WO2024157936A1 - 樹脂組成物、硬化膜、積層体、撮像装置、半導体装置、積層体の製造方法及び接合電極を有する素子の製造方法 - Google Patents

樹脂組成物、硬化膜、積層体、撮像装置、半導体装置、積層体の製造方法及び接合電極を有する素子の製造方法 Download PDF

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Publication number
WO2024157936A1
WO2024157936A1 PCT/JP2024/001676 JP2024001676W WO2024157936A1 WO 2024157936 A1 WO2024157936 A1 WO 2024157936A1 JP 2024001676 W JP2024001676 W JP 2024001676W WO 2024157936 A1 WO2024157936 A1 WO 2024157936A1
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Prior art keywords
resin composition
laminate
weight
cured film
modifier
Prior art date
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Ceased
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PCT/JP2024/001676
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English (en)
French (fr)
Japanese (ja)
Inventor
主 國澤
太郎 塩島
颯 野元
徳重 七里
憲一朗 佐藤
英寛 出口
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Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
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Priority to EP24747263.2A priority Critical patent/EP4656684A1/en
Priority to CN202480006271.XA priority patent/CN120380085A/zh
Priority to KR1020257019164A priority patent/KR20250135777A/ko
Priority to JP2024505608A priority patent/JPWO2024157936A1/ja
Publication of WO2024157936A1 publication Critical patent/WO2024157936A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W20/00—Interconnections in chips, wafers or substrates
    • H10W20/40—Interconnections external to wafers or substrates, e.g. back-end-of-line [BEOL] metallisations or vias connecting to gate electrodes
    • H10W20/45—Interconnections external to wafers or substrates, e.g. back-end-of-line [BEOL] metallisations or vias connecting to gate electrodes characterised by their insulating parts
    • H10W20/48—Insulating materials thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/283—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysiloxanes
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/452—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences
    • C08G77/458—Block-or graft-polymers containing polysiloxane sequences containing nitrogen-containing sequences containing polyurethane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C08L83/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W20/00—Interconnections in chips, wafers or substrates
    • H10W20/01—Manufacture or treatment
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/02—Polysilicates
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46—Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W72/00—Interconnections or connectors in packages
    • H10W72/01—Manufacture or treatment
    • H10W72/0198—Manufacture or treatment batch processes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W72/00—Interconnections or connectors in packages
    • H10W72/90—Bond pads, in general
    • H10W72/951—Materials of bond pads
    • H10W72/952—Materials of bond pads comprising metals or metalloids, e.g. PbSn, Ag or Cu
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W90/00—Package configurations
    • H10W90/701—Package configurations characterised by the relative positions of pads or connectors relative to package parts
    • H10W90/731—Package configurations characterised by the relative positions of pads or connectors relative to package parts of die-attach connectors
    • H10W90/732—Package configurations characterised by the relative positions of pads or connectors relative to package parts of die-attach connectors between stacked chips

Definitions

  • the present invention relates to a resin composition, a cured film using the resin composition, a laminate having the cured film, an imaging device and a semiconductor device having the laminate, a method for manufacturing the laminate, and a method for manufacturing an element having a joining electrode used in manufacturing the laminate.
  • a damascene process is first used to form a bonding surface on the electrode surface of an element on which two electrodes are formed, in which a bonding electrode made of copper is surrounded by an insulating film.
  • the two elements are then stacked so that the bonding electrodes on the bonding surfaces face each other, and a heat treatment is performed to manufacture the stack (Patent Document 1).
  • insulating inorganic materials such as SiN and SiO2 are used as the insulating layer.
  • insulating layers made of inorganic materials are prone to warping of the elements, and if the elements warp, the connection position of the electrodes may shift or the electrodes may crack when the laminate is formed, which may reduce the connection reliability of the laminate.
  • the performance of semiconductor devices has improved, and elements have become larger and thinner, making it easier for the elements to warp.
  • the surface of the element on which the insulating layer is formed may have irregularities of several ⁇ m to several tens of ⁇ m.
  • the present invention aims to provide a resin composition that has excellent heat resistance and flexibility, and can flatten the connection surface even when the element surface has irregularities, thereby providing high electrical connection reliability between elements; a cured film using the resin composition; a laminate having the cured film; an imaging device and a semiconductor device having the laminate; a method for manufacturing the laminate; and a method for manufacturing an element having a joining electrode used in manufacturing the laminate.
  • the present invention includes the following Disclosures 1 to 23.
  • the present invention will be described in detail below.
  • the organosilicon compound and 1 part by weight of the modifier per 100 parts by weight of the organosilicon compound are added to ethyl benzoate to prepare a sample having a viscosity of 45 cP at 25°C.
  • the contact angle of the sample with the silicon wafer is 9° or more and 20° or less.
  • the resin composition according to Disclosure 1 further comprising a solvent, the resin composition being made into a solution having a viscosity of 1200 cP using the solvent, the solution being spin-coated onto a silicon wafer at 1500 rpm for 10 sec, and after drying the solvent, being cured under conditions of 300° C. for 1 hour to form a cured resin film having a thickness of 10 ⁇ m or more.
  • the cured resin film has a surface free energy of 27 mJ/ m2 or more.
  • a resin composition containing an organosilicon compound and a modifier, The organosilicon compound has a structure represented by the following general formula (1): The resin composition, wherein the modifier has a polyether modifying group.
  • R0 , R1 , and R2 each independently represent a linear, branched, or cyclic aliphatic group, an aromatic group, or hydrogen. The aliphatic group and the aromatic group may or may not have a substituent.
  • m and n each represent an integer of 1 or more.
  • [Disclosure 11] A cured film formed using the resin composition according to any one of Disclosures 1 to 10.
  • [Disclosure 12] A laminate having the cured film according to Disclosure 11 between a first element having an electrode and a second element having an electrode, wherein the electrode of the first element and the electrode of the second element are electrically connected via a through hole penetrating the cured film.
  • the laminate according to disclosure 12 further comprising an inorganic layer between the first element and the second element.
  • [Disclosure 14] 14 14.
  • [Disclosure 15] An imaging device having the laminate according to any one of Disclosures 12 to 14.
  • Disclosure 20 Disclosure 20.
  • the laminate according to Disclosure 19 having an inorganic layer between the supporting substrate and the cured film.
  • the laminate according to Disclosure 19 or 20 further comprising a fourth element on the second surface of the third element, the third element and the fourth element being electrically connected to each other.
  • An imaging device having the laminate according to any one of Disclosures 19 to 21.
  • a semiconductor device having the laminate according to any one of Disclosures 19 to 21.
  • the resin composition of the present invention contains an organosilicon compound.
  • the insulating layer is made of a cured film of an organic resin composition, which increases the flexibility of the insulating layer and suppresses warping of the elements, thereby improving the reliability of electrical connection.
  • an organosilicon compound in the resin composition makes it possible to obtain an insulating layer having excellent heat resistance and flattening properties for elements.
  • the organosilicon compound is preferably silselquioxane.
