Resin composition, cured film, laminate, imaging device, semiconductor device, method for manufacturing laminate, and method for manufacturing element having bonding electrode

Abstract

The present invention provides: a resin composition which has excellent heat resistance and flexibility, can smooth a connection surface even when the surface of an element has irregularities, and can impart 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 bonding electrode and used for manufacturing the laminate. The present invention is a resin composition containing an organic silicon compound and a modifier, wherein the modifier is held for one hour after raising the temperature of the single substance from room temperature to 300°C in air at a temperature raising rate of 10°C / min, and then the temperature is raised to 400°C at a temperature raising rate of 10°C / min and the thermal weight reduction amount before and after the single substance is held for 3 hours at 400°C is 10% or less; the organic silicon compound and 1 part by weight of the modifier with respect to 100 parts by weight of the organic silicon compound are added to ethyl benzoate to prepare a sample having a viscosity of 45 cP at 25°C; and the contact angle of the sample with the silicon wafer when the sample is dropped onto the silicon wafer is at least 9° and at most 20°.

Description

Resin composition, cured film, laminate, imaging device, semiconductor device, method for manufacturing laminate, and method for manufacturing element having bonding electrode

[0001] 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 producing the laminate, and a method for producing an element having a bonding electrode used in producing the laminate.

[0002] As semiconductor devices become more sophisticated, three-dimensional structures are being developed, in which multiple semiconductor chips are stacked. To manufacture such a stack of multiple semiconductor chips, a damascene process is first used to form a bonding surface on the electrode surfaces of two elements, each of which has two electrodes. The bonding electrodes are then stacked on top of each other so that the bonding electrodes face each other, and a heat treatment is then performed to manufacture the stack (see Patent Document 1).

[0003] Japanese Patent Application Laid-Open No. 2006-191081

[0004] In the manufacture of the laminate, a high-temperature treatment of 400°C for 4 hours is carried out when bonding the electrodes, so the insulating layer used to form the bonding surface is required to have high heat resistance. ２ Insulating inorganic materials such as the above are used. However, insulating layers made of inorganic materials are prone to warping of elements. When warping occurs in elements, the connection positions of electrodes may shift or the electrodes may crack when the elements are formed into a laminate, which may reduce the connection reliability of the laminate. Furthermore, in recent years, the performance of semiconductor devices has improved, and elements have become larger and thinner, making element warping more likely to occur. Furthermore, as elements have become more multifunctional in recent years, unevenness of several μm to several tens of μm may be formed on the surface of the element on which the insulating layer is formed. When elements having unevenness are directly bonded, from the viewpoint of connection reliability between electrodes, it is necessary to fill the surface of the wafer on which the elements are formed with an insulating layer to flatten the connection surface before connection. Therefore, there is a demand for materials that can form insulating layers that are excellent in heat resistance, flexibility, and element flattening properties.

[0005] The present invention aims to provide a resin composition that has excellent heat resistance and flexibility, and is capable of flattening a connection surface even when the element surface has irregularities, thereby imparting 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.

[0006] The present invention includes the following Disclosures 1 to 23. The present invention is described in detail below. [Disclosure 1] A resin composition containing an organosilicon compound and a modifier, wherein the 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, and the thermal weight loss before and after holding at 400°C for 3 hours is 10% or less; 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, and when the sample is dropped onto a silicon wafer, the contact angle of the sample with the silicon wafer is 9° or more and 20° or less. [Disclosure 2] A resin composition further containing a solvent is prepared using the solvent to form a solution having a viscosity of 1200 cP, and the solution is spin-coated onto a silicon wafer at 1500 rpm for 10 seconds. After the solvent dries, the solution is cured at 300°C for 1 hour to form a cured resin film having a thickness of 10 μm or more. When the surface free energy of the cured resin film is 27 mJ / m ２ The resin composition according to Disclosure 1. [Disclosure 3] The resin composition according to Disclosure 1 or 2, comprising a metal catalyst, a crosslinking agent, and a heat-resistant additive. [Disclosure 4] The resin composition according to any one of Disclosures 1 to 3, wherein the organosilicon compound has a structure represented by the following general formula (1): Here, R ０ , R １ and R ２each 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. m and n each represent an integer of 1 or greater. [Disclosure 5] The resin composition according to any one of Disclosures 1 to 4, wherein the modifier has a polyether-modified group. [Disclosure 6] The resin composition according to any one of Disclosures 1 to 5, wherein the content of the modifier is 0.01 parts by weight or more and 10 parts by weight or less per 100 parts by weight of the organosilicon compound. [Disclosure 7] The resin composition according to any one of Disclosures 1 to 6, wherein the modifier has a weight-average molecular weight of 4,000 or more and 30,000 or less. [Disclosure 8] The resin composition according to Disclosure 2, wherein the resin composition, when cured at 300°C for 1 hour after drying the solvent, has a 1% weight loss temperature of 460°C or higher. [Disclosure 9] The resin composition according to any one of Disclosures 1 to 8, wherein the resin composition is used to form an insulating layer on the textured surface of a device having a textured surface. [Disclosure 10] A resin composition containing an organosilicon compound and a modifier, wherein the organosilicon compound has a structure represented by the following general formula (1), and the modifier has a polyether modifying group: Here, R ０ , R １ and R ２each 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. m and n each represent an integer of 1 or greater. [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. [Disclosure 13] The laminate according to Disclosure 12, having an inorganic layer between the first element and the second element. [Disclosure 14] The laminate according to Disclosure 12 or 13, having a barrier metal layer on the surface of the through-hole. [Disclosure 15] An imaging device having the laminate according to any one of Disclosures 12 to 14. [Disclosure 16] A semiconductor device having the laminate according to any one of Disclosures 12 to 14. [Disclosure 17] A method for manufacturing a laminate, comprising the steps of: forming a film of the resin composition according to any one of Disclosures 1 to 10 on the electrode-formed surfaces of a first element having electrodes and a second element having electrodes, and curing the film to form a cured film, forming through holes in each of the cured films, filling each of the through holes with a conductive material, polishing the surfaces of the first element and the second element on the sides filled with the conductive material to form bonding electrodes, and bonding the first element on which the bonding electrodes are formed and the second element on which the bonding electrodes are formed so that the bonding electrodes are bonded to each other. [Disclosure 18] A method for manufacturing an element having bonding electrodes, comprising the steps of forming a film of the resin composition according to any one of Disclosures 1 to 10 on the electrode-formed surfaces of an element having electrodes, 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 surfaces of the element on the sides filled with the conductive material to form bonding electrodes. [Disclosure 19] A laminate having the cured film according to Disclosure 11 between a support substrate and a third element, wherein the third element has a first surface and a second surface, the first surface having a plurality of chips, and the cured film is laminated on the first surface side. [Disclosure 20] The laminate according to Disclosure 19, having an inorganic layer between the support substrate and the cured film.[Disclosure 21] The stack 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. [Disclosure 22] An imaging device comprising the stack according to any one of Disclosures 19 to 21. [Disclosure 23] A semiconductor device comprising the stack according to any one of Disclosures 19 to 21.

