Curable resin composition, cured film, multilayer object, imaging device, semiconductor device, and method for producing multilayer object

Abstract

The purpose of the present invention is to provide: a curable resin composition capable of giving cured objects which, when an inorganic layer is formed thereon, prevent the inorganic layer from wrinkling, thereby suppressing process abnormality; a cured film formed from the curable resin composition; a multilayer object formed using the cured film; an imaging device and a semiconductor device which include the multilayer object; and a method for producing the multilayer object. This curable resin composition comprises a silsesquioxane, a solvent, and a silica filler as an inorganic filler. When the curable resin composition is dried under the conditions of 125°C and 10 minutes to remove the solvent and heat-cured by a heat treatment at 300°C for 1 hour, the resultant cured object has a modulus at 300°C of 0.2 MPa or greater.

Description

Curable resin composition, cured film, laminate, imaging device, semiconductor device, and method for manufacturing laminate

[0001] The present invention relates to a curable resin composition, a cured film, a laminate, an imaging device, a semiconductor device, and a method for producing the laminate.

[0002] As semiconductor devices become more sophisticated, they are increasingly being made three-dimensional by stacking multiple semiconductor chips. In the manufacture of such semiconductor devices with multiple stacked semiconductor chips, a damascene process is first used to form a bonding surface on the electrode surface of an element or circuit board (hereinafter simply referred to as a substrate) on which two electrodes are formed, whereby a bonding electrode made of copper is surrounded by an insulating film. The two substrates are then stacked so that the bonding electrodes on the bonding surfaces face each other, and a heat treatment is then performed to manufacture the semiconductor device (see Patent Document 1).

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

[0004] In the manufacturing of the semiconductor device, high-temperature treatment at 400°C for 4 hours is performed when bonding electrodes, so the insulating layer used to form the bonding surface must 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 the substrate, and warping of the substrate can cause electrode connection positions to shift or electrodes to crack when stacked, which can reduce the connection reliability of the semiconductor device. Furthermore, in recent years, semiconductor devices have become more highly functional, and substrates have become larger and thinner, making substrate warping more likely to occur, and thin substrates in particular can crack.

[0005] To prevent warping and cracking of the substrate due to high-temperature processing, it has been considered to use an organic compound, which is more flexible than inorganic materials, as an insulating layer. However, insulating layers made of organic compounds are vulnerable to heat, and outgassing generated by thermal decomposition can easily cause cracking of the insulating layer. To address this issue, the use of heat-resistant resins as insulating layers has also been considered. However, resins are permeable to moisture and therefore vulnerable to high-humidity environments. If moisture penetrates the electrodes in a high-humidity environment, the reliability of the semiconductor device may be reduced.

[0006] One method proposed to solve this moisture resistance problem is to laminate a thin inorganic layer made of an inorganic material on the organic layer. Since inorganic materials have high moisture resistance, covering the organic layer with an inorganic layer can improve moisture resistance. Furthermore, by making the inorganic layer thin, the organic layer's effect of suppressing warping and cracking of the substrate due to high-temperature treatment is not impaired.

[0007] However, forming an inorganic layer on an organic layer can cause wrinkles in the inorganic layer. While wrinkles in the inorganic layer are not a major problem from the standpoint of insulation performance, they can result in poor appearance. Furthermore, since alignment mechanisms are used to align the various components in the manufacture of semiconductor devices, wrinkles in the inorganic layer can cause alignment problems and lead to process abnormalities.

[0008] The present invention aims to provide a curable resin composition that is less likely to cause wrinkles in an inorganic layer even when an inorganic layer is formed on the cured product, and that can suppress process abnormalities; a cured film of the curable resin composition; a laminate using the cured film; an imaging device and a semiconductor device that have the laminate; and a method for manufacturing the laminate.