  • Silsesquioxane has high heat resistance while having the same degree of flexibility as organic compounds, so that by using a cured film mainly composed of silsesquioxane as the insulating layer of a laminate, it is possible to suppress warping and cracking of the substrate and improve the reliability of electrical connection.
  • the above-mentioned silsesquioxane is not particularly limited as long as it is thermosetting, but it is preferable that one molecule has a structure represented by the following structural formulas (A) and (B) in order to further suppress warping and cracking of the substrate.
  • R A and R B each independently represent an aliphatic group, an aromatic group, or hydrogen, and j and k each represent a repeating unit and an integer of 1 or more.
  • the organosilicon compound more preferably has a structure represented by the following general formula (1).
  • the organosilicon compound has the structure of the following general formula (1), the heat resistance is further increased, and when used in the insulating layer of the laminate, the electrode misalignment and cracking can be further suppressed, thereby improving the reliability of the electrical connection.
  • the organosilicon compound represented by the following general formula (1) can be bonded with the modifier described below, and therefore the modifier can be dispersed throughout the resin composition, thereby further improving the planarization of the element when used in the insulating layer of the laminate. Furthermore, it is possible to easily satisfy the contact angle with respect to the silicon wafer described below.
  • R0 , R1 , and R2 each independently represent a linear, branched, or cyclic aliphatic group, an aromatic group, or hydrogen.
  • the aliphatic group and the aromatic group may or may not have a substituent.
  • m and n each represent an integer of 1 or more.
  • R 0 each independently represents a linear, branched or cyclic aliphatic group, an aromatic group, or hydrogen.
  • the aliphatic group and the aromatic group may or may not have a substituent.
  • R 0 is preferably a phenyl group, an alkyl group having 1 to 20 carbon atoms, or an arylalkyl group, and more preferably a phenyl group.
  • R 0 is a phenyl group, an alkyl group having 1 to 20 carbon atoms, or an arylalkyl group, higher heat resistance can be exhibited.
  • R 1 and R 2 each independently represent a linear, branched or cyclic aliphatic group, an aromatic group, or hydrogen.
  • the aliphatic group and the aromatic group may or may not have a substituent.
  • R 1 and R 2 are preferably a phenyl group, an alkyl group having 1 to 20 carbon atoms, or an arylalkyl group, and more preferably a phenyl group or a methyl group.
  • R 1 and R 2 being a phenyl group, an alkyl group having 1 to 20 carbon atoms, or an arylalkyl group, higher heat resistance can be exhibited.
  • m and n are each an integer of 1 or more and represent the number of repeating units.
  • the above m is preferably 30 or more, more preferably 50 or more, and preferably 100 or less.
  • the above n is preferably 1 or more, more preferably 3 or more, even more preferably 4 or more, and preferably 8 or less, more preferably 6 or less.
  • the organosilicon compound preferably has a reactive site.
  • an organosilicon compound having a reactive site as the curable resin of the resin composition, warping of the element and misalignment or cracking of the electrode can be suppressed when used in the insulating layer of the laminate.
  • the organosilicon compound has excellent heat resistance, decomposition of the cured film due to high-temperature treatment performed during the manufacture of electronic components can be suppressed.
  • the reactive site include hydroxyl groups and alkoxy groups.
  • organosilicon compound having the reactive site include organosilicon compounds represented by the general formula (1).
  • the content of the organosilicon compound is preferably 80 parts by weight or more, more preferably 90 parts by weight or more, and even more preferably 95 parts by weight or more, per 100 parts by weight of the solid content (amount of components other than the solvent) in the resin composition.
  • the content of the organosilicon compound is preferably less than 100 parts by weight, more preferably 98 parts by weight or less, per 100 parts by weight of the solid content in the resin composition.
  • the weight average molecular weight of the organosilicon compound is not particularly limited, but is preferably 5000 or more and 150000 or less.
  • the molecular weight of the organosilicon compound is in the above range, which improves the film-forming property during application, improves the flattening performance, and can further suppress the warping of the element and the misalignment and cracking of the electrode when used in the insulating layer of the laminate.
  • the molecular weight of the organosilicon compound is more preferably 10000 or more, more preferably 30000 or more, more preferably 100000 or less, and more preferably 70000 or less.
  • the weight average molecular weight of the organosilicon compound is measured as a polystyrene-equivalent molecular weight by gel permeation chromatography (GPC) using THF as an elution solvent and a Time-MB-M 6.0 x 150 mm (manufactured by Waters Corporation) or an equivalent column, and can be calculated with a polystyrene standard.
  • GPC gel permeation chromatography
  • the above-mentioned organosilicon compound is preferably dissolved in the resin composition, and is preferably not present in a dispersed state having a specific shape such as particulate form, from the viewpoints of improving the film-forming properties during application and further enhancing the planarization performance, as well as of being able to further suppress warping of elements and misalignment and cracking of electrodes when used in the insulating layer of a laminate.
  • the resin composition of the present invention contains a modifier.
  • a modifier that has a thermal weight loss amount described later and satisfies the contact angle with respect to silicon wafer described later when used in combination with the above-mentioned organosilicon compound, the connection surface can be flattened even when used on an element having an uneven surface, and high electrical connection reliability can be provided between elements. In order to flatten the connection surface, it is required to form a film stably even at high temperatures. Therefore, simply using a modifier with an organosilicon compound that has flexibility may cause film cracking and poor flattening of the connection surface.
  • the above-mentioned modifier alone is heated in air from room temperature to 300°C at a heating rate of 10°C/min, held for 1 hour, and then heated to 400°C at a heating rate of 10°C/min and held at 400°C for 3 hours.
  • the thermal weight loss before and after holding at 400°C for 3 hours is 10% or less.
  • the thermal weight loss of the modifier is preferably 8% or less, and more preferably 5% or less.
  • the weight loss due to heat can be adjusted by adjusting the molecular weight and the type of functional group.
  • the weight loss due to heat can be measured using a thermogravimetric and differential thermal analyzer (TG-DTA; STA7200, manufactured by Hitachi High-Tech Science Corporation or an equivalent product), and specifically, can be measured by the following method.
  • thermogravimetry and differential thermal analyzer (TG-DTA; STA7200, Hitachi High-Tech Science Corporation or equivalent)
  • the modifier is heated in air from 25°C to 300°C at a heating rate of 10°C/min and held at that temperature for 1 hour. After holding for 1 hour, it is further heated to 400°C at a heating rate of 10°C/min and held at 400°C for 3 hours.
  • the amount of thermal weight loss is calculated from the weight at each temperature when it first reaches 400°C and the weight after 3 hours at 400°C.
  • the modifier is not particularly limited as long as it satisfies the above-mentioned thermal weight loss amount and the contact angle with respect to the silicon wafer described below, but examples of compounds that easily satisfy these include polyether-based compounds, aralkyl-based compounds, polyester-based compounds, and silicone-based compounds.
  • the modifier preferably has a polyether-modified group, and more preferably is a silicone-based compound having a polyether-modified group, because it easily satisfies the above-mentioned thermal weight loss amount and the contact angle with respect to the silicon wafer described below, and can flatten the connection surface even when used on an element having an uneven surface.
