,000であった。具体的には、A1 0.5mgを溶剤[テトラヒドロフラン(THF)/ジメチルホルムアミド(DMF)=1/1(容積比)]1mLに溶解させた溶液を用い、以下の条件で測定した。
(測定条件)
測定装置:株式会社島津製作所SPD-M20A
ポンプ:株式会社島津製作所LC-20AD
カラムオーブン:株式会社島津製作所:CTO-20A
測定条件:カラムGelpack GL-S300MDT-5×2本
溶離液:THF/DMF=1/1(容積比)
LiBr(0.03mol/L)、H3PO4(0.06mol/L)
流速:1.0mL/min、検出器:UV270nm、カラム温度:40℃
標準ポリスチレン:東ソー製 TSKgel standard Polystyrene Type F-1,F-4,F-20,F-80,A-2500にて検量線を作成
以下の条件でNMR測定を行うことで、A1のエステル化率(HEMAと反応してなるエステル基及びHEMAと未反応のカルボキシ基の合計に対するHEMAと反応してなるエステル基の割合)を算出した。エステル化率は80モル%であり、未反応のカルボキシ基の割合は20モル%であった。
(測定条件)
測定機器:ブルカー・バイオスピン社 AV400M
磁場強度:400MHz
基準物質:テトラメチルシラン(TMS)
溶剤:ジメチルスルホキシド(DMSO)
合成例1にてNMPを3-メトキシ-N,N-ジメチルプロパンアミドへ変更した以外は同様の方法でポリイミド前駆体の合成を実施し、ポリイミド前駆体A2を得た。A2の重量平均分子量は22,000であった。
合成例1の2,2’-ジメチルビフェニル-4,4’-ジアミン(DMAP)を、4.4’-ジアミノジフェニルエーテル3.6g及びm-フェニレンジアミン0.2gに変更した以外は同様の操作を行い、ポリイミド前駆体A3を得た。A3の重量平均分子量は25,000であった。
合成例3のNMPを3-メトキシ-N,N-ジメチルプロパンアミドへ変更した以外は同様の方法でポリイミド前駆体の合成を実施し、ポリイミド前駆体A4を得た。A4の重量平均分子量は22000であった。
3,3’,4,4’-ジフェニルエーテルテトラカルボン酸二無水物(ODPA)61.0g、と1,3-ビス(3-アミノフェノキシ)ベンゼン52.0gとを3-メトキシ-N,N-ジメチルプロパンアミド200gに溶解させた。得られた溶液を30℃で2時間、その後室温下で一晩撹拌し、ポリアミド酸を得た。そこに室温にてトリフルオロ酢酸無水物を80g加え所定時間攪拌したのちメタクリル酸2-ヒドロキシエチル(HEMA)7.2gを加え、45℃で10時間撹拌した。この反応液を蒸留水に滴下し、沈殿物をろ別して集め、減圧乾燥することによってポリイミド前駆体A5を得た。A5の重量平均分子量は25,000であった。
反応容器中において、ODPA155gとHEMA131.2gとをγ-ブチロラクトン400mLへ溶解し室温下で撹拌し、撹拌しながらピリジン81gを加えて反応混合物を得た。反応による発熱の終了後に反応混合物を室温まで放冷し、15時間放置した。
-ブチロラクトン180mLに溶解させた溶液を撹拌しながら40分かけて反応混合物に加えた。次いで、4,4’-ジアミノジフェニルエーテル93gをγ-ブチロラクトン350mLに懸濁させた懸濁液を撹拌しながら60分かけて反応混合物に加えた。さらに室温で反応混合物を2時間撹拌した後、エチルアルコール30mLを加えて1時間撹拌し、次に、γ-ブチロラクトン400mLを反応混合物に加えた。反応混合物に生じた沈殿物をろ過により取り除き、反応液を得た。