[0009] The present invention includes the following Disclosures 1 to 17. The present invention is described in detail below. [Disclosure 1] A curable resin composition comprising a silsesquioxane, a solvent, and a silica filler as an inorganic filler, wherein the cured product obtained by drying the solvent at 125°C for 10 minutes and heat-curing the product by heat-treating at 300°C for 1 hour has an elastic modulus at 300°C of 0.2 MPa or more. [Disclosure 2] The curable resin composition according to Disclosure 1, wherein the cured product obtained by drying the solvent at 125°C for 10 minutes and heat-curing the product by heat-treating at 300°C for 1 hour has a coefficient of linear expansion (CTE) of 500 ppm / °C or less in the range of -40°C to 100°C. [Disclosure 3] The curable resin composition according to Disclosure 1 or 2, wherein the silsesquioxane has structures represented by the following structural formulas (A) and (B) in one molecule. In structural formulas (A) and (B), R Ａ , R Ｂeach independently represents an aliphatic group, an aromatic group, or hydrogen. j and k each represent an integer of 1 or greater. [Disclosure 4] The curable resin composition according to any one of Disclosures 1 to 3, wherein the silsesquioxane has a structure represented by the following structural formula (1): In structural formula (1), 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 curable resin composition according to any one of Disclosures 1 to 4, wherein the content of the silica filler is 15 parts by weight or more and 40 parts by weight or less per 100 parts by weight of the silsesquioxane. [Disclosure 6] The curable resin composition according to any one of Disclosures 1 to 5, wherein the solvent has a boiling point of 130°C or more and 250°C or less. [Disclosure 7] The curable resin composition according to any one of Disclosures 1 to 6, wherein an inorganic layer is laminated on a heat-cured cured product. [Disclosure 8] A cured film obtained by heat-curing the curable resin composition according to any one of Disclosures 1 to 6. [Disclosure 9] A laminate including an organic layer made of the cured film according to Disclosure 8 on a first substrate, and an inorganic layer on the organic layer, wherein the first substrate has a first surface having a plurality of chips and a second surface opposite thereto, and the organic layer and the inorganic layer are on the first surface side. [Disclosure 10] The laminate according to Disclosure 9, wherein a support substrate is laminated on the inorganic layer. [Disclosure 11] The laminate according to Disclosure 9 or 10, wherein a second substrate is further provided on the second surface of the first substrate, and the first substrate and the second substrate are electrically connected. [Disclosure 12] A laminate including an organic layer made of the cured film according to Disclosure 8 and an inorganic layer between a third substrate having an electrode and a fourth substrate having an electrode, wherein the electrode of the third substrate and the electrode of the fourth substrate are electrically connected via a through hole penetrating the organic layer and the inorganic layer. [Disclosure 13] The laminate according to Disclosure 12, wherein a barrier metal layer is provided on the surface of the through hole. [Disclosure 14] An imaging device including the laminate according to any one of Disclosures 9 to 13. [Disclosure 15] A semiconductor device having the laminate according to any one of Disclosures 9 to 13. [Disclosure 16] A method for manufacturing a laminate, comprising the steps of: applying the curable resin composition according to any one of Disclosures 1 to 6 onto a first surface of a first substrate having a first surface having a plurality of chips and a second surface opposite the first surface; and forming an organic layer by solvent drying and thermal curing; and forming an inorganic layer on the organic layer.[Disclosure 17] A method for manufacturing a laminate, comprising the steps of: applying the curable resin composition according to any one of Disclosures 1 to 6 onto a surface of a third substrate having an electrode and a fourth substrate having an electrode, drying the solvent, and thermally curing the composition to form an organic layer; forming an inorganic layer on the organic layer; forming through holes in each of the organic layers and the inorganic layer; filling each of the through holes with a conductive material; polishing the surfaces of the third substrate having an electrode and the fourth substrate having an electrode on the side filled with the conductive material to form bonding electrodes; and bonding the third substrate having an electrode and the fourth substrate having an electrode so that the bonding electrodes are bonded to each other.

[0010] The curable resin composition of the present invention contains a silsesquioxane. Silsesquioxanes have high heat resistance while maintaining flexibility comparable to that of organic compounds. Therefore, by using a cured film containing silsesquioxane as the insulating layer of a laminate, warping and cracking of the substrate can be suppressed, thereby improving the reliability of electrical connection. The silsesquioxane is not particularly limited as long as it is thermosetting, but it is preferable that the silsesquioxane have structures represented by the following structural formulas (A) and (B) in one molecule, as this further suppresses warping and cracking of the substrate.

[0011] 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.

[0012] The silsesquioxane preferably has a reactive moiety. By using a silsesquioxane having a reactive moiety as the curable resin of the curable resin composition, warping and cracking of the element can be further suppressed. Furthermore, since silsesquioxane has excellent heat resistance, decomposition of the organic layer due to high-temperature treatment carried out during the manufacture of a semiconductor device in which multiple laminates are stacked can be further suppressed. Examples of the reactive moiety include a hydroxyl group and an alkoxy group.

[0013] The content of the silsesquioxane having the reactive site is preferably 60 parts by weight or more, more preferably 70 parts by weight or more, and even more preferably 75 parts by weight or more, per 100 parts by weight of the resin solid content in the curable resin composition. The content of the silsesquioxane having the reactive site is preferably less than 100 parts by weight, more preferably 90 parts by weight or less, per 100 parts by weight of the resin solid content in the curable resin composition.

[0014] The silsesquioxane preferably has a structure represented by the following structural formula (1): When the silsesquioxane has the structure of structural formula (1), warping of the element can be further suppressed. In particular, it is more preferable that the silsesquioxane further has an aromatic ring structure, since this further improves heat resistance and further suppresses warping and cracking of the element.

[0015] In structural formula (1), 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.

[0016] In the above structural 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.