  • the content of the modifier is not particularly limited, but since it can further flatten the connection surface of the element, it is preferably 0.01 parts by weight or more relative to 100 parts by weight of the organosilicon compound, more preferably 0.1 parts by weight or more, even more preferably 0.3 parts by weight or more, and preferably 10 parts by weight or less, more preferably 1 part by weight or less, and even more preferably 0.7 parts by weight or less.
  • the modifier preferably has a weight average molecular weight of 4,000 or more and 30,000 or less.
  • the connection surface of the element can be made more flat.
  • the modifier more preferably has a weight average molecular weight of 15,000 or more, even more preferably has a weight average molecular weight of 20,000 or more, even more preferably has a weight average molecular weight of 30,000 or less, and even more preferably has a weight average molecular weight of 25,000 or less.
  • the weight average molecular weight of the modifier can be measured in the same manner as the weight average molecular weight of the organosilicon compound.
  • the resin composition of the present invention preferably contains a solvent.
  • a solvent By including a solvent in the resin composition, it is possible to easily adjust the viscosity of the organosilicon compound to a level that allows it to be applied onto an element, and when used on an element, it is possible to fill in the unevenness of the element surface to make it more flat.
  • the solvent may be composed of a single component or a mixture of multiple components.
  • the above-mentioned solvent is not particularly limited, but examples thereof include ketone-based solvents such as cyclopentanone, ester-based solvents such as ethyl benzoate, lactone-based solvents, lactam-based solvents, glycol ether-based solvents, etc.
  • ketone-based solvents such as cyclopentanone
  • ester-based solvents such as ethyl benzoate
  • lactone-based solvents such as lactone-based solvents
  • lactam-based solvents lactam-based solvents
  • glycol ether-based solvents glycol ether-based solvents
  • the solvent preferably has a boiling point of 150° C. or higher and 250° C. or lower.
  • the boiling point of the solvent is within the above range, so that the flattening performance can be further improved.
  • the boiling point of the solvent satisfies the above lower limit, so that the foreign matter abnormality caused by the solvent volatilizing in string form and adhering to the coating film during spin coating can be suppressed.
  • the boiling point of the solvent is more preferably 170° C. or higher, even more preferably 180° C. or higher, more preferably 230° C. or lower, and even more preferably 220° C. or lower.
  • solvents having a boiling point within the above range include aromatic organic solvents, lactam organic solvents, and lactone organic solvents.
  • R represents a hydrocarbon.
  • the compound examples include cyclopentanone (boiling point: 131° C.), propylene glycol monomethyl ether acetate (boiling point: 146° C.), anisole (boiling point: 154° C.), ethyl benzoate (boiling point: 211 to 213° C.), N-methyl-2-pyrrolidone (boiling point: 202° C.), 2-piperidone (boiling point: 256° C.), 2-pyrrolidone (boiling point: 245° C.), ⁇ -butyrolactone (boiling point: 204° C.), and ⁇ -valerolactone (boiling point: 207° C.).
  • the content of the solvent in the resin composition is preferably 50% by weight or less.
  • the content of the solvent in the resin composition is preferably 45% by weight or less, more preferably 40% by weight or less, and even more preferably 35% by weight or less.
  • the lower limit of the content of the solvent is not particularly limited, but is preferably 30% by weight or more from the viewpoint of further improving the flattening performance.
  • the content of the solvent is preferably 50 parts by weight or more and 100 parts by weight or less based on 100 parts by weight of the organosilicon compound.
  • the content of the solvent relative to the organosilicon compound in the above range can further improve the flattening performance of the element surface.
  • the content of the solvent relative to the organosilicon compound is more preferably 55 parts by weight or more, even more preferably 60 parts by weight or more, more preferably 80 parts by weight or less, and even more preferably 70 parts by weight or less.
  • the resin composition of the present invention preferably contains a metal catalyst that accelerates the curing reaction.
  • a metal catalyst include dibutyltin dilaurate, organotin compounds such as stannous acetate, metal carboxylates such as zinc naphthenate, zirconia compounds such as zirconium tetraacetylacetonate, titanium compounds, etc.
  • zirconium tetraacetylacetonate and dibutyltin dilaurate are preferred because they can further accelerate the curing of the resin composition.
  • the metal catalyst is present even after the resin composition is cured. That is, the cured film formed by curing the resin composition of the present invention preferably contains a metal catalyst that promotes the curing reaction.
  • the content of the catalyst is not particularly limited, but is preferably 0.01 parts by weight or more and 10 parts by weight or less per 100 parts by weight of the organosilicon compound in the resin composition. By setting the content of the catalyst within the above range, the curing of the resin composition can be further promoted.
  • the content of the catalyst is more preferably 0.1 parts by weight or more, even more preferably 0.2 parts by weight or more, more preferably 7 parts by weight or less, and even more preferably 5 parts by weight or less.
  • the resin composition of the present invention preferably contains a crosslinking agent.
  • the crosslinking agent capable of reacting with the reactive site of the organosilicon compound crosslinks between the polymers of the organosilicon compound having the reactive site, thereby increasing the crosslink density of the cured product and further suppressing decomposition at high temperatures.
  • the crosslinking agent may be an alkoxysilane compound such as a dimethoxysilane compound, a trimethoxysilane compound, a diethoxysilane compound, or a triethoxysilane compound, or a silicate oligomer obtained by condensation of a tetramethoxysilane compound and a tetraethoxysilane compound.
  • silicate oligomers are preferred from the viewpoint of improving crosslink density and heat resistance.
  • alkoxysilane compounds include dimethoxydimethylsilane, trimethoxymethylsilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane.
  • silicate oligomers include silicate MS51, MS56, MS57, and MS56S (all manufactured by Mitsubishi Chemical Corporation), ethyl silicate 40, ethyl silicate 48, and EMS485 (all manufactured by Colcoat Co., Ltd.).
  • the content of the crosslinking agent is not particularly limited, but is preferably 1 part by weight or more and 50 parts by weight or less per 100 parts by weight of the organosilicon compound in the resin composition.
  • the content of the crosslinking agent is more preferably 3 parts by weight or more, even more preferably 3.2 parts by weight or more, more preferably 30 parts by weight or less, and even more preferably 20 parts by weight or less.
  • the resin composition of the present invention preferably contains a heat resistance additive.
  • a heat-resistant additive in the resin composition, the cured product of the resin composition can be made more heat-resistant.
  • the heat-resistant additive include polyimide resin, epoxy resin, silicone resin, benzoxazine resin, cyanate resin, and phenolic resin. Among them, polyimide resin is preferable because it can improve heat resistance.
  • the molecular weight of the heat resistance additive is not particularly limited, but is preferably 5,000 or more and 150,000 or less. By having the weight average molecular weight of the heat resistance additive in the above range, it is possible to easily adjust the viscosity and solids concentration of the resin composition to the range of the present invention.
  • the molecular weight of the heat resistance additive is more preferably 10,000 or more, even more preferably 30,000 or more, more preferably 100,000 or less, and even more preferably 70,000 or less.
  • the content of the heat resistance additive is not particularly limited, but from the viewpoint of further improving heat resistance, it is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more, and preferably 10 parts by weight or less, more preferably 5 parts by weight or less, per 100 parts by weight of the organosilicon compound.