合成例6にて、ODPA155gを3,3’-4.4’-ビフェニルテトラカルボン酸二無水物147gに変更した以外は、同様の方法でポリイミド前駆体の合成を実施し、ポリイミド前駆体A7を得た。A7の重量平均分子量は28,000であった。
A8:クレゾール-ホルムアルデヒド樹脂(旭有機材株式会社製)、重量平均分子量12000
A9:アクリル酸重合物(ブチルアクリレート/アクリル酸/4-ヒドロキシブチルアクリレート)
160℃の乾燥機で24時間乾燥させたODPA 18.7gとPMDA 6.54gを3-メトキシ-N,N-ジメチルプロパンアミド400gに加えた。撹拌により得られた溶液に、1,3-ビス(3-アミノフェノキシ)ベンゼン29.1gを3-メトキシ-N,N-ジメチルプロパンアミド100gに懸濁させた懸濁液を滴下して混合液を準備した。混合液を30℃で4時間撹拌した後、混合液にジアザビシクロウンデセンを1.5g加え、150℃で2時間撹拌した。混合液を蒸留水に滴下し、沈殿物をろ別して集め、減圧乾燥することによってポリイミド樹脂A10を得た。A10の重量平均分子量は10,000であった。
(樹脂組成物の調製)
表1に示した成分及び配合量にて、実施例1~8及び比較例1の樹脂組成物を以下のようにして調製した。表1の各成分の配合量の単位は質量部である。また、表1中の空欄は該当成分が未配合であることを意味する。各実施例及び比較例にて、各成分の混合物を一般的な耐溶剤性容器内にて室温で一晩混練した後、0.2μm孔のフィルターを用いて加圧ろ過を行った。得られた樹脂組成物を用いて以下の評価を行った。
・高分子成分
上述のA1~A10
・(B)成分(溶剤)
B1:3-メトキシ-N,N-ジメチルプロピオンアミド
B2:N-メチル-2-ピロリドン
B3:乳酸メチル
B4:γ-ブチロラクトン
・(D)成分(重合性モノマー)
D1:トリエチレングリコールジメタアクリレート(TEGDMA)
D2:1,6-ヘキサンジオールジグリシジルエーテル
D3:トリグリシジル-p-アミノフェノール
D4:ヘキサキス(メトキシメチル)メラミン(Cymel)
D5:尿素・アルキル(C1~5)アルデヒド・アルキル(C2~10)多価(2~4)アルデヒド・アルキル(C1~12)モノアルコール重縮合物(MX270)
D6:4,4’-(1,1,1,3,3,3-ヘキサフルオロプロパン-2,2-ジイル)ビス[2,6-ビス(ヒドロキシメチル)フェノール]
・防錆剤
防錆剤1:ベンゾトリアゾール
防錆剤2:5-アミノ-1H-テトラゾール
防錆剤3:1-H-テトラゾール
・接着助剤
接着助剤1:3-ウレイドプロピルトリエトキシシランの50%メタノール溶液
接着助剤2:N,N’-ビス(2-ヒドロキシエチル)-3-アミノプロピルトリエトキシシランの60%エタノール溶液(SIB1140)
・(C)成分(光重合開始剤)
C1:1-フェニル-1,2-プロパンジオン-2-(o-エトキシカルボニル)オキシム
C2:エタノン,1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-,1-(O-アセチルオキシム)
C3:4,4’-ビス(ジエチルアミノ)ベンゾフェノン
C4:Irgacure OXE01
C5:下記式(Y)で表される化合物
・(E)成分(熱重合開始剤)
E1:ビス(1-フェニル-1-メチルエチル)ペルオキシド
・(F)成分(重合禁止剤)
F1:N,N’-ヘキサン-1,6-ジイルビス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオンアミド]