[0007] The resin composition of the present invention contains an organosilicon compound. When the resin composition of the present invention is used for an insulating layer of a laminate in which elements are stacked, the insulating layer is formed as a cured film of an organic resin composition, thereby increasing the flexibility of the insulating layer, suppressing warpage of the elements and improving the reliability of electrical connection. Furthermore, by using an organosilicon compound in the resin composition, an insulating layer having excellent heat resistance and flattening properties for elements can be obtained.

[0008] The organosilicon compound is preferably silsesquioxane. Silsesquioxane has high heat resistance while having flexibility comparable to that of organic compounds, so by using a cured film containing silsesquioxane as the insulating layer of a laminate, warping and cracking of the substrate can be suppressed and electrical connection reliability can be improved. The silsesquioxane is not particularly limited as long as it is thermosetting, but it is preferable that one molecule contains structures represented by the following structural formulas (A) and (B), as this further suppresses warping and cracking of the substrate.

[0009] In structural formulas (A) and (B), R Ａ , R Ｂ each independently represents an aliphatic group, an aromatic group, or hydrogen, j and k are repeating units, and each represents an integer of 1 or more.

[0010] The organosilicon compound more preferably has a structure represented by the following general formula (1). When the organosilicon compound has the structure of the following general formula (1), heat resistance is further improved, and when used in the insulating layer of a laminate, electrode misalignment and cracking can be further suppressed, thereby improving electrical connection reliability. Furthermore, the organosilicon compound represented by the following general formula (1) can bond with the modifier described below, allowing the modifier to be dispersed throughout the resin composition, thereby further improving the planarization of the element when used in the insulating layer of a laminate. Furthermore, it can more easily satisfy the contact angle with a silicon wafer described below.

[0011] Here, R ０ , R １ and R ２ 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. m and n each represent an integer of 1 or greater.

[0012] In the above general formula (1), R ０ Each of R 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. 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. ０ When the alkyl group is a phenyl group, an alkyl group having 1 to 20 carbon atoms, or an arylalkyl group, higher heat resistance can be exhibited.

[0013] In the above general formula (1), R １ and R ２ Each of R 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. １ and R ２ is preferably a phenyl group, an alkyl group or an arylalkyl group having 1 to 20 carbon atoms, and more preferably a phenyl group or a methyl group. １ and R２ When the alkyl group is a phenyl group, an alkyl group having 1 to 20 carbon atoms, or an arylalkyl group, higher heat resistance can be exhibited.

[0014] In the general formula (1), m and n each represent an integer of 1 or greater and represent the number of repeating units. m is preferably 30 or greater, more preferably 50 or greater, and preferably 100 or less. n is preferably 1 or greater, more preferably 3 or greater, and even more preferably 4 or greater, and is preferably 8 or less, more preferably 6 or less.

[0015] The organosilicon compound preferably has a reactive site. By using 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 further suppressed when used in the insulating layer of a laminate. In addition, since organosilicon compounds have excellent heat resistance, decomposition of the cured film due to high-temperature treatment performed during the manufacture of electronic components can be further suppressed. Examples of the reactive site include a hydroxyl group and an alkoxy group. Examples of the organosilicon compound having the reactive site include organosilicon compounds represented by the general formula (1) above.

[0016] 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.

[0017] The weight-average molecular weight of the organosilicon compound is not particularly limited, but is preferably 5,000 or more and 150,000 or less. Having the molecular weight of the organosilicon compound within this range improves film-forming properties during application, further enhancing planarization performance, and further suppressing element warpage and electrode misalignment and cracking when used in the insulating layer of a laminate. The molecular weight of the organosilicon compound 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 weight-average molecular weight of the organosilicon compound is measured as a polystyrene-equivalent molecular weight by gel permeation chromatography (GPC). Using THF as the elution solvent and a Time-MB-M 6.0 x 150 mm (manufactured by Waters Corporation) or an equivalent column, the weight-average molecular weight can be calculated using polystyrene standards.

[0018] The organosilicon compound is preferably dissolved in the resin composition, and is preferably not present in a dispersed state having a particular shape such as particulate form, from the viewpoints of improving film-forming properties during application, further enhancing planarization performance, and further suppressing warping of elements and misalignment or cracking of electrodes when used in the insulating layer of a laminate.

[0019] The resin composition of the present invention contains a modifier. By selecting a modifier that has a thermal weight loss amount described below and that satisfies the contact angle with a silicon wafer described below when used in combination with the 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 imparted between the elements. In order to flatten the connection surface, it is necessary to form a film that is stable even at high temperatures. Therefore, simply using a modifier with a flexible organosilicon compound may cause film cracking and poor flatness of the connection surface.

[0020] The modifier alone is heated in air at a rate of 10°C / min from room temperature to 300°C, held for 1 hour, then heated to 400°C at a rate of 10°C / min, and held at 400°C for 3 hours. The modifier exhibits a thermal weight loss of 10% or less before and after 3 hours at 400°C. By ensuring that the modifier's thermal weight loss under the above conditions falls within the above range, thermal decomposition of the modifier and resulting cracking of the insulating layer can be suppressed even after high-temperature treatment, and when used on a device, the modifier can adequately fill in the irregularities on the device surface. From the perspective of further enhancing the heat resistance of the cured resin composition, the thermal weight loss is preferably 8% or less, and more preferably 5% or less. The thermal weight loss can be adjusted by adjusting the molecular weight and the type of functional group. The thermal weight loss can be measured using a simultaneous thermogravimetry and differential thermal analyzer (TG-DTA; STA7200, manufactured by Hitachi High-Tech Science Corporation or an equivalent), specifically by the following method.

[0021] Using a thermogravimetric differential thermal analyzer (TG-DTA; STA7200, manufactured by Hitachi High-Tech Science Corporation or an equivalent), the modifier is heated in air from 25°C to 300°C at a heating rate of 10°C / min and held 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 for 3 hours after reaching 400°C. The thermal weight loss is calculated from the weight at each temperature when it first reaches 400°C and the weight at 400°C after 3 hours have passed.

[0022] The modifier is not particularly limited as long as it satisfies the requirements for the thermal weight loss and the contact angle with respect to the silicon wafer described below, but examples of compounds that easily satisfy these requirements include polyether compounds, aralkyl compounds, polyester compounds, silicone compounds, etc. Among these, 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 requirements for the thermal weight loss 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.

[0023] The content of the modifier is not particularly limited, but since this allows for a more planar 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, and even more preferably 0.3 parts by weight or more, and is 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.

[0024] The modifier preferably has a weight-average molecular weight of 4,000 or more and 30,000 or less. When the modifier has a polymerization average molecular weight within the above range, 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 20,000 or more, more preferably 30,000 or less, and even more preferably 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.

[0025] The resin composition of the present invention preferably contains 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 to an element, and when used on an element, it is possible to fill in the irregularities on the element surface to make it more flat. The solvent may be composed of a single component or a mixture of multiple components.