  • the polyimide preferably has a siloxane bond.
  • the polyimide has a siloxane bond, which enhances compatibility with the organosilicon compound contained in the resin composition, and therefore makes it possible to further suppress unevenness (surface roughness) caused by precipitation of the polyimide during application.
  • the polyimide When the polyimide has a siloxane bond, the polyimide preferably has a ratio of carbon atoms to silicon atoms in the main chain structure, C/Si, of 17 or less.
  • C/Si a ratio of carbon atoms to silicon atoms in the main chain structure of the polyimide
  • the C/Si is more preferably 16.5 or less, and even more preferably 16 or less.
  • the lower limit of the C/Si is not particularly limited, but is preferably 4 or more from the viewpoint of practical use and further increasing the heat resistance at 400°C.
  • the ratio C/Si of carbon atoms to silicon atoms in the main chain structure of the polyimide is the ratio of C and Si in the repeating unit, and does not include C and Si at both ends.
  • the C/Si can be obtained by obtaining the structure of the polyimide by 1 H-NMR, 13 C-NMR, and 29 Si-NMR, and measuring the number of C atoms and Si atoms from the repeating unit of the main chain.
  • the polyimide preferably has a plurality of aromatic rings.
  • the polyimide has a plurality of aromatic rings, so that even when a thick cured film is formed, it is possible to obtain a cured film that is less susceptible to film cracking when subjected to high-temperature treatment under various conditions.
  • the polyimide preferably has an oxazine ring or imide ring structure at least at one of its terminals, and more preferably has an oxazine ring or imide ring structure at both terminals.
  • an oxazine ring or imide ring structure at the terminal of the polyimide surface roughness can be further suppressed when the polyimide is made into a thick film.
  • the oxazine ring and imide ring structures may have a substituent.
  • the polyimide has any one of the structures represented by the following formulae (2) to (7) at at least one terminal, and it is particularly preferable that both terminals have any one of the structures represented by the following formulae (2) to (7).
  • "*" in the following formulae represents a bonding site with a portion other than the terminal of the polyimide.
  • the polyimide preferably has a weight average molecular weight of 1,000 or more and 50,000 or less.
  • the weight-average molecular weight of the polyimide is more preferably 2000 or more, and even more preferably 3000 or more, and more preferably 35000 or less, and even more preferably 30000 or less.
  • the weight average molecular weight of the polyimide is measured as a polystyrene-equivalent molecular weight by gel permeation chromatography (GPC) using THF as an elution solvent and a Time-MB-M 6.0 ⁇ 150 mm (manufactured by Waters Corporation) or an equivalent column, and can be calculated with a polystyrene standard.
  • GPC gel permeation chromatography
  • the content of the polyimide is preferably 0.5 parts by weight or more and 50 parts by weight or less based on 100 parts by weight of the organosilicon compound. By setting the polyimide content within the above range, it is possible to obtain a cured film that is less susceptible to film cracking during high-temperature treatment, even in the case where the cured film has a large thickness.
  • the content of the polyimide is preferably 0.7 parts by weight or more, more preferably 0.75 parts by weight or more, and even more preferably 1 part by weight or more, per 100 parts by weight of the organosilicon compound, and is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, and even more preferably 5 parts by weight or less.
  • the resin composition of the present invention may contain other additives such as viscosity modifiers, fillers, and adhesion promoters as necessary. However, from the viewpoint of suppressing the amount of thermal decomposition at high temperatures and increasing heat resistance, it is preferable that the composition does not contain a fluorescent agent.
  • the resin composition of the present invention is prepared by adding the above-mentioned organosilicon compound and 1 part by weight of the above-mentioned modifier per 100 parts by weight of the above-mentioned organosilicon compound to ethyl benzoate to prepare a sample having a viscosity of 45 cP at 25°C, and when the above sample is dropped onto a silicon wafer, the contact angle of the above sample with the silicon wafer is 9° or more and 20° or less.
  • the resin composition can be allowed to reach the bottom surface of the recess, thereby making the connection surface flat.
  • the contact angle is preferably 12° or more, more preferably 14° or more, preferably 18° or less, and more preferably 15° or less.
  • the contact angle can be adjusted by combining the types of the organosilicon compound and the modifier.
  • the contact angle can be easily adjusted to the above range.
  • the viscosity at 25° C. can be measured by using an E-type viscometer (TVE100H, manufactured by Toki Sangyo Co., Ltd., or an equivalent product) to measure the kinetic viscosity at 25° C. and 10.0 rpm shear.
  • the contact angle can be measured by a method in accordance with JIS R3257, and specifically, can be measured by the following method.
  • An organosilicon compound and 1 part by weight of a modifier per 100 parts by weight of the organosilicon compound are added to ethyl benzoate to prepare a sample with a viscosity of 45 cP at 25°C.
  • the resulting sample is dropped onto a silicon wafer using a contact angle measuring device (fully automatic contact angle meter DMo-702, manufactured by Kyowa Interface Science Co., Ltd. or an equivalent product) to measure the contact angle of the sample with the silicon wafer.
  • the resin composition of the present invention further contains a solvent, and the resin composition is made into a solution having a viscosity of 1200 cP at 25° C. using the solvent, and the solution is spin-coated onto a silicon wafer at 1500 rpm for 10 sec. After the solvent is dried, the solution is cured at 300° C. for 1 hour to form a cured resin film having a thickness of 10 ⁇ m or more. It is preferable that the surface free energy of the cured resin film is 27 mJ/ m2 or more.
  • the surface free energy of the resin cured film is within the above range, the wettability to the Si wafer can be reduced, and the outflow of the resin composition can be suppressed, so that even when used on an element having an uneven surface, the connection surface can be flattened.
  • the surface free energy of the resin cured film is more preferably 30 mJ/m 2 or more, even more preferably 33 mJ/m 2 or more, more preferably 38 mJ/m 2 or less, and even more preferably 35 mJ/m 2 or less.
  • the surface free energy of the cured resin film can be adjusted by the type and content of the organosilicon compound, the type and content of the modifier, the type and content of the catalyst, the type and content of the crosslinking agent, the type and content of the heat-resistant additive, the type of solvent, etc.
  • the surface energy of the cured resin film can be measured by a contact angle meter (fully automatic contact angle meter DMo-702, manufactured by Kyowa Interface Science Co., Ltd. or an equivalent product), and specifically, can be measured by the following method.
  • the solvent can have the above viscosity and is not particularly limited as long as it completely volatilizes when made into a cured resin film, and for example, the same solvent as described above can be used.
  • a solvent is added to the resin composition to obtain a solution with a viscosity of 1200 cP at 25°C.
  • the solution is dropped onto the center of an 8-inch silicon wafer, and the resin composition is applied onto the silicon wafer at 1500 rpm for 10 seconds using a spin coater (ACT-400II, manufactured by ACTIVE or equivalent).
  • the wafer coated with the solution is heated at 125°C for 10 minutes to dry the solvent.