感光性樹脂組成物である実施例1~4、7、8及び比較例1の樹脂組成物を用いて以下のように硬化膜を形成し、次いで貯蔵弾性率を測定した。感光性樹脂組成物をSi基板上にスピンコートし、ホットプレート上で、表1の製膜時乾燥条件における温度(℃)及び時間(秒、表1中のs)で加熱乾燥し、硬化後約10μmとなるよう感光性樹脂膜を形成した。
得られた感光性樹脂膜を、マスクアライナーMA-8(ズース・マイクロテック社製)を用いて、表1に示す露光量にて広帯域(BB)露光した。露光後の樹脂膜を、実施例1~4、7及び8についてはシクロペンタノン(表1中のDev1に対応)により、比較例1については2.38%TMAH水溶液(表1中のDev2に対応)により、コーターデベロッパーACT8(東京エレクトロン株式会社製)を用いて表1に示す時間現像し、10mm幅の短冊状のパターン樹脂膜を得た。
得られたパターン樹脂膜を、縦型拡散炉μ-TFを用いて、窒素雰囲気下、表1に示す温度及び時間にて硬化し膜厚10μmのパターン硬化物を得た。
得られたパターン硬化物を、4.9質量%フッ酸水溶液に浸漬して、10mm幅のパターン硬化物をSi基板から剥離した。
TAインスツルメント製のRSA-G2を用い、試験周波数1Hz、昇温速度5℃/min、測定モード:引張り、N2雰囲気下、測定範囲-50℃~400℃、チャック間距離10mm、サンプル幅2.0mmの条件にてSi基板より剥離したパターン硬化物の貯蔵弾性率及び損失弾性率を測定した。
得られた貯蔵弾性率及び損失弾性率から損失正接を求め、損失正接のピークをTg(ガラス転移温度)とした。さらに、Tgよりも100℃低い温度での貯蔵弾性率(表2中のG1)及びTgよりも100℃高い温度での貯蔵弾性率(表2中のG2)からG2/G1を求めた。結果を表2に示す。
表2中のG2/G1については、0.3以下であることが好ましく、0.1以下であることがより好ましく、0.05以下であることがさらに好ましい。
実施例1~8及び比較例1の樹脂組成物を、塗布装置スピンコーターを用いて、8インチSiウェハー上にスピンコートし、乾燥工程を行い樹脂膜を形成した。樹脂組成物が感光性樹脂組成物である場合、得られた樹脂膜に対して直径180mmの円形状の樹脂膜が作製できるマスクを載せ、波長365nmの光を所定露光量照射した。その後、シクロペンタノン又は2.38%TMAHで所定時間現像し、Siウェハー上の樹脂膜のうち、外周から10mmを取り除きパターン樹脂膜を作製した。樹脂組成物が感光樹脂組成物ではない場合は、スピンコート後の樹脂膜のエッジ部分をシクロペンタノンでエッジリンスすることでウェハ外周部約10mmを除去し、直径約180mmの円形状の樹脂膜を作製した。樹脂膜を、クリーンオーブンを用いて、窒素雰囲気下で、表3に示す温度で所定時間加熱し、硬化後膜厚2μm~8μmである硬化膜を得た。
(チップ付きSiO2ウェハーの作製)
熱酸化法で作製されたSiO2ウェハーを用意し、上記の接着性評価用サンプルの作製方法に記載の方法で研磨し研磨済みSiO2ウェハーを作製した。作製した研磨済みSiO2ウェハーの一部に対し個片化を行い、SiO2チップを作製した。得られたSiO2チップを研磨済みSiO2ウェハーに対し、前述のチップ付き硬化膜を作製する際と同様の方法で接着し、チップ付きSiO2ウェハーを作製した。チップ付きSiO2ウェハーでは、研磨済みSiO2ウェハーに対して5つのSiO2チップを圧着させた、
-ボイドの評価基準-
A:5つのチップの中でボイドが観察されたチップが2つ以下である。
B:5つのチップの中でボイドが観察されたチップが2つより多い。