[0017] In the above structural 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 R２ 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 R ２ 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.

[0018] In the structural formula (1), m and n each represent an integer of 1 or more and represent the number of repeating units. The m is preferably 30 or more, more preferably 50 or more, and preferably 100 or less. The n is preferably 1 or more, more preferably 3 or more, and preferably 8 or less.

[0019] The weight-average molecular weight of the silsesquioxane is not particularly limited, but is preferably 5,000 or more and 150,000 or less. Having a weight-average molecular weight of the silsesquioxane within this range improves film-forming properties during application, further enhancing planarization performance and further suppressing warpage and cracking of elements. The weight-average molecular weight of the silsesquioxane 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 silsesquioxane 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 a polystyrene standard.

[0020] The content of the silsesquioxane is preferably 65% ​​by weight or more and 99% by weight or less based on 100% by weight of the solid components of the curable resin composition. By having the content of silsesquioxane in the curable resin composition within the above range, warping and cracking of the element can be suppressed, thereby further improving the reliability of electrical connection. The content of silsesquioxane in 100% by weight of the solid components of the curable resin composition is more preferably 70% by weight or more, even more preferably 75% by weight or more, more preferably 98% by weight or less, and even more preferably 97% by weight or less.

[0021] The curable resin composition of the present invention contains a solvent. By including a solvent in the curable resin composition, the viscosity of the silsesquioxane can be adjusted to a level that allows it to be applied to a substrate, and irregularities on the substrate surface can be filled and made flat. As a result, the bonding reliability of the substrate can be improved, and the electrical connection reliability of the laminate can also be improved. The solvent may be composed of a single component or a mixture of multiple components.

[0022] The solvent in the curable resin composition preferably has a boiling point of 130°C or higher and 250°C or lower. Having a boiling point within the above range of the solvent prevents aggregation of the silica filler due to solvent evaporation, allowing the silica filler to be uniformly dispersed in the resin composition. The boiling point of the solvent is more preferably 150°C or higher, even more preferably 180°C or higher, and 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, ketone 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).

[0023] The content of the solvent in the curable resin composition is preferably 50% by weight or less. When the content of the solvent in the curable resin composition is within the above range, shrinkage due to solvent volatilization 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 substrates is improved and the electrical connection reliability can also be improved. The content of the solvent is more preferably 45% by weight or less, even 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 from the viewpoint of further improving flattening performance, it is preferably 30% by weight or more.

[0024] 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 silsesquioxane. By having the content of the solvent relative to the silsesquioxane in the above range, the planarization performance of the substrate surface can be further improved. The content of the solvent relative to the silsesquioxane 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.

[0025] The curable resin composition of the present invention contains a silica filler as an inorganic filler. By using the silica filler in the curable resin composition and satisfying the elastic modulus described below, even when an inorganic layer is formed on the cured film of the silsesquioxane, wrinkles are unlikely to occur in the inorganic layer, and process abnormalities due to wrinkles in the inorganic layer can be suppressed.

[0026] It is preferable that the silica filler is not spherical. Having a non-spherical shape of the silica filler increases the elastic modulus, making it easier to satisfy the elastic modulus requirements described below. Furthermore, using a silica filler with a shape other than spherical makes it possible to control the elastic modulus without using a crosslinking agent, thereby avoiding increases in storage stability and viscosity that would otherwise occur with the use of a crosslinking agent. The reason why the elastic modulus increases when the silica filler has a shape other than spherical is unclear, but it is thought that this is because a spherical shape reduces the contact area with other fillers, making it difficult for them to interact. Examples of shapes of the silica filler other than spherical include needles, pulverized particles, and fibers. Even when using a spherical silica filler, it is possible to adjust the elastic modulus to the range described below by combining it with a crosslinking agent.

[0027] The silica filler has a bulk density of 0.01 g / cm ３ Above, 0.2g / cm ３ When the bulk density of the silica filler is in the above range, it is easier to satisfy the elastic modulus described below. The bulk density of the silica filler is preferably 0.05 g / cm or less. ３ More preferably, it is 0.1 g / cm or more.３ More preferably, it is:

[0028] The content of the silica filler is preferably 15 parts by weight or more and 40 parts by weight or less relative to 100 parts by weight of the silsesquioxane. By setting the content of the silica filler within this range, warping and cracking of the substrate can be further suppressed and the elastic modulus described below can be more easily satisfied. The content of the silica filler is more preferably 20 parts by weight or more relative to 100 parts by weight of the silsesquioxane, even more preferably 25 parts by weight or more, more preferably 35 parts by weight or less, and even more preferably 30 parts by weight or less.