  • the wafer is then heated at 300°C for 1 hour to obtain a cured resin film with a thickness of 10 ⁇ m or more.
  • the resin composition of the present invention preferably has a 1% weight loss temperature of 440° C. or higher when cured at 300° C. for 1 hour after drying the solvent.
  • the weight loss temperature is more preferably 450° C. or higher, and even more preferably 460° C. or higher. There is no particular upper limit to the weight loss temperature, and the higher the better, but the manufacturing technology limits it to about 480° C.
  • the weight loss temperature can be adjusted by adjusting the composition of the resin composition, the type of resin material constituting the resin composition, the curing conditions of the resin composition, and the like. Specifically, for example, the weight loss temperature can be improved by using a resin material or inorganic component having high heat resistance in the resin composition, increasing the content of the crosslinking agent, or the like. Furthermore, by using a resin material having high heat resistance (for example, a resin having a large molecular weight or a resin having a main chain or substituents having high heat resistance), the weight loss temperature can be improved.
  • a resin material having high heat resistance for example, a resin having a large molecular weight or a resin having a main chain or substituents having high heat resistance
  • the weight loss temperature of the cured product of the resin composition can be measured by the following method.
  • the resin composition applied in a sheet form using an applicator or the like is dried by heating at 125°C for 10 minutes, and then heated at 300°C for 1 hour to obtain a 35 ⁇ m thick film (cured film) of the cured resin composition.
  • About 3 to 10 mg of the obtained film is weighed, and the temperature at which the weight loss rate reaches 1% when heated at a heating rate of 10°C/min under a nitrogen flow (50 mL/min) is measured using a simultaneous thermogravimetry and differential thermal analyzer (TG-DTA; STA7200, Hitachi High-Tech Science Corporation, or an equivalent product).
  • TG-DTA simultaneous thermogravimetry and differential thermal analyzer
  • the method for producing the resin composition of the present invention is not particularly limited, and it can be produced, for example, by mixing the above-mentioned organosilicon compound and the above-mentioned modifier with additives such as the above-mentioned catalyst and the above-mentioned crosslinking agent as necessary.
  • the resin composition of the present invention contains an organosilicon compound and a modifier, and the modifier satisfies the above weight loss amount and the above contact angle with the silicon wafer, so that the composition has excellent heat resistance and flexibility, and can flatten the connection surface even when the element surface has irregularities, thereby providing high electrical connection reliability between elements.
  • the organosilicon compound is an organosilicon compound represented by the above general formula (1)
  • the modifier has a polyether modifying group, so that the effect of the present invention can be achieved.
  • the present invention also includes a resin composition containing an organosilicon compound and a modifier, the organosilicon compound having a structure represented by the following general formula (1), and the modifier having a polyether modified group. Details of the organosilicon compound, the modifier, other additives, and various physical properties are the same as those described above.
  • R0 , R1 , and R2 each independently represent a linear, branched, or cyclic aliphatic group, an aromatic group, or hydrogen.
  • the aliphatic group and the aromatic group may or may not have a substituent.
  • m and n each represent an integer of 1 or more.
  • the uses of the resin composition of the present invention are not particularly limited, but since the resin composition has excellent performance in filling in unevenness and flattening the surface, and the cured film has heat resistance and flexibility, the resin composition can be suitably used for forming an insulating layer on the uneven surface of an element having an uneven surface, or as an insulating layer when electrically connecting the electrodes of two elements having electrodes to produce a laminate.
  • the resin composition of the present invention which is used for forming an insulating layer on the uneven surface of an element having such unevenness on its surface, and a cured film formed using the resin composition of the present invention, also constitute the present invention.
  • Examples of the above elements include a sensor circuit element provided with a pixel section (pixel region), and a circuit element equipped with a peripheral circuit section such as a logic circuit that executes various signal processing related to the operation of the solid-state imaging device.
  • the cured film of the present invention preferably has a 1% weight loss temperature of 440° C. or higher.
  • the weight loss temperature is more preferably 450° C. or higher, and even more preferably 460° C. or higher.
  • the weight loss temperature can be adjusted by adjusting the composition of the resin composition, the type of resin material constituting the resin composition, the curing conditions of the resin composition, and the like. Specifically, for example, the weight loss temperature can be improved by using a resin material or inorganic component having high heat resistance in the resin composition, increasing the content of the crosslinking agent, or the like. In addition, the weight loss temperature can be improved by using a resin material constituting the cured film that has high heat resistance (for example, a resin with a large molecular weight or a resin having a main chain or substituent with high heat resistance), or by setting the curing conditions of the resin composition that is the raw material of the cured film to a high temperature at which curing proceeds sufficiently or by setting the curing time to a long time.
  • a resin material constituting the cured film that has high heat resistance
  • the weight loss temperature of the cured film can be measured by the following method. Approximately 3-10 mg of the cured film is weighed out, and heated at a temperature increase rate of 10° C./min under a nitrogen flow (50 mL/min) using a thermogravimetric and differential thermal analyzer (TG-DTA; STA7200, manufactured by Hitachi High-Tech Science Corporation, or an equivalent product), and the temperature at which the weight loss rate reaches 1% is measured.
  • TG-DTA thermogravimetric and differential thermal analyzer
  • the present invention also includes a laminate having the cured film of the present invention between a first element having an electrode and a second element having an electrode, in which the electrode of the first element and the electrode of the second element are electrically connected via a through hole penetrating the cured film.
  • this laminate will also be referred to as laminate A.
  • laminate of the present invention will be described below.
  • the laminate A of the present invention has the cured film of the present invention between a first element having an electrode and a second element having an electrode, and the electrode of the first element and the electrode of the second element are electrically connected via a through hole that penetrates the cured film.
  • the cured film provided between the electrode of the first element (hereinafter also referred to as the first electrode) and the electrode of the second element (hereinafter also referred to as the second electrode) acts as an insulating layer, thereby suppressing short circuit of current.
  • the conventional insulating layer used a hard inorganic material such as SiN or SiO 2 , if warping occurs during the formation of the insulating layer or the formation of the laminate, it cannot be resolved by stress relaxation, and as a result, the element warps and the electrodes are easily displaced or cracked due to this.
  • high electrical connection reliability can be achieved by using a cured film made of a resin that is more flexible than inorganic materials as an insulating layer.
  • the resin composition of the present invention that is the source of the cured film can fill the unevenness and make the bonding surface flat even if the element has unevenness, so that a laminate having high electrical connection reliability can be obtained.
  • the conventional insulating layer was formed by vapor deposition, it took a long time to form it, but the cured film of the laminate of the present invention can be formed, for example, by applying and curing a resin composition, so that production efficiency can be improved.
  • being electrically connected refers to a state in which the first electrode and the second electrode are connected by a conductive material or the like filled in the through hole.
  • the first element and the second element are not particularly limited, and circuit elements in which elements, wiring, and electrodes are formed can be used.
  • a sensor circuit element provided with a pixel section (pixel region), a circuit element equipped with a peripheral circuit section such as a logic circuit that executes various signal processing related to the operation of the solid-state imaging device, etc. can be used.
  • the material of the electrodes of the first element and the second element and the conductive material are not particularly limited, and conventional electrode materials such as gold, copper, and aluminum can be used.