[0026] The solvent is not particularly limited, but examples thereof include ketone solvents such as cyclopentanone, ester solvents such as ethyl benzoate, lactone solvents, lactam solvents, glycol ether solvents, etc. Among these, cyclopentanone is preferred because it can further flatten the connection surface of the element.

[0027] The solvent preferably has a boiling point of 150°C or higher and 250°C or lower. Having the boiling point of the solvent within the above range can further enhance planarization performance. Furthermore, having the boiling point of the solvent satisfy the lower limit can suppress the occurrence of foreign matter abnormalities caused by the solvent volatilizing in string-like forms and adhering to the coating film during spin coating. 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. Examples of solvents having a boiling point within the above range include aromatic organic solvents, lactam organic solvents, and lactone organic solvents. Lactam organic solvents are organic solvents of heterocyclic compounds having -C(=O)NR- in the ring, and lactone organic solvents are organic solvents of heterocyclic compounds having -C(=O)- in the ring. Here, R represents a hydrocarbon. Specific examples of the compound 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), γ-butyrolactone (boiling point: 204°C), and γ-valerolactone (boiling point: 207°C).

[0028] The content of the solvent in the resin composition is preferably 50% by weight or less. When the content of the solvent in the resin composition is within the above range, shrinkage due to volatilization of the solvent during curing is reduced, making it less likely that unevenness will occur in the resulting cured film and allowing the connection surface to be flat. As a result, the bonding reliability of the element can be improved and the electrical connection reliability can also be improved. The content of the solvent is preferably 45% by weight or less, more preferably 40% by weight or less, and even more preferably 35% by weight or less. There is no particular limitation on the lower limit of the content of the solvent, but from the viewpoint of further improving flattening performance, it is preferably 30% by weight or more.

[0029] The content of the solvent is preferably 50 parts by weight or more and 100 parts by weight or less relative to 100 parts by weight of the organosilicon compound. By having the content of the solvent relative to the organosilicon compound in the above range, the planarization performance of the element surface can be further improved. 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.

[0030] The resin composition of the present invention preferably contains a metal catalyst that promotes the curing reaction. By including a metal catalyst in the resin composition, the resin composition can be cured more completely, and decomposition of the cured film due to high-temperature treatment can be further suppressed. Examples of the metal catalyst include organotin compounds such as dibutyltin dilaurate and stannous acetate, metal carboxylates such as zinc naphthenate, zirconia compounds such as zirconium tetraacetylacetonate, and titanium compounds. Among these, zirconium tetraacetylacetonate and dibutyltin dilaurate are preferred because they can further promote the curing of the resin composition. The metal catalyst remains even after the resin composition has cured. In other words, the cured film formed by curing the resin composition of the present invention preferably contains a metal catalyst that promotes the curing reaction.

[0031] 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.

[0032] The resin composition of the present invention preferably contains a crosslinking agent. By crosslinking between polymers of organosilicon compounds having the reactive sites with a crosslinking agent capable of reacting with the reactive sites of the organosilicon compounds, the crosslink density of the cured product is increased, and decomposition at high temperatures is further suppressed. As a result, when used in the insulating layer of a laminate, the generation of voids due to decomposition gases during high-temperature treatment, as well as the resulting electrode misalignment and deterioration of electrical connection reliability during connection, can be further suppressed. Examples of the crosslinking agent include, when the reactive sites are silanol groups, alkoxysilane compounds such as dimethoxysilane compounds, trimethoxysilane compounds, diethoxysilane compounds, and triethoxysilane compounds, or silicate oligomers obtained by condensation of tetramethoxysilane compounds and tetraethoxysilane compounds. Among these, silicate oligomers are preferred from the viewpoints of improving crosslink density and heat resistance. Examples of alkoxysilane compounds include dimethoxydimethylsilane, trimethoxymethylsilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane. Examples of 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.).

[0033] 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 relative to 100 parts by weight of the organosilicon compound in the resin composition.By setting the content of the crosslinking agent within the above range, the crosslinking density of the cured film can be set within a suitable range.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.

[0034] The resin composition of the present invention preferably contains a heat-resistant additive. By using a heat-resistant additive in the resin composition, the cured product of the resin composition can be made to have better heat resistance. Examples of the heat-resistant additive include polyimide resins, epoxy resins, silicone resins, benzoxazine resins, cyanate resins, and phenolic resins. Among these, polyimide resins are preferred because they can particularly improve heat resistance.

[0035] The molecular weight of the heat-resistant additive is not particularly limited, but is preferably 5,000 or more and 150,000 or less. When the weight-average molecular weight of the heat-resistant additive is in the above range, it is possible to easily adjust the viscosity and solid content concentration of the resin composition within the range of the present invention. The molecular weight of the heat-resistant 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.

[0036] The content of the heat-resistant additive is not particularly limited, but from the viewpoint of further improving heat resistance, it is preferably 0.1 part by weight or more, more preferably 0.5 part 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.

[0037] When the heat-resistant additive is a polyimide, the polyimide preferably has a siloxane bond, which enhances compatibility with the organosilicon compound contained in the resin composition, thereby further suppressing surface roughness caused by precipitation of the polyimide during application.

[0038] When the polyimide has a siloxane bond, the ratio C / Si of carbon atoms to silicon atoms in the main chain structure of the polyimide is preferably 17 or less. When the ratio of carbon atoms to silicon atoms in the main chain structure of the polyimide is within the above range, compatibility with the organosilicon compound contained in the resin composition is further improved, and surface roughening during application can be further suppressed. The C / Si is more preferably 16.5 or less, and even more preferably 16 or less. There is no particular restriction on the lower limit of the C / Si, but from the viewpoint of practical use and further improving heat resistance at 400°C, it is preferably 4 or more. Note that the ratio C / Si of carbon atoms to silicon atoms in the main chain structure of the polyimide is the ratio of C to Si in the repeating unit and does not include C and Si at both ends. Furthermore, the C / Si is １ H-NMR, １３ C-NMR and ２９ The polyimide structure is obtained by Si-NMR, and the number of C atoms and Si atoms can be determined by measuring the number of repeating units of the main chain.

[0039] The polyimide preferably has a plurality of aromatic rings, which makes it possible to form a thick cured film that is less likely to crack when subjected to high-temperature treatment under various conditions.

[0040] The polyimide preferably has an oxazine ring or imide ring structure at at least one of its terminals, and more preferably has an oxazine ring or imide ring structure at both terminals. When the polyimide has an oxazine ring or imide ring structure at its terminal, surface roughening can be further suppressed when it is formed into a thick film. The oxazine ring and imide ring structure may have a substituent. In particular, the polyimide more preferably has any one of the structures represented by the following formulas (2) to (7) at at least one terminal, and particularly preferably has any one of the structures represented by the following formulas (2) to (7) at both terminals. In the following formulas, "*" represents the bonding site to a portion other than the terminal of the polyimide.