[0029] The curable resin composition of the present invention preferably contains a catalyst. The catalyst serves to promote the curing reaction. By including a catalyst in the curable resin composition of the present invention, the curable resin composition can be cured more completely, decomposition of the organic layer (cured film) due to high-temperature treatment can be further suppressed, and control of the elastic modulus can be facilitated. Examples of the catalyst include organotin compounds such as dibutyltin dilaurate and stannous acetate, metal carboxylates such as zinc naphthenate, acetylacetonate complexes having a zirconium central metal, and titanium compounds. Among these, acetylacetonate complexes having a zirconium central metal are preferred because they can further promote the curing of the curable resin composition. Note that the catalyst remains even after the curable resin composition has cured. In other words, when the curable resin composition of the present invention contains a catalyst, the catalyst is also contained in the cured film obtained by curing the curable resin composition.

[0030] 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 silsesquioxane. By setting the content of the catalyst within this range, curing can be further promoted and decomposition of the cured film due to high-temperature treatment can be further suppressed. 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 per 100 parts by weight of the silsesquioxane.

[0031] The curable resin composition may contain a crosslinking agent. When the curable resin composition contains a crosslinking agent, the crosslinking agent crosslinks between the curable resins, increasing the crosslink density of the cured product and further suppressing decomposition at high temperatures. As a result, warping and cracking of the substrate can be suppressed, thereby further improving connection reliability. Furthermore, the elastic modulus described below can be controlled by adjusting the amount and structure of the crosslinking agent. Furthermore, by including a crosslinking agent, the elastic modulus described below can be controlled even when the silica filler has a spherical shape. Examples of the crosslinking agent include 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, polyalkoxysilanes are preferred from the viewpoints of improving crosslink density and heat resistance.

[0032] 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 silsesquioxane. By setting the content of the crosslinking agent within the above range, the crosslinking density of the cured product can be controlled, and by combining it with the silica filler described above, it is possible to easily adjust the elastic modulus to the range described below. 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, even more preferably 20 parts by weight or less per 100 parts by weight of the silsesquioxane.

[0033] The curable resin composition preferably contains a heat-resistant resin. By using a heat-resistant resin in the curable resin composition, it is possible to obtain a cured film that is less likely to crack when subjected to high-temperature treatment, even when the cured film is thick.

[0034] Examples of the heat-resistant resin include polyimide, epoxy resin, silicone resin, benzoxazine resin, cyanate resin, and phenolic resin, and polyimide is particularly preferred from the viewpoint of heat resistance.

[0035] The molecular weight of the heat-resistant resin 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 resin is within the above range, even if a thick cured film is formed, it can be a cured film that is less likely to crack during high-temperature treatment. The molecular weight of the heat-resistant resin 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 resin is preferably 0.5 parts by weight or more and 50 parts by weight or less relative to 100 parts by weight of the silsesquioxane.By setting the content of the heat-resistant resin within the above range, even if a thick cured film is formed, it is possible to obtain a cured film that is less likely to crack during high-temperature treatment.The content of the heat-resistant resin is more preferably 0.7 parts by weight or more relative to 100 parts by weight of the silsesquioxane, more preferably 0.75 parts by weight or more, particularly preferably 1 part by weight or more, more preferably 20 parts by weight or less, more preferably 10 parts by weight or less, particularly preferably 5 parts by weight or less.

[0037] When the heat-resistant resin is a polyimide, the polyimide preferably has a siloxane bond, which enhances compatibility with the silsesquioxane, 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 silsesquioxane 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 and 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 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 one of the structures represented by the following structural formulas (2) to (7) at at least one terminal, and particularly preferably has one of the structures represented by the following structural formulas (2) to (7) at both terminals. In the structural formulas below, "*" represents the bonding site with a portion other than the terminal of the polyimide.

[0040]

[0041] 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 the silsesquioxane, further enhancing handleability. The weight-average molecular weight is more preferably 2,000 or more, even more preferably 3,000 or more, more preferably 35,000 or less, and 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.

[0042] The content of the polyimide is preferably 0.5 parts by weight or more and 50 parts by weight or less relative to 100 parts by weight of the silsesquioxane.By making the content of polyimide within the above range, even if a thick cured film is formed, it can be made into a cured film that is less likely to crack during high-temperature treatment.The content of the polyimide is preferably 0.7 parts by weight or more relative to 100 parts by weight of the silsesquioxane, 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.

[0043] The curable resin composition of the present invention may contain other additives such as a viscosity modifier, a filler other than silica filler, and an adhesion promoter, as needed, within the range that does not impair the effects of the present invention.