  • the thickness of the cured film is not particularly limited, but is preferably from 10 ⁇ m to 300 ⁇ m. When the thickness of the cured film is within the above range, the function as an insulating layer can be more effectively exhibited, and the displacement or cracking of the electrodes can be more effectively suppressed.
  • the thickness of the cured film is more preferably 20 ⁇ m or more, and even more preferably 30 ⁇ m or more, and more preferably 200 ⁇ m or less, and even more preferably 100 ⁇ m or less.
  • the laminate A of the present invention preferably has an inorganic layer between the first element and the second element.
  • the insulating properties are improved, and a laminate having better connection reliability can be obtained.
  • the insulating layer is mainly the cured film, the effect of the inorganic layer can be exerted while the warping generated in the element and the laminate can be eliminated by reducing the thickness of the inorganic layer.
  • the material of the inorganic layer is not particularly limited, and examples thereof include SiN, SiO 2 , and Al 2 O 3. Among these, SiN and SiO 2 are preferred because of their excellent insulating properties and heat resistance.
  • the thickness of the inorganic layer is preferably 1 nm or more, more preferably 5 nm or more, and even more preferably 10 nm or more, and is preferably 1 ⁇ m or less, more preferably 500 nm or less, and even more preferably 100 nm or less.
  • the laminate A of the present invention preferably has a barrier metal layer on the surface of the through hole.
  • the barrier metal layer has a role of preventing the diffusion of the conductive material (e.g., Cu atoms in the case of a Cu electrode) filled in the through hole into the cured film.
  • the conductive material e.g., Cu atoms in the case of a Cu electrode
  • the material of the barrier metal layer can be a known material such as tantalum, tantalum nitride, titanium nitride, silicon oxide, silicon nitride, etc.
  • the thickness of the barrier metal layer is not particularly limited, but from the viewpoint of further improving the connection reliability of the laminate, it is preferably 1 nm or more, more preferably 10 nm or more, more preferably 100 nm or less, and even more preferably 50 nm or less.
  • FIG. 1 shows a schematic diagram of one embodiment of the laminate A of the present invention.
  • the laminate A of the present invention has a structure in which a first element 1 and a second element 2 having electrodes 3 are bonded via a cured film 4, and the electrodes 3 on the first element 1 and the second element 2 are electrically connected through a conductive material filled in a through hole 5 provided in the cured film 4.
  • the cured film 4 portion corresponding to the insulating layer was made of a hard inorganic material, so when warping occurred in the element or laminate, it was not possible to eliminate this by stress relaxation, and the electrodes were prone to misalignment and cracking.
  • the use of an organic compound having flexibility in the insulating layer can eliminate warping of the element or laminate, and therefore, misalignment and cracking of the electrodes can be suppressed.
  • Figure 2 shows a schematic diagram of one embodiment of the laminate A of the present invention.
  • an inorganic layer 6 is provided between the cured films 4, which enhances the insulating properties.
  • the thickness of the inorganic layer 6 of the present invention may be much thinner than the insulating layer of a conventional laminate, so it does not hinder the elimination of warping of the element or laminate.
  • the inorganic layer 6 is provided between the cured films 4, but it may be provided on the first element 1 and the second element 2.
  • the inorganic layer 6 is provided on the cured film 4 on the first element 1 side and the second element 2 side, but it may be provided on only one of them.
  • a barrier metal layer 7 is provided on the surface of the through hole 5.
  • the conductive material filled in the through hole 5 is less likely to diffuse into the cured film 4, so that short circuits and poor conduction can be further suppressed.
  • the method for producing the laminate A of the present invention includes, for example, a process for forming a cured film by forming a film of the resin composition of the present invention on the electrode-formed surfaces of a first element having an electrode and a second element having an electrode, and curing the film; a process for forming a through hole in each of the cured films; a process for filling each of the through holes with a conductive material; a process for polishing the surfaces of the first element and the second element on which the conductive material is filled to form a bonding electrode; and a process for bonding the first element on which the bonding electrode is formed and the second element on which the bonding electrode is formed so that the bonding electrodes are bonded to each other.
  • Such a method for producing a laminate is also one aspect of the present invention.
  • the method for producing the laminate of the present invention first involves forming a film of the resin composition of the present invention on the electrode-formed surfaces of a first element having an electrode and a second element having an electrode, and curing the film to form a cured film.
  • the first and second elements having the electrodes and the resin composition may be the same as the first and second elements having the electrodes of the laminate of the present invention and the resin composition of the present invention.
  • the step of forming the cured film is performed after forming a film of the resin composition of the present invention and drying the solvent.
  • the method for forming the film is not particularly limited, and a conventionally known method such as spin coating can be used.
  • the solvent drying conditions are not particularly limited, but from the viewpoint of reducing the remaining solvent and improving the heat resistance of the cured film, it is preferable to heat the film at a temperature of preferably 70° C. or higher, more preferably 100° C. or higher, and preferably 250° C. or lower, more preferably 200° C. or lower, for example, for 30 minutes, more preferably for about 1 hour.
  • the curing conditions are not particularly limited, but from the viewpoint of sufficiently progressing the curing reaction and further improving the heat resistance, it is preferable to heat for, for example, 1 hour or more, more preferably 2 hours or more at a temperature of preferably 200° C.
  • the upper limit of the heating time is not particularly limited, but from the viewpoint of suppressing thermal decomposition of the cured film, it is preferably 3 hours or less.
  • the method for producing a laminate of the present invention then carries out a step of forming through holes in each of the cured films.
  • the through-hole may be patterned.
  • the method for forming the through-hole is not particularly limited, and the through-hole may be formed by laser irradiation such as CO2 laser or etching.
  • the through-hole is formed so as to penetrate the other layers and expose the electrode surface of the element.
  • the method for producing a laminate of the present invention then includes a step of forming an inorganic layer and/or a barrier metal layer, if necessary.
  • the inorganic layer and the barrier metal layer may be the same as those in the laminate of the present invention.
  • the inorganic layer and the barrier metal layer may be formed by sputtering, vapor deposition, or the like.
  • the step of forming the inorganic layer is preferably carried out before and/or after the step of forming the cured film, and the step of forming the barrier metal layer is preferably carried out after the step of forming the through hole.
  • the method for producing a laminate of the present invention then includes a step of filling each of the through holes with a conductive material.
  • the method for filling the through holes with the conductive material can be plating or the like.
  • the conductive material may be the same as the conductive material of the laminate of the present invention.
  • the method for producing a laminate of the present invention then includes a step of polishing the surfaces of the first element and the second element on the side filled with the conductive material to form bonding electrodes.
  • the conductive material formed in the unnecessary portion is removed by grinding to form a bonding electrode connecting the electrodes formed on the two elements.
  • the polishing is preferably performed by planarizing and removing the layer formed of the conductive material until the cured film is exposed or, if there is an inorganic layer, the inorganic layer is exposed.
  • the polishing method is not particularly limited, and for example, a chemical mechanical polishing method can be used.