C:SATを測定する際にチップが1つ以上剥離している。
-接着力の評価基準-
A:5つのチップのシェア強度の平均が1Mpa以上である。
B:5つのチップのシェア強度の平均が1Mpa以下である。
C:接着力が低く測定不能である。
1MPa以上の接着力があればチップ付き硬化膜の作製以降の工程を問題なく実施することができた。
銅端子を絶縁層と共にハイブリッドボンディングする場合、銅端子の信頼性の問題から一般的には200℃~400℃の温度にて圧力を加えてボンディングを実施する。絶縁層が絶縁樹脂の硬化膜である場合、ボンディングの際に絶縁樹脂が熱分解し発生した揮発分によるボイド等が生じる可能性がある。そのため、前述のチップ付き硬化膜について、さらに高温の熱圧着を実施しボイド等が生じないか、及び、接着力が低下しないかについて評価を実施した。
前述のチップ付き硬化膜の上に段差吸収用のカーボンシートを被せ、圧着装置(EVG製)を用いて、所定の真空度の条件にて300℃で4時間、8インチサイズの加圧エリアに7200Nの荷重を加え圧着を実施した。その後、前述と同様の方法で熱圧着後でのボイドの有無及び硬化膜同士の接着力について評価を実施した。ボイドの有無及び接着力の評価基準はそれぞれ以下の通りである。結果を表3に示す。
-熱圧着後でのボイドの評価基準-
A:5つのチップの中でボイドが観察されたチップが2つ以下である。
B:5つのチップの中でボイドが観察されたチップが2つより多い。
C:SATを測定する際にチップが1つ以上剥離している。
-熱圧着後での接着力の評価基準-
A+:5つのチップのうち少なくとも3つのチップの破壊モードがSi部の凝集破壊である。
A :5つのチップのシェア強度の平均が5MPa以上である。
B :5つのチップのシェア強度の平均が5MPa未満である。
C :接着力が低く測定不能である。
一方、比較例2では、チップ付きSiO2ウェハーにてボイドの影響によりチップの剥離が確認された。
本明細書に記載された全ての文献、特許出願、及び技術規格は、個々の文献、特許出願、及び技術規格が参照により取り込まれることが具体的且つ個々に記された場合と同程度に、本明細書中に参照により取り込まれる。
Claims (25)
- (A)ポリアミド酸、ポリアミド酸エステル、ポリアミド酸塩及びポリアミド酸アミドからなる群より選択される少なくとも1種の樹脂であるポリイミド前駆体、並びにポリイミド樹脂の少なくとも一方と、(B)溶剤と、を含み、
以下の工程(1)~工程(5)を含む半導体装置の製造方法での第1有機絶縁膜及び第2有機絶縁膜の少なくとも一方の有機絶縁膜の作製に用いるための樹脂組成物。
工程(1) 第1基板本体と、前記第1基板本体の一面に設けられた前記第1有機絶縁膜及び第1電極とを有する第1半導体基板を準備する。
工程(2) 第2基板本体と、前記第2基板本体の一面に設けられた前記第2有機絶縁膜及び複数の第2電極とを有する第2半導体基板を準備する。
工程(3) 前記第2半導体基板を個片化し、前記第2有機絶縁膜の一部に対応する有機絶縁膜部分と少なくとも1つの前記第2電極とをそれぞれが備えた複数の半導体チップを取得する。
工程(4) 前記第1半導体基板の前記第1有機絶縁膜と前記半導体チップの前記有機絶縁膜部分とを互いに貼り合わせる。
工程(5) 前記第1半導体基板の前記第1電極と前記半導体チップの前記第2電極とを接合する。 - (A)ポリアミド酸、ポリアミド酸エステル、ポリアミド酸塩及びポリアミド酸アミドからなる群より選択される少なくとも1種の樹脂であるポリイミド前駆体、並びにポリイミド樹脂の少なくとも一方と、(B)溶剤と、を含み、