[0041]

[0042] The polyimide preferably has a weight-average molecular weight of 1,000 or more and 50,000 or less. Having the weight-average molecular weight of the polyimide within this range improves compatibility with organosilicon compounds and enhances handleability. The weight-average molecular weight is more preferably 2,000 or more, even more preferably 3,000 or more, and more preferably 35,000 or less, even more preferably 30,000 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 the elution solvent and a Time-MB-M 6.0 x 150 mm (manufactured by Waters Corporation) or an equivalent column, the weight-average molecular weight can be calculated using polystyrene standards.

[0043] The content of above-mentioned polyimide is preferably 0.5 parts by weight or more and 50 parts by weight or less with respect to 100 parts by weight of above-mentioned organosilicon compound.By making the content of polyimide within the above range, even if it is made into a thick cured film, it can be made into a cured film that is less likely to crack under high temperature treatment.The content of above-mentioned polyimide is preferably 0.7 parts by weight or more with respect to 100 parts by weight of organosilicon compound, more preferably 0.75 parts by weight or more, even more preferably 1 part by weight or more, 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.

[0044] The resin composition of the present invention may contain other additives such as a viscosity modifier, a filler, an adhesion promoter, etc. as needed. However, from the viewpoint of suppressing the amount of thermal decomposition at high temperatures and improving heat resistance, it is preferable that the resin composition does not contain a fluorescent agent.

[0045] The resin composition of the present invention is prepared by adding the organosilicon compound and 1 part by weight of the modifier per 100 parts by weight of the organosilicon compound to ethyl benzoate to prepare a sample having a viscosity of 45 cP at 25°C. When the sample is dropped onto a silicon wafer, the contact angle of the sample with the silicon wafer is 9° or more and 20° or less. The organosilicon compound and a specific amount of the modifier are dissolved in an ethyl benzoate solution having a specific viscosity, and the contact angle when dropped onto the silicon wafer is within the above range. This allows the resin composition to spread to the bottom of the recess, flattening the connection surface. From the viewpoint of further flattening the connection surface of the element, the contact angle is preferably 12° or more, more preferably 14° or more, and 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. More specifically, for example, when a compound having the structure represented by the above general formula (1) is used as the organosilicon compound and a compound having a polyether-modified group is used as the modifier, the contact angle can be easily adjusted to within the above range. The viscosity at 25°C can be measured by measuring the kinematic viscosity at 25°C and 10.0 rpm shear using an E-type viscometer (TVE100H, manufactured by Toki Sangyo Co., Ltd., or an equivalent product). The contact angle can be measured according to a method in accordance with JIS R3257, specifically, by the following method.

[0046] 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), and the contact angle of the sample with respect to the silicon wafer is measured.

[0047] The resin composition of the present invention further contains a solvent, and the resin composition is converted into a solution having a viscosity of 1200 cP at 25°C using the solvent. The solution is spin-coated onto a silicon wafer at 1500 rpm for 10 seconds, and 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 µm or more. When the surface free energy of the cured resin film is 27 mJ / m ２ When the surface free energy of the cured resin 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 the connection surface can be flattened even when used on an element having an uneven surface. From the viewpoint of further flattening the connection surface of the element, the surface free energy of the cured resin film is 30 mJ / m or more. ２ More preferably, it is 33 mJ / m or more. ２ More preferably, it is 38 mJ / m or more. ２ More preferably, 35 mJ / m or less ２ It is more preferable that the surface free energy of the cured resin film is equal to or less than 1000 kJ / cm 2 . 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 using 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 is not particularly limited as long as it can have the above viscosity and is completely volatilized when formed into a cured resin film, and for example, the same solvents as those described above can be used.

[0048] A solvent is added to the resin composition to make a solution with a viscosity of 1200 cP at 25°C. At room temperature, the solution is dropped onto the center of an 8-inch silicon wafer, and the resin composition is applied to the silicon wafer using a spin coater (ACT-400II, manufactured by ACTIVE Corporation or equivalent) at 1500 rpm for 10 seconds. The wafer with the solution applied is heated at 125°C for 10 minutes to dry the solvent. It is then heated at 300°C for 1 hour to obtain a cured resin film with a thickness of 10 μm or more. Water and diiodomethane are dropped onto the obtained cured resin film using a contact angle measuring device (fully automatic contact angle meter DMo-702, manufactured by Kyowa Interface Science Co., Ltd. or equivalent), and the contact angle of each liquid with the cured resin film is measured, thereby determining the dispersion energy γ ｄ , interaction energy γ ｈ are measured, and the surface free energy γ is calculated from the sum of these.

[0049] 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. Having the weight loss rate of the cured product within the above range allows for more reliable bonding of elements and further suppresses the generation of bubbles and cracks at the interface and peeling at the interface caused by the cured product decomposing during electrode bonding. 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 limit is approximately 480°C due to manufacturing technology.

[0050] The weight loss temperature can be adjusted by the composition of the resin composition, the type of resin material constituting the resin composition, the curing conditions of the resin composition, etc. Specifically, the weight loss temperature can be improved by, for example, using a resin material or inorganic component with high heat resistance in the resin composition, increasing the content of a crosslinking agent, etc. Furthermore, the weight loss temperature can be improved by using a resin with high heat resistance (for example, a resin with a high molecular weight, or a resin having a main chain or substituent with high heat resistance) as the type of resin material.

[0051] Specifically, the weight loss temperature of the cured resin composition can be measured by the following method. The resin composition is applied to a sheet using an applicator or the like, heated at 125°C for 10 minutes to dry, and then heated at 300°C for 1 hour to obtain a 35 μm-thick film (cured film) of the cured resin composition. Approximately 3 to 10 mg of the resulting film is weighed, and the temperature at which the weight loss rate reaches 1% is measured using a simultaneous thermogravimetry and differential thermal analyzer (TG-DTA; STA7200, manufactured by Hitachi High-Tech Science Corporation, or an equivalent) under a nitrogen flow (50 mL / min) at a heating rate of 10°C / min.

[0052] 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 organosilicon compound and the modifier with additives such as the catalyst and the crosslinking agent as needed.

[0053] The resin composition of the present invention contains an organosilicon compound and a modifier, and by the modifier satisfying the weight loss amount and the contact angle with the silicon wafer, the resin composition has excellent heat resistance and flexibility, and can flatten the connection surface even when the element surface has irregularities, thereby imparting high electrical connection reliability between elements. On the other hand, when the organosilicon compound is an organosilicon compound represented by the general formula (1), the effects of the present invention can be achieved by the modifier having a polyether-modified group. Such a resin composition containing an organosilicon compound and a modifier, wherein the organosilicon compound has a structure represented by the following general formula (1) and the modifier has a polyether-modified group, also constitutes one aspect of the present invention. Note that details of the organosilicon compound, the modifier, other additives, and various physical properties are the same as those described above.

[0054] Here, R ０ , R １ and R ２ 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. m and n each represent an integer of 1 or greater.