  • the present invention also provides a method for producing an element having a bonding electrode, the method comprising the steps of forming a film of the resin composition of the present invention on a surface of the element having an electrode, and curing the film to form a cured film, forming through-holes in the cured film, filling the through-holes with a conductive material, and polishing the surface of the element to form a bonding electrode.
  • the element having the bonding electrode is a member for forming a laminate by bonding the bonding electrodes between the elements together.
  • the method for producing a laminate of the present invention then includes a step of bonding the first element having the bonding electrode formed thereon and the second element having the bonding electrode formed thereon such that the bonding electrodes are bonded to each other.
  • the resin composition of the present invention can fill in the unevenness even when the element surface has unevenness, and therefore the bonding surface of the obtained cured film is flat and can be bonded reliably, thereby improving the reliability of electrical connection.
  • the first element and the second element can be bonded to each other by a method of melting and connecting the electrodes and the connecting electrodes by heat treatment, etc.
  • the heat treatment is usually performed at 400° C. for about 4 hours.
  • the uses of the laminate of the present invention are not particularly limited, but since it has high electrical connection reliability and can suppress warping and cracking of the elements and the laminate, especially when thin elements are bonded to each other, it can be suitably used for laminates that constitute semiconductor devices and imaging devices.
  • a semiconductor device and an imaging device having such a laminate of the present invention also constitute the present invention.
  • the cured film of the present invention can be suitably used as an insulating layer for a laminate having a structure such as the laminate A described above, but can also be suitably used as an insulating layer for a laminate having a structure in which a support substrate is laminated on the chip-bearing surface of an element having a plurality of chips.
  • a laminate having the cured film of the present invention between such a support substrate and a third element, the third element having a first surface and a second surface, the first surface having a plurality of chips, and the cured film laminated on the first surface side is also one aspect of the present invention (hereinafter also referred to as laminate B).
  • the laminate B of the present invention has the cured film of the present invention between the supporting substrate and the third element.
  • the supporting substrate may be, for example, glass, single crystal silicone, etc.
  • the third element is the same as the first and second elements.
  • the cured film is also as described above.
  • the third element has a first surface and a second surface, the first surface has a plurality of chips, and the cured film is laminated on the first surface side.
  • the surface of the third element having a plurality of chips has a larger surface unevenness due to the chips.
  • the resin composition that is the base of the cured film can sufficiently fill the gaps and make the connection surface flat even if the surface has a large unevenness, so that the connection reliability with the support substrate can be improved and warping and cracking of the element can be suppressed.
  • the number of the chips is not particularly limited as long as it is two or more.
  • the laminate B of the present invention preferably has an inorganic layer between the supporting substrate and the cured film.
  • the inorganic layer may be the same as the inorganic layer of the laminate A.
  • the laminate B of the present invention further has a fourth element on the second surface of the third element, and that the third element and the fourth element are electrically connected to each other.
  • the laminate B of the present invention has a large unevenness on the surface due to the chip, but is sufficiently bonded to the support substrate by the cured film of the present invention. Therefore, warping and cracking of the third element are suppressed, and warping and cracking of the fourth element laminated on the third element are also suppressed. As a result, the misalignment and cracking of the electrodes between elements are also suppressed, and the reliability of the electrical connection can be improved.
  • the fourth element can be the same as the first to third elements.
  • FIG. 3 shows a schematic diagram of one embodiment of the laminate B of the present invention.
  • the laminate B of the present invention has a structure in which a plurality of chips 9 electrically connected to the third element 8 are laminated on the first surface of the third element 8, a fourth element 10 electrically connected to the third element 8 is laminated on the second surface, which is the opposite surface of the first surface, and the first surface of the third element 8 and the supporting substrate 11 are laminated via a cured film 4.
  • the cured film of the resin composition of the present invention is used as the cured film, which sufficiently fills the unevenness between the chip 9 and the supporting substrate 11 to flatten the connection surface, and warping and poor adhesion of the elements and chips can be eliminated, thereby providing high electrical connection reliability between the elements.
  • Figure 4 shows a schematic diagram of one embodiment of the laminate B of the present invention.
  • an inorganic layer 6 is provided between the cured film 4 and the support substrate 11, which further enhances the insulating properties.
  • the thickness of the inorganic layer 6 of the present invention can be significantly thinner than the insulating layer of a conventional laminate, so it does not hinder the elimination of warping of the element or laminate.
  • the application of the laminate B of the present invention is not particularly limited, but like the laminate A, it is suitable for use in imaging devices and semiconductor devices. Such an imaging device and a semiconductor device having the laminate B of the present invention are also part of the present invention.
  • the present invention provides a resin composition that has excellent heat resistance and flexibility, and can flatten the connection surface even when the element surface has irregularities, thereby providing high electrical connection reliability between elements; a cured film using the resin composition; a laminate having the cured film; an imaging device and a semiconductor device having the laminate; a method for manufacturing the laminate; and a method for manufacturing an element having a joining electrode used in manufacturing the laminate.
  • FIG. 1 is a schematic diagram showing one embodiment of a laminate of the present invention.
  • FIG. 1 is a schematic diagram showing one embodiment of a laminate of the present invention.
  • FIG. 1 is a schematic diagram showing one embodiment of a laminate of the present invention.
  • FIG. 1 is a schematic diagram showing one embodiment of a laminate of the present invention.
  • organosilicon compound a 320 g of phenyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 198.29), 8.8 g of sodium hydroxide, 6.6 g of water, and 263 mL of 2-propanol were added to a reaction vessel equipped with a reflux condenser, a thermometer, and a dropping funnel. Heating was started with stirring under a nitrogen stream. Stirring was continued for 6 hours from the start of reflux, and then the mixture was allowed to stand overnight at room temperature. The reaction mixture was then transferred to a filter, pressurized with nitrogen gas, and filtered. The obtained solid was washed once with 2-propyl alcohol, filtered, and then dried under reduced pressure at 80°C to obtain 330 g of a colorless solid (DD-ONa).
  • a 100 mL flask was fitted with a cooling tube, mechanical stirrer, Dean-Stark tube, oil bath and thermometer protection tube, and the inside of the flask was replaced with nitrogen.
  • 5.0 g of (DD(Me)-OH), 2.5 g of octamethylcyclotetrasiloxane (D4), 0.5 g of RCP-160M (strongly acidic cation exchange resin, manufactured by Mitsubishi Chemical Corporation: water content 23.4 mass%) and 51.0 mL of dehydrated toluene were placed in the flask. Reflux was performed for 1 hour, and 22.4 mL of toluene and 0.12 g of water contained in RCP-160M at 23.4 mass% were extracted.
  • organosilicon compound a having the structure of the following formula (8), where m is 30 and n (the number of DMS chains) is an average of 4.
  • organosilicon compound b SST-3PM4 manufactured by Gelest was used as organosilicon compound b. Note that SST-3PM4 is an organosilicon compound that does not satisfy the above general formula (1).
  • a Dean-Stark trap and a condenser were attached to the flask, and the mixture was heated to reflux at 100 ° C. for 1 hour, and further refluxed at 170 ° C. for 4 hours to obtain an imide compound having amines at both ends.