[0044] The curable resin composition of the present invention is prepared by drying the solvent at 125°C for 10 minutes and then heat-curing the composition by heat treatment at 300°C for 1 hour. The cured product has a modulus of elasticity at 300°C of 0.2 MPa or more. Having the modulus of elasticity at 300°C within the above range can prevent wrinkles in the inorganic layer and process abnormalities caused by wrinkles in the inorganic layer. The modulus of elasticity at 300°C of the cured product is preferably 0.2 MPa or more, more preferably 0.5 MPa or more, and even more preferably 1 MPa or more. While there is no particular upper limit to the modulus of elasticity of the cured product at 300°C, it is preferably 100 MPa or less, more preferably 50 MPa or less, from the viewpoint of further preventing warpage and cracking of the substrate. The modulus of elasticity can be adjusted by the type of silsesquioxane, the type, shape and amount of the silica filler, the crosslinking structure, etc. The modulus of elasticity can be measured specifically by the following method.

[0045] The curable resin composition is applied in sheet form using an applicator or the like, dried at 125°C for 10 minutes, and then heated at 300°C for 1 hour to obtain a 500 μm thick film of the cured curable resin composition. The obtained film sample is punched out to a size of 5 mm x 35 mm to prepare a measurement sample. The tensile modulus of the obtained measurement sample at 300°C is measured using a dynamic viscoelasticity measuring device (IT Measurement Control Co., Ltd., DVA-200 or equivalent) under conditions of a constant temperature rise tensile mode, a temperature rise rate of 5°C / min, and a frequency of 1 Hz.

[0046] The curable resin composition of the present invention preferably has a linear expansion coefficient (CTE) of 500 ppm / °C or less in the range of -40°C to 100°C after drying the solvent at 125°C for 10 minutes and heat-curing by heat treatment at 300°C for 1 hour. When the curable resin composition satisfies this linear expansion coefficient, wrinkles are less likely to occur in the inorganic layer even when an inorganic layer is formed on the cured film, thereby preventing process abnormalities caused by wrinkles in the inorganic layer. The linear expansion coefficient is more preferably 400 ppm / °C or less, and even more preferably 300 ppm / °C or less. The lower limit of the linear expansion coefficient is not particularly limited, but is preferably 10 ppm / °C or more from the viewpoint of suppressing warping due to stress relaxation of the inorganic film. The linear expansion coefficient can be adjusted by the type of silsesquioxane, the type, shape and amount of the silica filler, the crosslinking structure, etc. The linear expansion coefficient can be measured by the following method.

[0047] The curable resin composition is applied to a sheet using an applicator or the like, dried at 125°C for 10 minutes, and then heated at 300°C for 1 hour to obtain a 300 μm-thick film of the cured curable resin composition. The obtained film sample is punched out to a size of 4 mm x 22 mm to prepare a measurement sample. The obtained measurement sample is cooled to -70°C and then heated to 400°C at a heating rate of 5°C / min using a thermomechanical analyzer (TMA7100 or equivalent, manufactured by Hitachi High-Tech Science Corporation), and the linear thermal expansion is measured, and the linear expansion coefficient in the range of -40°C to 100°C is calculated.

[0048] The method for producing the curable resin composition of the present invention is not particularly limited, and the composition can be produced, for example, by mixing the silsesquioxane, the solvent, the silica filler, and, if necessary, additives such as the catalyst and the heat-resistant resin with the solvent.

[0049] The curable resin composition of the present invention is preferably used as an insulating layer in a laminate consisting of a plurality of substrates, the cured product of which is heat-cured and used in semiconductor devices, imaging devices, etc., and more preferably used by laminating an inorganic layer on the heat-cured cured product. By using such an insulating layer, high moisture resistance can be exhibited while suppressing warping and cracking of the substrate, and further, wrinkles are less likely to occur in the inorganic layer, thereby suppressing process abnormalities caused by wrinkles in the inorganic layer.

[0050] Such a cured film obtained by thermally curing the curable resin composition of the present invention also constitutes one aspect of the present invention. Also, a laminate using the cured film of the present invention, i.e., a laminate comprising an organic layer made of the cured film of the present invention on a first substrate and an inorganic layer laminated on the organic layer, the first substrate having a first surface having a plurality of chips and a second surface opposite to the first surface, and the organic layer and the inorganic layer on the first surface side (hereinafter also referred to as laminate A) also constitutes one aspect of the present invention.

[0051] The laminate A of the present invention is a laminate in which an organic layer is laminated on a first element and an inorganic layer is laminated on the organic layer. In a semiconductor device in which multiple elements and substrates are laminated, the organic layer and inorganic layer serve as insulating layers between each element and substrate. Conventional insulating layers have used hard inorganic materials to withstand high-temperature processing during manufacturing, which means that they are unable to relieve stress when the substrate deforms, making the substrate prone to warping and cracking. In the laminate of the present invention, the use of a flexible organic compound capable of stress relief as the insulating layer makes the substrate less prone to warping and cracking. As a result, electrode misalignment and cracking caused by substrate warping and cracking can be suppressed, thereby improving the connection reliability between substrates. Furthermore, by providing an inorganic layer as an auxiliary insulating layer on the organic layer, moisture in the atmosphere is less likely to permeate than through an organic layer alone, thereby achieving high connection reliability even under high temperature and high humidity. Furthermore, because the organic layer is made of a cured film of the curable resin composition of the present invention, wrinkles are less likely to form in the inorganic layer even when the inorganic layer is laminated. As a result, process abnormalities such as alignment problems caused by wrinkles in the inorganic layer can be suppressed. In the laminate of the present invention, the inorganic layer is thin, so that the organic layer does not hinder the elimination of warpage of the substrate.