[0055] The use of the resin composition of the present invention is not particularly limited, but because it has excellent performance in filling irregularities and flattening, and the cured film has heat resistance and flexibility, it can be suitably used for forming an insulating layer on the irregular surface of an element having an irregular 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 used for forming an insulating layer on the irregular surface of such an element having an irregular surface, and the cured film formed using the resin composition of the present invention also constitute one aspect of the present invention. Examples of the above-mentioned element 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 performs various signal processing related to the operation of a solid-state imaging device.

[0056] The cured film of the present invention preferably has a 1% weight loss temperature of 440°C or higher. When the weight loss rate of the cured film after heating with nitrogen is within the above range, elements can be bonded more reliably, and the generation of bubbles and cracks at the interface and peeling at the interface caused by the cured product decomposing during electrode bonding can be further suppressed. 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 for the weight loss temperature, and the higher the better, but the limit is approximately 480°C due to manufacturing technology.

[0057] The weight loss temperature can be adjusted by the composition of the resin composition, the type of resin material constituting the resin composition, the curing conditions of the resin composition, etc. Specifically, for example, the weight loss temperature can be improved by using a highly heat-resistant resin material or inorganic component in the resin composition, increasing the content of the crosslinking agent, etc. Furthermore, the weight loss temperature can be improved by using a highly heat-resistant resin (e.g., a resin with a large molecular weight or a resin having a highly heat-resistant main chain or substituent) as the type of resin material constituting the cured film, or by setting the curing conditions of the resin composition, which is the raw material of the cured film, to a high temperature so that curing proceeds sufficiently, or by extending the curing time.

[0058] Specifically, the weight loss temperature of the cured film can be measured by the following method: Approximately 3 to 10 mg of the cured film is weighed 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), and the temperature at which the weight loss rate reaches 1% is measured.

[0059] 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, wherein 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 (hereinafter also referred to as laminate A). The laminate of the present invention will be described below.

[0060] 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 through holes that penetrate 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 preventing current short circuits. Conventional insulating layers are made of SiN or SiO ２Because hard inorganic materials such as SiO2 and SiO2 were used, if warpage occurred during the formation of the insulating layer or the formation of the laminate, it could not be resolved by stress relaxation, resulting in element warpage and the resulting electrode misalignment and cracking. In the present invention, high electrical connection reliability can be achieved by using a cured film made of a resin that is more flexible than inorganic materials as the insulating layer. In particular, the resin composition of the present invention, which is the basis for the cured film, can fill in the unevenness and flatten the bonding surface even when the element has unevenness, thereby resulting in a laminate with high electrical connection reliability. Furthermore, while conventional insulating layers were formed by vapor deposition and therefore took a long time to form, the cured film of the laminate of the present invention can be formed, for example, by applying and curing a resin composition, thereby improving production efficiency. Here, "electrically connected" refers to a state in which the first electrode and the second electrode are connected by a conductive material, etc., filled in the through-hole.

[0061] The first element and the second element are not particularly limited, and may be circuit elements in which elements, wiring, and electrodes are formed, such as a sensor circuit element provided with a pixel section (pixel region), or a circuit element equipped with a peripheral circuit section such as a logic circuit that performs various signal processing related to the operation of the solid-state imaging device.

[0062] The materials of the electrodes of the first element and the second element and the conductive material are not particularly limited, and conventionally known electrode materials such as gold, copper, and aluminum can be used.

[0063] The thickness of the cured film is not particularly limited, but is preferably 10 μm or more and 300 μm or less. When the thickness of the cured film is in the above range, the function as an insulating layer can be more effectively exhibited and displacement and cracking of the electrode can be more effectively suppressed. The thickness of the cured film is more preferably 20 μm or more, even more preferably 30 μm or more, more preferably 200 μm or less, and even more preferably 100 μm or less.

[0064] The laminate A of the present invention preferably has an inorganic layer between the first element and the second element. By providing an inorganic layer between the first element and the second element, the insulation properties are improved, resulting in a laminate with better connection reliability. Note that conventional laminates use an insulating layer made of an inorganic material having a thickness of about 10 to 20 μm, which makes it difficult to eliminate warping of the element and the laminate, resulting in reduced connection reliability. However, in the present invention, the insulating layer is mainly the cured film, so by reducing the thickness of the inorganic layer, the effects of the inorganic layer can be exerted while also eliminating warping that occurs in the element and the laminate.

[0065] The material of the inorganic layer is not particularly limited, and may be, for example, SiN, SiO ２ , Al ２ O ３ Among them, SiN and SiO are preferred because of their excellent insulating properties and heat resistance. ２ is preferred.

[0066] 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, from the viewpoint of further improving the connection reliability of the laminate, and is preferably 1 μm or less, more preferably 500 nm or less, and even more preferably 100 nm or less.

[0067] The laminate A of the present invention preferably has a barrier metal layer on the surface of the through hole. The barrier metal layer serves to prevent the conductive material (e.g., Cu atoms in the case of a Cu electrode) filled in the through hole from diffusing into the cured film. By providing a barrier metal layer on the surface of the through hole, the conductive material filling the through hole is covered with the barrier metal layer except for the surface that contacts the electrode, thereby further suppressing short circuits and poor conduction due to the diffusion of the conductive material into the cured film. The material for the barrier metal layer can be a known material such as tantalum, tantalum nitride, titanium nitride, silicon oxide, or silicon nitride.

[0068] 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, even more preferably 10 nm or more, more preferably 100 nm or less, and even more preferably 50 nm or less.

[0069] FIG. 1 shows a schematic diagram of one embodiment of the laminate A of the present invention. As shown in FIG. 1, the laminate A of the present invention has a structure in which a first element 1 and a second element 2 each having an electrode 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 via a conductive material filled in a through-hole 5 provided in the cured film 4. In conventional laminates, the cured film 4, which corresponds to the insulating layer, is made of a hard inorganic material. Therefore, when warping occurs in the element or laminate, this cannot be resolved by stress relaxation, and electrode misalignment and cracking are likely to occur. In the present invention, by using a flexible organic compound in the insulating layer, warping of the element or laminate can be resolved, thereby suppressing electrode misalignment and cracking.

[0070] FIG. 2 is a schematic diagram illustrating one embodiment of the laminate A of the present invention. In the embodiment of FIG. 2, an inorganic layer 6 is provided between the cured films 4, thereby further enhancing insulation. The thickness of the inorganic layer 6 of the present invention can be significantly thinner than the insulating layers of conventional laminates, and therefore does not interfere with eliminating warpage of the element or laminate. Although the inorganic layer 6 is provided between the cured films 4 in FIG. 2, it may also be provided on the first element 1 and the second element 2. Although the inorganic layer 6 is provided on both the cured films 4 on the first element 1 side and the second element 2 side in FIG. 2, it may also be provided on only one of them. Furthermore, in the embodiment of FIG. 2, a barrier metal layer 7 is provided on the surface of the through hole 5. By forming the barrier metal layer 7 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, thereby further reducing short circuits and poor conductivity.

[0071] A method for producing the laminate A of the present invention includes, for example, a process for 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, 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 having the bonding electrode formed thereon and the second element having the bonding electrode formed thereon so that the bonding electrodes are bonded to each other. Such a method for producing a laminate also constitutes one aspect of the present invention.