電極と共に化学機械研磨法により研磨される硬化物の作製に用いるための樹脂組成物。 - 前記一般式(1)中、前記Xで表される4価の有機基は、下記式(E)で表される基である請求項3に記載の樹脂組成物。
式(E)において、Cは、単結合、アルキレン基、ハロゲン化アルキレン基、カルボニル基、スルホニル基、エーテル結合(-O-)、スルフィド結合(-S-)、フェニレン基、エステル結合(-O-C(=O)-)、シリレン結合(-Si(RA)2-;2つのRAは、それぞれ独立に、水素原子、アルキル基又はフェニル基を表す。)、シロキサン結合(-O-(Si(RB)2-O-)n;2つのRBは、それぞれ独立に、水素原子、アルキル基又はフェニル基を表し、nは1又は2以上の整数を表す。)又はこれらを少なくとも2つ組み合わせた2価の基を表す。 - 前記一般式(1)中、前記Yで表される2価の有機基は、下記式(H)で表される基である請求項3又は請求項4に記載の樹脂組成物。
式(H)において、Rは、それぞれ独立に、アルキル基、アルコキシ基、ハロゲン化アルキル基、フェニル基又はハロゲン原子を表し、nは、それぞれ独立に、0~4の整数を表す。Dは、単結合、アルキレン基、ハロゲン化アルキレン基、カルボニル基、スルホニル基、エーテル結合(-O-)、スルフィド結合(-S-)、フェニレン基、エステル結合(-O-C(=O)-)、シリレン結合(-Si(RA)2-;2つのRAは、それぞれ独立に、水素原子、アルキル基又はフェニル基を表す。)、シロキサン結合(-O-(Si(RB)2-O-)n;2つのRBは、それぞれ独立に、水素原子、アルキル基又はフェニル基を表し、nは1又は2以上の整数を表す。)又はこれらを少なくとも2つ組み合わせた2価の基を表す。 - 前記(B)溶剤の含有量は、前記(A)ポリイミド前駆体及びポリイミド樹脂の合計100質量部に対して1質量部~10000質量部である請求項1~請求項6のいずれか1項に記載の樹脂組成物。
- 前記樹脂組成物を硬化してなる硬化物の5%熱重量減少温度が200℃以上である請求項1~請求項8のいずれか1項に記載の樹脂組成物。
- 前記樹脂組成物を硬化してなる硬化物のガラス転移温度が100℃~400℃である請求項1~請求項9のいずれか1項に記載の樹脂組成物。
- 前記樹脂組成物を硬化してなる硬化物について、動的粘弾性測定で求めた前記硬化物のガラス転移温度(Tg)よりも100℃低い温度での貯蔵弾性率G1に対する前記動的粘弾性測定で求めた前記硬化物のガラス転移温度(Tg)よりも100℃高い温度での貯蔵弾性率G2の比率であるG2/G1は、0.001~0.02である請求項1~請求項10のいずれか1項に記載の樹脂組成物。
- (C)光重合開始剤及び(D)重合性モノマーをさらに含む請求項1~請求項11のいずれか1項に記載の樹脂組成物。
- ネガ型感光性樹脂組成物又はポジ型感光性樹脂組成物であり、フォトリソグラフィ工法により、基板本体の一面上に設けられた有機絶縁膜に複数の端子電極を配置するための貫通孔を複数設けることに用いるための請求項1~請求項12のいずれか1項に記載の樹脂組成物。
- 硬化してなる硬化物の25℃での引張弾性率が7.0GPa以下である請求項1~請求項13のいずれか1項に記載の樹脂組成物。
- 硬化してなる硬化物の熱膨張率が150ppm/K以下である請求項1~請求項14のいずれか1項に記載の樹脂組成物。
- 請求項1~請求項15のいずれか1項に記載の樹脂組成物を第1有機絶縁膜及び第2有機絶縁膜の少なくとも一方の有機絶縁膜の作製に用い、以下の工程(1)~工程(5)を経て半導体装置を製造する半導体装置の製造方法。