[0052] The first substrate is not particularly limited, and may be a circuit substrate on which elements and wiring are formed, such as a sensor circuit substrate on which a pixel portion (pixel region) is provided, a circuit substrate on which a peripheral circuit portion such as a logic circuit that performs various signal processing related to the operation of the solid-state imaging device is mounted, or a circuit substrate on which a peripheral circuit such as a memory circuit is mounted.

[0053] The first substrate has a first surface having a plurality of chips and a second surface opposite the first surface, and the organic layer and the inorganic layer are disposed on the first surface. When a plurality of chips are disposed on the first substrate and an insulating layer is formed on the surface of the first substrate on which the chips are disposed, the chips form irregularities, resulting in an uneven connection surface and a decrease in connection reliability. In the laminate of the present invention, even on substrates having such irregularities, the organic layer fills the irregularities to flatten the connection surface, thereby suppressing warping and cracking of the first substrate and chips. Furthermore, by forming a thin inorganic layer on the organic layer, it is possible to eliminate substrate warpage while improving connection reliability under high temperature and high humidity. Furthermore, since connection reliability is improved under higher temperatures and high humidity, it is preferable that the inorganic layer cover the entire exposed surface of the organic layer.

[0054] Examples of the chips include memory circuit elements, logic circuit elements, etc. The number of chips is not particularly limited as long as it is two or more.

[0055] The organic layer preferably has a thickness of 10 μm or more. By setting the thickness of the organic layer within the above range, it can fulfill its role as an insulating layer and suppress warping and cracking of the substrate, thereby improving connection reliability. Furthermore, conventional laminates in which an inorganic layer is formed on an organic layer have been particularly prone to cracking in the inorganic layer when the organic layer is made into a thick film. However, the laminate of the present invention is less likely to crack the inorganic layer even when the organic layer is made into a thick film, and can exhibit high moisture resistance. The thickness of the organic layer is preferably 20 μm or more, more preferably 30 μm or more, and preferably 200 μm or less, and more preferably 100 μm or less.

[0056] 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.

[0057] 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, from the viewpoint of not interfering with the elimination of warpage of the substrate.

[0058] The laminate A of the present invention may further have a support substrate laminated on the inorganic layer. By laminating a support substrate on the inorganic layer, it becomes easy to fix the laminate A of the present invention to the housing of an electronic component, such as an imaging device or semiconductor device. Examples of the support substrate include glass and single crystal silicon.

[0059] The laminate A of the present invention may further have a second substrate on the second surface of the first substrate, and the first substrate and the second substrate may be electrically connected. In the laminate A of the present invention, the warping and cracking of the first substrate are suppressed by the organic layer, so that the warping and cracking of the second substrate further laminated on the first substrate are also suppressed, thereby improving connection reliability. The second substrate may be the same as the first substrate.

[0060] FIG. 1 shows a schematic diagram illustrating an example of a laminate A of the present invention. As shown in FIG. 1, the laminate A of the present invention has a structure in which an organic layer 3 and an inorganic layer 4 are laminated on the surface (first surface) of a first substrate 1 having a plurality of chips 2 on which the chips are laminated, and the organic layer 3 and the inorganic layer 4 function as insulating layers. Conventional insulating layers consisting of an organic layer and an inorganic layer exhibit excellent connection reliability by suppressing warping and cracking of the substrate through the organic layer 3 and suppressing moisture permeation through the inorganic layer 4, but are prone to wrinkling in the inorganic layer, which can cause process abnormalities. In the laminate of the present invention, by using the curable resin composition of the present invention as the material for the organic layer, wrinkling in the inorganic layer is less likely to occur, thereby suppressing process abnormalities such as alignment defects. Furthermore, the laminate A of the present invention may have a support substrate 5 laminated on the inorganic layer 4, or a second substrate 6 may be laminated on the surface (second surface) of the first substrate 1 opposite the surface on which the organic layer 3 is laminated, and the first substrate 1 and the second substrate 6 may be electrically connected. Although the organic layer 3 and the inorganic layer 4 are each a single layer in FIG. 1, they may each be made up of a plurality of layers.

[0061] The present invention also provides a method for manufacturing a laminate A of the present invention, which includes a step of applying the curable resin composition of the present invention to a first surface of a first substrate having a first surface having a plurality of chips and a second surface opposite the first surface, and forming an organic layer by solvent drying and thermal curing, and a step of forming an inorganic layer on the organic layer.