[0072] The method for producing a 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 electrodes and the resin composition can be the same as those used for the first and second elements having electrodes of the laminate of the present invention and the resin composition of the present invention. Furthermore, when the resin composition of the present invention contains a solvent, 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.

[0073] The film formation method is not particularly limited, and conventionally known methods such as spin coating can be used. The solvent drying conditions are not particularly limited, but from the viewpoint of reducing residual solvent and improving the heat resistance of the cured film, it is preferable to heat at a temperature of preferably 70°C or higher, more preferably 100°C or higher, preferably 250°C or lower, and more preferably 200°C or lower, for example, for 30 minutes, more preferably 1 hour. The curing conditions are not particularly limited, but from the viewpoint of sufficiently progressing the curing reaction and further improving heat resistance, it is preferable to heat at a temperature of preferably 200°C or higher, more preferably 220°C or higher, preferably 400°C or lower, and more preferably 300°C or lower, for example, for 1 hour or more, more preferably 2 hours or more. 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 preferable to heat for 3 hours or less.

[0074] The method for producing a laminate of the present invention then involves a step of forming through-holes in each of the cured films. The through-holes may be patterned. The method for forming the through-holes is not particularly limited, and may be carried out by CO ２ They can be formed by laser irradiation such as laser or etching, etc. When other layers are formed on the electrode surface of the element, the through-holes are formed so as to penetrate the other layers as well and expose the electrode surface of the element.

[0075] 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 as needed. The inorganic layer and barrier metal layer can be the same as those used in the laminate of the present invention. The inorganic layer and barrier metal layer can 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. The formation of the barrier metal layer is preferably carried out after the step of forming the through-holes.

[0076] 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. Plating or the like can be used as a method for filling the conductive material. The conductive material can be the same as the conductive material used in the laminate of the present invention.

[0077] The method for producing a laminate of the present invention then includes a step of polishing the surfaces of the first and second elements filled with the conductive material to form a bonding electrode. The unnecessary conductive material formed on the first and second elements is removed by grinding to form a bonding electrode connecting the electrodes formed on the two elements. The polishing preferably involves planarizing and removing the layer formed of the conductive material until the cured film is exposed, or until the inorganic layer, if present, is exposed. The polishing method is not particularly limited, and for example, chemical mechanical polishing or the like can be used.

[0078] 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 the electrode-formed surface of the element 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 component for forming a laminate by bonding the elements together so that the bonding electrodes are bonded to each other. The element, cured film, resin composition, and other components and each step are the same as those described for the resin composition, laminate, and laminate production method of the present invention.

[0079] The method for producing a laminate of the present invention then involves bonding the first element having the bonding electrode formed thereon and the second element having the bonding electrode formed thereon so 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, resulting in a flat bonding surface of the resulting cured film, and bonding can be performed reliably, thereby improving the reliability of electrical connection. Examples of methods for bonding the first element and the second element include a method in which the electrodes and connecting electrodes are melted and connected by heat treatment. The heat treatment is typically performed at 400°C for about 4 hours.

[0080] The use of the laminate of the present invention is not particularly limited, but since it has high electrical connection reliability and suppresses warping and cracking of the elements and the laminate, even when bonding particularly thin elements together, it can be suitably used for laminates constituting semiconductor devices and imaging devices. Semiconductor devices and imaging devices having such laminates of the present invention also constitute the present invention.

[0081] 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, 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 side of an element having multiple 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 multiple 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).

[0082] The laminate B of the present invention has the cured film of the present invention between a support substrate and a third element. Examples of the support substrate include glass and single crystal silicone. The third element is the same as the first and second elements. The cured film is also as described above.

[0083] The third element has a first surface and a second surface, the first surface having 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 greater surface irregularities due to the chips. In the present invention, the resin composition that is the base of the cured film can sufficiently fill gaps even on a surface with large irregularities to make the connection surface flat, thereby improving the connection reliability with the support substrate and suppressing warping and cracking of the element. The number of chips is not particularly limited as long as it is two or more.

[0084] The laminate B of the present invention preferably has an inorganic layer between the support substrate and the cured film. By providing an inorganic layer between the support substrate and the cured film, the insulating properties can be further improved. The inorganic layer can be the same as the inorganic layer of the laminate A.

[0085] The laminate B of the present invention preferably further comprises a fourth element on the second surface of the third element, and the third element and the fourth element are electrically connected. The laminate B of the present invention is sufficiently adhered to the support substrate by the cured film of the present invention, even though the surface has large irregularities due to the chip. Therefore, warping and cracking of the third element are suppressed, and warping and cracking of the fourth element stacked on the third element are also suppressed. As a result, misalignment and cracking of the inter-element electrodes are suppressed, thereby improving the reliability of the electrical connection. The fourth element can be the same as the first to third elements.

[0086] Here, a schematic diagram of one embodiment of the laminate B of the present invention is shown in Figure 3. As shown in Figure 3, 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 stacked on a first surface of the third element 8, a fourth element 10 electrically connected to the third element 8 is stacked on a second surface opposite the first surface, and the first surface of the third element 8 and a supporting substrate 11 are stacked via a cured film 4. In the laminate B of the present invention, by using a cured film of the resin composition of the present invention as the cured film, the unevenness between the chip 9 and the supporting substrate 11 can be sufficiently filled, the connection surface can be flattened, and warping and poor adhesion of the elements or chips can be eliminated, thereby imparting high electrical connection reliability between the elements.

[0087] Fig. 4 is a schematic diagram showing one embodiment of the laminate B of the present invention. In the embodiment of Fig. 4, in addition to the embodiment of Fig. 3, an inorganic layer 6 is provided between the cured film 4 and the support substrate 11, thereby further enhancing the insulating properties. Note that the thickness of the inorganic layer 6 of the present invention may be significantly thinner than the insulating layer of a conventional laminate, and therefore does not hinder the elimination of warpage of the element or laminate.

[0088] The use of the laminate B of the present invention is not particularly limited, but it is suitable for imaging devices and semiconductor devices, similar to the laminate A. Such imaging devices and semiconductor devices having the laminate B of the present invention also constitute the present invention.

[0089] According to the present invention, it is possible to provide a resin composition that has excellent heat resistance and flexibility, and is capable of flattening a connection surface even when the element surface has irregularities, thereby imparting 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.

[0090] Fig. 1 is a diagram schematically showing one embodiment of a laminate of the present invention. Fig. 2 is a diagram schematically showing one embodiment of a laminate of the present invention. Fig. 3 is a diagram schematically showing one embodiment of a laminate of the present invention. Fig. 4 is a diagram schematically showing one embodiment of a laminate of the present invention.

[0091] The following examples will further illustrate the present invention, but the present invention is not limited to these examples.

[0092] (1) Production of 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 initiated 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 and filtered under pressure with nitrogen gas. The resulting 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).