工程(1) 第1基板本体と、前記第1基板本体の一面に設けられ前記第1有機絶縁膜及び第1電極とを有する第1半導体基板を準備する。
工程(2) 第2基板本体と、前記第2基板本体の一面に設けられた前記第2有機絶縁膜及び複数の第2電極とを有する第2半導体基板を準備する。
工程(3) 前記第2半導体基板を個片化し、前記第2有機絶縁膜の一部に対応する有機絶縁膜部分と少なくとも1つの前記第2電極とをそれぞれが備えた複数の半導体チップを取得する。
工程(4) 前記第1半導体基板の前記第1有機絶縁膜と前記半導体チップの前記有機絶縁膜部分とを互いに貼り合わせる。
工程(5) 前記第1半導体基板の前記第1電極と前記半導体チップの前記第2電極とを接合する。 - 前記工程(4)において、前記半導体チップと前記第1半導体基板との温度差が10℃以内となる温度で前記第1有機絶縁膜と前記有機絶縁膜部分とを貼り合わせる請求項16に記載の半導体装置の製造方法。
- 製造された半導体装置において、前記第1有機絶縁膜と前記有機絶縁膜部分との接合により形成された有機絶縁膜の厚さが0.1μm以上である請求項16又は請求項17に記載の半導体装置の製造方法。
- 前記工程(1)が前記第1半導体基板の前記一面側を研磨する工程を含むこと、及び、前記工程(2)が前記第2半導体基板の前記一面側を研磨する工程を含むことの少なくとも一方を満たし、前記第1有機絶縁膜の研磨レートは、前記第1電極の研磨レートの0.1倍~5倍であること、及び、前記第2有機絶縁膜の研磨レートは、前記第2電極の研磨レートの0.1倍~5倍であることの少なくとも一方を満たす請求項16~請求項18のいずれか1項に記載の半導体装置の製造方法。
- 前記第2絶縁膜の厚さは、前記第1絶縁膜の厚さよりも大きい請求項16~請求項19のいずれか1項に記載の半導体装置の製造方法。
- 前記第2絶縁膜の厚さは、前記第1絶縁膜の厚さよりも小さい請求項16~請求項19のいずれか1項に記載の半導体装置の製造方法。
- 請求項1~請求項15のいずれか1項に記載の樹脂組成物を硬化してなる硬化物。
- 第1基板本体と、前記第1基板本体の一面に設けられた前記第1有機絶縁膜及び第1電極とを有する第1半導体基板と、
半導体チップ基板本体と、前記半導体チップ基板本体の一面に設けられた有機絶縁膜部分及び第2電極とを有する半導体チップと、
を備え、前記第1半導体基板の前記第1有機絶縁膜と、前記半導体チップの前記有機絶縁膜部分と、が接合し、前記第1半導体基板の前記第1電極と、前記半導体チップの前記第2電極と、が接合し、
前記第1有機絶縁膜及び前記有機絶縁膜部分の少なくとも一方が請求項1~請求項15のいずれか1項に記載の樹脂組成物を硬化してなる有機絶縁膜である半導体装置。 - テトラカルボン酸二無水物と、H2N-Y-NH2で表されるジアミン化合物(式中、Yは2価の有機基である。)と、を3-メトキシ-N,N-ジメチルプロパンアミド中にて反応させポリアミド酸溶液を得る工程と、
前記ポリアミド酸溶液に脱水縮合剤及びR-OHで表される化合物(式中、Rは1価の有機基である。)を作用させる工程と、
を含む、ポリイミド前駆体の合成方法。 - 前記脱水縮合剤は、トリフルオロ酢酸無水物、N,N’-ジシクロヘキシルカルボジイミド(DCC)及び1,3-ジイソプロピルカルボジイミド(DIC)からなる群より選択される少なくとも1種を含む、請求項24に記載のポリイミド前駆体の合成方法。
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