  • citraconic anhydride manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 112.08 was added, and the mixture was stirred while heating at 120° C. for 10 minutes, and further heated at 170° C. for 20 minutes to obtain a compound having an imide structure represented by the following formula (9) (resin A, weight average molecular weight 9000).
  • l represents the number of repeating units.
  • Modifier A (BYK-320, manufactured by BYK-Chemie): polymethylalkylsiloxane having a polyether modifying group, molecular weight 22,000 Modifier B (BYK-325N, manufactured by BYK-Chemie): polymethylalkylsiloxane having a polyether modifying group, molecular weight 17,000 Modifier C (KP-341, manufactured by Shin-Etsu Chemical Co., Ltd.): a silicone compound having a polyether modifying group, molecular weight 18,000 Modifier D (KP-112, Shin-Etsu Chemical Co., Ltd.): a silicone compound having a polyether modifying group, molecular weight 20,000 Modifier E (BYK-326, manufactured by BYK-Chemie): polymethylalkylsiloxane having a polyether modifying group, molecular weight 25,000 Modifier F (BYK-307, manufactured by BYK-320, manufactured by BYK-Chemie): poly
  • Example 1 A resin composition was obtained by adding cyclopentanone as a solvent to 100 parts by weight of the organosilicon compound, 0.5 parts by weight of modifier A, 3.2 parts by weight of a crosslinking agent (silicate MS-51, manufactured by Mitsubishi Chemical Corporation), 0.2 parts by weight of a catalyst (ZC-162, manufactured by Matsumoto Fine Chemical Co., Ltd.), and 1.0 part by weight of resin A (heat-resistant additive) so that the viscosity of the resulting composition was 1200 cP.
  • a crosslinking agent silicate MS-51, manufactured by Mitsubishi Chemical Corporation
  • ZC-162 0.2 parts by weight of a catalyst
  • resin A heat-resistant additive
  • Example 2 to 12 Comparative Examples 1 to 8
  • Resin compositions were obtained in the same manner as in Example 1, except that the types and amounts of the organosilicon compound, modifier, and solvent were changed so as to obtain the compositions shown in Tables 1 and 2.
  • the resin compositions in the examples and comparative examples all had a viscosity of 1200 cP.
  • thermogravimetric and differential thermal analyzer STA7200, manufactured by Hitachi High-Tech Science Corporation
  • the grooved portion of the silicon wafer on the surface of the cured product after heating and curing was observed using a laser microscope (OLS4100; manufactured by Olympus), and the depth of the grooved portion was measured.
  • the groove depth measured by a laser microscope was divided by the original groove depth of the wafer, 10 ⁇ m, to obtain the amount of recess (%) (value expressed by the following formula), and the groove filling ability (flattening ability) was evaluated according to the following criteria.
  • the values in the table are the values of the amount of recess (%).
  • Dimple amount (%) (groove depth ( ⁇ m) after applying and curing resin composition)/10 ( ⁇ m) ⁇ 100 ⁇ : Dent is less than 7% ⁇ : Dent is 7% or more but less than 10% ⁇ : Dent is 10% or more
  • the present invention provides a resin composition that has excellent heat resistance and flexibility, and can flatten the connection surface even when the element surface has irregularities, thereby providing high electrical connection reliability between elements; a cured film using the resin composition; a laminate having the cured film; an imaging device and a semiconductor device having the laminate; a method for manufacturing the laminate; and a method for manufacturing an element having a joining electrode used in manufacturing the laminate.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Formation Of Insulating Films (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
PCT/JP2024/001676 2023-01-23 2024-01-22 樹脂組成物、硬化膜、積層体、撮像装置、半導体装置、積層体の製造方法及び接合電極を有する素子の製造方法 Ceased WO2024157936A1 (ja)

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EP24747263.2A EP4656684A1 (en) 2023-01-23 2024-01-22 Resin composition, cured film, laminate, imaging device, semiconductor device, method for manufacturing laminate, and method for manufacturing element having bonding electrode
CN202480006271.XA CN120380085A (zh) 2023-01-23 2024-01-22 树脂组合物、固化膜、层叠体、拍摄装置、半导体装置、层叠体的制造方法和具有接合电极的元件的制造方法
KR1020257019164A KR20250135777A (ko) 2023-01-23 2024-01-22 수지 조성물, 경화막, 적층체, 촬상 장치, 반도체 장치, 적층체의 제조 방법 및 접합 전극을 갖는 소자의 제조 방법
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006191081A (ja) 2004-12-30 2006-07-20 Magnachip Semiconductor Ltd 受光領域が拡張されたイメージセンサ及びその製造方法
JP2020100819A (ja) * 2018-12-20 2020-07-02 東レ株式会社 樹脂組成物、硬化膜およびその製造方法
WO2021261403A1 (ja) * 2020-06-22 2021-12-30 積水化学工業株式会社 積層体、硬化性樹脂組成物、積層体の製造方法、接合電極を有する基板の製造方法、半導体装置及び撮像装置
WO2022112662A1 (en) * 2020-11-30 2022-06-02 Brightplus Oy Coating for glass articles
WO2022215759A2 (ja) * 2021-08-11 2022-10-13 Jnc株式会社 シロキサンポリマー組成物、硬化物、電子部品、光学部品および複合部材
WO2023120625A1 (ja) * 2021-12-23 2023-06-29 積水化学工業株式会社 硬化性樹脂組成物、硬化膜、積層体、撮像装置、半導体装置、積層体の製造方法及び接合電極を有する素子の製造方法
JP2023094125A (ja) * 2021-12-23 2023-07-05 積水化学工業株式会社 樹脂硬化物、硬化性樹脂組成物、積層体、撮像装置、半導体装置、積層体の製造方法及び接合電極を有する素子の製造方法

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006191081A (ja) 2004-12-30 2006-07-20 Magnachip Semiconductor Ltd 受光領域が拡張されたイメージセンサ及びその製造方法
JP2020100819A (ja) * 2018-12-20 2020-07-02 東レ株式会社 樹脂組成物、硬化膜およびその製造方法
WO2021261403A1 (ja) * 2020-06-22 2021-12-30 積水化学工業株式会社 積層体、硬化性樹脂組成物、積層体の製造方法、接合電極を有する基板の製造方法、半導体装置及び撮像装置
WO2022112662A1 (en) * 2020-11-30 2022-06-02 Brightplus Oy Coating for glass articles
WO2022215759A2 (ja) * 2021-08-11 2022-10-13 Jnc株式会社 シロキサンポリマー組成物、硬化物、電子部品、光学部品および複合部材
WO2023120625A1 (ja) * 2021-12-23 2023-06-29 積水化学工業株式会社 硬化性樹脂組成物、硬化膜、積層体、撮像装置、半導体装置、積層体の製造方法及び接合電極を有する素子の製造方法
JP2023094125A (ja) * 2021-12-23 2023-07-05 積水化学工業株式会社 樹脂硬化物、硬化性樹脂組成物、積層体、撮像装置、半導体装置、積層体の製造方法及び接合電極を有する素子の製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4656684A1

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TW202449031A (zh) 2024-12-16

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