[0093] Next, 20 g of cyclopentyl methyl ether, 2.4 g of 2-propanol, 14 g of ion-exchanged water, and 7.25 g of trichloromethylsilane (Tokyo Chemical Industry Co., Ltd., molecular weight 149.48) were added to a reaction vessel equipped with a reflux condenser, a thermometer, and a dropping funnel, and the mixture was stirred at room temperature under a nitrogen atmosphere. Subsequently, 8 g of the compound (DD-ONa) obtained above and 20 g of cyclopentyl methyl ether were added to the dropping funnel, and the resulting slurry was added dropwise to the reaction vessel over 30 minutes. After the addition was completed, stirring was continued for 30 minutes. After the reaction, stirring was stopped, the mixture was allowed to stand, and the organic layer and aqueous layer were separated. The resulting organic layer was neutralized by washing with water, after which dust was removed using a membrane filter. The mixture was then concentrated under reduced pressure at 60°C using a rotary evaporator to obtain 9.5 g of a colorless solid. This colorless solid was washed with 10 g of methyl acetate and dried under reduced pressure to obtain 6.2 g of a colorless powdery solid (DD(Me)-OH).

[0094] A 100 mL flask was equipped with a condenser, 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 23.4 mass% of RCP-160M ​​were extracted. After completion of reflux, the mixture was cooled to 80 ° C., and 0.55 g of pure water was added and aged at 80 ° C., reaching equilibrium in 5 hours. After cooling to room temperature, the RCP-160M ​​was filtered off, and the obtained filtrate was washed once with water. Thereafter, the solvent and low-boiling components were distilled off from the filtrate, and the resulting crude product was purified by reprecipitation with heptane to obtain an organosilicon compound (organosilicon compound a, weight-average molecular weight 36,000) having the structure of the following formula (8), in which m is 30 and n (the number of DMS chains) is an average of 4.

[0095]

[0096] (2) Preparation of Organosilicon Compound b SST-3PM4 manufactured by Gelest was used as the organosilicon compound b. Note that SST-3PM4 is an organosilicon compound that does not satisfy the above general formula (1).

[0097] (3) Production of Resin A (Heat-Resistant Additive) 10.00 g of tetracarboxylic dianhydride 4,4'-(Hexafluoroisopropylidene) diphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 444.24) and 92.72 g of anisole were placed in a reaction vessel equipped with a stirrer, a water divider, a thermometer, and a nitrogen gas inlet, and the solution in the reaction vessel was heated to 60 ° C. Next, 7.573 g of aromatic diamine PAM-E (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 280.51) was added to the reaction vessel. 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 then further refluxed at 170 ° C. for 4 hours to obtain an imide compound having amines at both ends. After cooling, 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, thereby obtaining a compound having an imide structure represented by the following formula (9) (resin A, weight average molecular weight 9000).

[0098] Here, l represents the number of repeating units.

[0099] (4) Preparation of modifiers The following compounds were prepared as modifiers. Modifier A (BYK-320, manufactured by BYK-Chemie): polymethylalkylsiloxane having a polyether-modified group, molecular weight 22,000 Modifier B (BYK-325N, manufactured by BYK-Chemie): polymethylalkylsiloxane having a polyether-modified group, molecular weight 17,000 Modifier C (KP-341, manufactured by Shin-Etsu Chemical Co., Ltd.): silicone-based compound having a polyether-modified group, molecular weight 18,000 Modifier D (KP-112, manufactured by Shin-Etsu Chemical Co., Ltd.): silicone-based compound having a polyether-modified group, molecular weight 20,000 Modifier E (BYK-326, manufactured by BYK-Chemie): polymethylalkylsiloxane having a polyether-modified group, molecular weight 25,000 Modifier F (BYK-307, manufactured by BYK-Chemie): polydimethylsiloxane having a polyether-modified group, molecular weight 31,000 Modifier G (BYK-330, manufactured by BYK-Chemie): Polydimethylsiloxane having a polyether modified group, molecular weight 19,000 Modifier H (BYK-327, manufactured by BYK-Chemie): Polydimethylsiloxane having a polyether modified group, molecular weight 6,700 Modifier I (BYK-310, manufactured by BYK-Chemie): Polymethylalkylsiloxane having a polyether modified group, molecular weight 4,400 Modifier J (BYK-322, manufactured by BYK-Chemie): Polymethylalkylsiloxane having an aralkyl modified group, molecular weight 12,000 Modifier K (BYK-323, manufactured by BYK-Chemie): Polymethylalkylsiloxane having an aralkyl modified group, molecular weight 27,000 Modifier L (KF-96-100cs, manufactured by Shin-Etsu Chemical Co., Ltd.): Silicone oil, molecular weight 12,000 Modifier M (KF-96-1000cs, manufactured by Shin-Etsu Chemical Co., Ltd.): silicone oil, molecular weight 34,000 Modifier N: fluorine-based surfactant, molecular weight 14,000 Modifier O (BYK-394, manufactured by BYK-Chemie): polyacrylate-based surface conditioner, molecular weight 7,000

[0100] (5) Measurement of thermal weight loss of modifier Using a differential thermal thermogravimetric simultaneous analyzer (TG-DTA; STA7200, manufactured by Hitachi High-Tech Science Corporation), each modifier was heated in air from 25 ° C. to 300 ° C. at a heating rate of 10 ° C. / min and held for 1 hour. After holding for 1 hour, it was further heated to 400 ° C. at a heating rate of 10 ° C. / min and held for 3 hours after reaching 400 ° C. The thermal weight loss was calculated from the weight at each temperature when it first reached 400 ° C. and the weight at 400 ° C. after 3 hours had elapsed.

[0101] Example 1 A resin composition was obtained by adding cyclopentanone as a solvent to 100 parts by weight of an 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.

[0102] (Examples 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 to obtain the compositions shown in Tables 1 and 2. The viscosity of all of the resin compositions in the examples and comparative examples was set to 1200 cP.

[0103] <Physical Properties> The resulting resin compositions were subjected to the following measurements, and the results are shown in Tables 1 and 2.

[0104] (Measurement of Contact Angle) The organosilicon compound and 1 part by weight of the modifier per 100 parts by weight of the organosilicon compound were added to ethyl benzoate to prepare a sample having a viscosity of 45 cP at 25°C. The sample was dropped onto a silicon wafer using a contact angle measuring instrument (fully automatic contact angle meter DMo-702, manufactured by Kyowa Interface Science Co., Ltd.), and the contact angle of the sample with respect to the silicon wafer was measured. Note that for Comparative Examples 4 and 5, the modifier was not dissolved in the solvent, so contact angle measurement and the following measurements and evaluations were not performed.