[0062] The method for producing the laminate A of the present invention first involves applying the curable resin composition of the present invention to the first surface of a first substrate having a first surface bearing a plurality of chips and a second surface opposite the first surface, followed by solvent drying and thermal curing to form an organic layer. Conventional laminates using inorganic materials for the insulating layer have been produced by time-consuming methods such as chemical vapor deposition (CVD) and sputtering. Because the insulating layer of the laminate of the present invention is primarily an organic compound, it can be produced by applying a solution and drying, thereby improving not only connection reliability but also production efficiency. The first substrate and curable resin composition are the same as the first substrate and curable resin composition of the present invention in the laminate A of the present invention.

[0063] 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. However, from the viewpoint of reducing residual solvent and improving the heat resistance of the organic layer, 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. However, 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. However, from the viewpoint of suppressing thermal decomposition of the organic layer, 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.

[0064] The method for producing the laminate A of the present invention then carries out a step of forming an inorganic layer on the organic layer. Methods for forming the inorganic layer include chemical vapor deposition (CVD), sputtering, vapor deposition, and the like.

[0065] When the laminate A of the present invention has a supporting substrate, the method for producing the laminate A of the present invention further includes a step of bonding the supporting substrate onto the inorganic layer.

[0066] When the laminate A of the present invention has a second substrate, the method for producing the laminate A of the present invention includes a step of laminating the second substrate on the second surface of the first substrate and electrically connecting the first substrate and the second substrate. Examples of a method for electrically connecting the first and second substrates include a method in which electrodes of the first and second substrates are melted and connected by heat treatment. The heat treatment is usually performed at 400°C for about 4 hours.

[0067] The laminate using the cured film of the present invention can also be a laminate having a structure in which two substrates having electrodes are electrically connected, and an insulating layer consisting of the cured film of the present invention and an inorganic layer is disposed between the two substrates. Such a laminate having an organic layer and an inorganic layer consisting of the cured film of the present invention between a third substrate having an electrode and a fourth substrate having an electrode, in which the electrodes of the third substrate and the electrodes of the fourth substrate are electrically connected via through-holes penetrating the organic layer and the inorganic layer (hereinafter also referred to as laminate B) is also one aspect of the present invention.

[0068] The laminate B of the present invention is a laminate having an organic layer and an inorganic layer made of the cured film of the present invention between a third substrate having an electrode and a fourth substrate having an electrode, and the electrode of the third substrate and the electrode of the fourth substrate are electrically connected via through holes that penetrate the organic layer and the inorganic layer. The cured film and the inorganic layer provided between the electrode of the third substrate (hereinafter also referred to as the first electrode) and the electrode of the fourth substrate (hereinafter also referred to as the second electrode) act as insulating layers, thereby preventing current short circuits. Conventional insulating layers are made of SiN or SiO ２ Since only hard inorganic materials such as these have been used, if warpage occurs during the formation of an insulating layer or a laminate, it cannot be resolved by stress relaxation, resulting in warpage of the substrate and resulting electrode misalignment and cracking. In the present invention, by using a cured film made of a curable resin composition that is more flexible than inorganic materials as the main insulating layer, warpage of the substrate can be resolved, thereby achieving high connection reliability. Furthermore, by using an inorganic layer that is thin enough not to interfere with the elimination of warpage of the substrate as an auxiliary insulating layer, moisture resistance can be improved. Furthermore, the cured film of the present invention is less likely to wrinkle even when an inorganic layer is laminated on the cured film, thereby reducing process defects such as poor alignment. Here, "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.

[0069] The third substrate and the fourth substrate can be the same as the first substrate. The organic layer and the inorganic layer can be the same as the organic layer and the inorganic layer of the laminate A of the present invention. The inorganic layer may be formed on both the organic layers of the third substrate and the fourth substrate, or on only one of the organic layers. In particular, since this improves connection reliability under high temperature and high humidity, it is preferable that the inorganic layer be formed on the organic layers of both the third substrate and the fourth substrate, and it is more preferable that the inorganic layer cover the entire side surface of the organic layer.

[0070] The materials of the electrodes of the third substrate and the fourth substrate and the conductive material are not particularly limited, and conventionally known electrode materials such as gold, copper, and aluminum can be used.

[0071] The laminate B 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 organic layer. 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 organic layer. The material for the barrier metal layer can be a known material such as tantalum, tantalum nitride, titanium nitride, silicon oxide, or silicon nitride.

[0072] 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.