[0105] (Measurement of Surface Free Energy) The following measurements were carried out using the resin compositions listed in Tables 1 and 2 as solutions. At room temperature, 6 g of the solution was dropped onto the center of an 8-inch silicon wafer, and the resin composition was applied to the silicon wafer (surface roughness <0.1 μm) using a spin coater (ACT-400II, manufactured by ACTIVE Corporation) at 1500 rpm for 10 seconds. The wafer onto which the solution was applied was heated at 125°C for 10 minutes to dry the solvent. It was then heated at 300°C for 1 hour to obtain a cured resin film with a thickness of 35 μm. Water and diiodomethane were dropped onto the obtained cured resin film using a contact angle measuring instrument (fully automatic contact angle meter DMo-702, manufactured by Kyowa Interface Science Co., Ltd.), and the contact angle of each liquid with the cured resin film was measured, thereby determining the dispersion energy γ ｄ , interaction energy γ ｈ The surface free energy γ was calculated from the sum of these values.

[0106] <Evaluation> The resin compositions obtained in the examples and comparative examples were evaluated as follows. The results are shown in Tables 1 and 2.

[0107] (Evaluation of Film Cracking) 6 g of the solution obtained in the same manner as in the measurement of surface free energy above was dropped onto the center of an 8-inch silicon wafer at room temperature, and the resin composition was applied onto a silicon wafer (surface roughness <0.1 μm) using a spin coater (ACT-400II, manufactured by ACTIVE Corporation) at 1500 rpm for 10 seconds. The wafer onto which the solution had been applied was heated at 125° C. for 10 minutes to dry the solvent. The rotation time of the spin coater was adjusted so that the thickness of the resin composition after drying would be 35 μm. The resin composition was then further cured by heating at 300° C. for 1 hour. After cooling to room temperature, the coated surface (surface) of the cured film was observed to evaluate the presence or absence of film cracking.

[0108] (Evaluation of 1% Thermal Weight Loss Temperature) A cured film was prepared in the same manner as in the evaluation of film cracking. The obtained cured film was heated at a temperature increase rate of 10°C / min under a nitrogen flow of 200 mL / min using a thermogravimetric and differential thermal analyzer (TG-DTA; STA7200, manufactured by Hitachi High-Tech Science Corporation), and the temperature at which the weight loss rate reached 1% was measured.

[0109] (Evaluation of Groove Filling Property) 6 g of the solution obtained by the same method as in the measurement of surface free energy described above was dropped onto the center of an 8-inch silicon wafer on which grooves 10 μm deep and 300 μm wide were dug at 40 mm intervals, and a film was formed on the silicon wafer (surface roughness other than the grooves: <0.1 μm) using a spin coater (ACT-400II, manufactured by ACTIVE Corporation). The wafer coated with the solution was heated at 125°C for 10 minutes to dry the solvent. The rotation time of the spin coater was adjusted so that the thickness of the resin composition after drying would be 35 μm. The resin composition was then further cured by heating at 300°C for 1 hour. The groove portions of the silicon wafer on the surface of the cured product after heat curing were observed using a laser microscope (OLS4100; manufactured by Olympus Corporation), and the depth of the groove portions was measured. The groove depth measured with a laser microscope was divided by the original groove depth of the wafer (10 μm) to obtain the recess amount (%) (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 recess amount values ​​(%). Recess amount (%) = (groove depth (μm) after application and curing of resin composition) / 10 (μm) × 100. Good: Recess is less than 7%. Fair: Recess is 7% or more but less than 10%. Bad: Recess is 10% or more.

[0110]

[0111]

[0112] According to the present invention, it is possible to provide a resin composition that has excellent heat resistance and flexibility, and is capable of flattening a connection surface even when the element surface has irregularities, thereby imparting 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.

[0113] REFERENCE SIGNS LIST 1 First element 2 Second element 3 Electrode 4 Hardened film 5 Through-hole 6 Inorganic layer 7 Barrier metal layer 8 Third element 9 Chip 10 Fourth element 11 Support substrate

Claims

1. A resin composition containing an organosilicon compound and a modifier, the modifier alone is heated in air from room temperature to 300°C at a temperature increase rate of 10°C / min, maintained at this temperature for 1 hour, and then heated to 400°C at a temperature increase rate of 10°C / min and maintained at 400°C for 3 hours, the thermal weight loss before and after maintaining at 400°C for 3 hours is 10% or less, 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. When the sample is dropped onto a silicon wafer, the contact angle of the sample with the silicon wafer is 9° or more and 20° or less.

2. The resin composition further contains a solvent, and the solvent is used to prepare a solution having a viscosity of 1200 cP. The solution is spin-coated onto a silicon wafer at 1500 rpm for 10 seconds, and after the solvent dries, the solution is cured at 300°C for 1 hour to form a cured resin film having a thickness of 10 μm or more. When the surface free energy of the cured resin film is 27 mJ / m ２ The resin composition according to claim 1 .

3. The resin composition according to claim 1 or 2, which contains a metal catalyst, a crosslinking agent, and a heat-resistant additive.

4. 3. The resin composition according to claim 1, wherein the organosilicon compound has a structure represented by the following general formula (1): 【Chemical 1】 Here, R ０ , R １ and R ２ 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. m and n each represent an integer of 1 or greater.

5. The resin composition according to claim 1 or 2, wherein the modifier has a polyether modifying group.

6. 3. The resin composition according to claim 1, wherein the content of the modifier is 0.01 parts by weight or more and 10 parts by weight or less per 100 parts by weight of the organosilicon compound.

7. 3. The resin composition according to claim 1, wherein the modifier has a weight average molecular weight of 4,000 or more and 30,000 or less.

8. 3. The resin composition according to claim 2, wherein the resin composition is cured at 300°C for 1 hour after the solvent has been dried, and the cured product has a 1% weight loss temperature of 460°C or higher.

9. 3. The resin composition according to claim 1, which is used to form an insulating layer on the uneven surface of a device having an uneven surface.

10. 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. 【Chemistry 2】 Here, R ０ , R １ and R ２ 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. m and n each represent an integer of 1 or greater.

11. A cured film formed using the resin composition described in claim 1 or 2.

12. A laminate having the cured film according to claim 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.

13. The laminate according to claim 12 , further comprising an inorganic layer between the first element and the second element.

14. The laminate according to claim 12 , further comprising a barrier metal layer on the surface of the through hole.

15. An imaging device having the laminate described in claim 12.

16. A semiconductor device having the laminate of claim 12.

17. forming a film of the resin composition according to claim 1 or 2 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; forming through holes in each of the cured films; filling each of the through holes with a conductive material; a step of polishing the surfaces of the first element and the second element on the side where the conductive material is filled to form bonding electrodes; and 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.

18. forming a film of the resin composition according to claim 1 or 2 on a surface of an element having electrodes, on which the electrodes are formed, 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 having the electrode on the side filled with the conductive material to form a bonding electrode.

19. A laminate having the cured film according to claim 11 between a supporting substrate and a third element, the third element has a first surface and a second surface, the first surface having a plurality of chips; A laminate having the cured film laminated on the first surface side.

20. The laminate according to claim 19 , further comprising an inorganic layer between the support substrate and the cured film.

21. 20. The stack of claim 19, further comprising a fourth element on the second surface of the third element, the third element and the fourth element being electrically connected.

22. An imaging device having the laminate described in claim 19.

23. A semiconductor device having the laminate described in claim 19.

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