[0073] FIG. 2 shows a schematic diagram illustrating an example of a laminate B of the present invention. As shown in FIG. 2, the laminate B of the present invention has a structure in which a third substrate 7 and a fourth substrate 9 each having an electrode 8 are bonded via an organic layer 3 and an inorganic layer 4, and the electrodes 8 on the third substrate 7 and the fourth substrate 9 are electrically connected via a conductive material filled in through-holes 10 provided in the organic layer 3. In conventional laminates, the organic layer 3, which corresponds to the insulating layer, is made of a hard inorganic material. Therefore, when warping occurs in the substrate or laminate, this cannot be resolved by stress relaxation, making the electrodes more susceptible to misalignment and cracking. The laminate B of the present invention uses an organic layer made of the flexible cured film of the present invention as an insulating layer, thereby eliminating warping of the substrate or laminate and suppressing electrode misalignment and cracking. Furthermore, moisture resistance can be improved by using a thin inorganic layer 4 as an auxiliary insulating layer that is thin enough not to interfere with the elimination of substrate warping. The inorganic layer 4 can further improve moisture resistance if it covers the entire side surface of the organic layer 3. Furthermore, the cured film of the present invention is less likely to wrinkle even when an inorganic layer is laminated on the cured film, thereby preventing process defects such as poor alignment. Furthermore, the laminate B of the present invention may have a barrier metal layer 11 provided on the surface of the through hole 10. The provision of the barrier metal layer 11 makes it difficult for the conductive material filled in the through hole 10 to diffuse into the organic layer 3, thereby further preventing short circuits and poor conduction. Note that, although the inorganic layer 4 is provided on each of the organic layers 3 on the third substrate 7 side and the fourth substrate 9 side in FIG. 2 , it may be provided on only one of them.

[0074] The present invention also provides a method for producing a laminate B, the method comprising the steps of: applying the curable resin composition of the present invention to the electrode-bearing surfaces of a third substrate having an electrode and a fourth substrate having an electrode, and then drying the solvent and thermally curing the composition to form an organic layer; forming an inorganic layer on the organic layer; forming through holes in each of the organic layers and the inorganic layer; filling each of the through holes with a conductive material; polishing the surfaces of the third substrate having an electrode and the fourth substrate having an electrode on the side filled with the conductive material to form bonding electrodes; and bonding the third substrate having an electrode and the fourth substrate having an electrode so that the bonding electrodes are bonded to each other.

[0075] The method for producing the laminate B of the present invention first involves a step of applying the curable resin composition of the present invention to a third substrate having an electrode and a fourth substrate having an electrode, followed by solvent drying and thermal curing to form an organic layer, and a step of forming an inorganic layer on the organic layer. The steps of forming the organic layer and the inorganic layer can be performed using the same methods as in the method for producing the laminate A. The inorganic layer may be formed on each of the organic layers on the third substrate side and the fourth substrate side, or on only one of them.

[0076] The method for producing the laminate B of the present invention then includes a step of forming through holes in each of the organic layers and the inorganic layers. 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 substrate, the through holes are formed so as to penetrate the other layers as well and expose the electrode surface of the substrate.

[0077] The method for producing the laminate B of the present invention then includes a step of forming a barrier metal layer as needed. The barrier metal layer can be the same as that of the laminate B of the present invention. The barrier metal layer can be formed by sputtering, vapor deposition, or the like.

[0078] The method for producing the laminate B 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 B of the present invention.

[0079] The method for producing the laminate B of the present invention then includes a step of polishing the surfaces of the third substrate having the electrode and the fourth substrate having the electrode, which are filled with the conductive material, to form a bonding electrode. The conductive material formed in the unnecessary portion is removed by grinding, thereby forming 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 inorganic layer is exposed. The polishing method is not particularly limited, and for example, chemical mechanical polishing or the like can be used.

[0080] The method for producing the laminate B of the present invention then involves a step of bonding the third substrate having the electrode and the fourth substrate having the electrode together so that the bonding electrodes of the third substrate and the fourth substrate are bonded to each other. Examples of a method for bonding the third substrate and the fourth substrate include a method in which the electrodes and the connecting electrodes are melted and connected by heat treatment. The heat treatment is typically performed at 400°C for about 4 hours.

[0081] The uses of the laminates A and B of the present invention are not particularly limited, but they are suitable for imaging devices and semiconductor devices because even when an inorganic layer is formed on an organic layer, wrinkles are unlikely to occur in the inorganic layer and process abnormalities can be suppressed. Such imaging devices having the laminates of the present invention and semiconductor devices having the laminates of the present invention also constitute the present invention.

[0082] According to the present invention, it is possible to provide a curable resin composition that is less likely to cause wrinkles in an inorganic layer even when an inorganic layer is formed on the cured product, and that can suppress process abnormalities; a cured film of the curable resin composition; a laminate using the cured film; an imaging device and a semiconductor device that have the laminate; and a method for manufacturing the laminate.

[0083] 1A and 1B are schematic diagrams showing an example of a laminate A of the present invention, and FIG. 1C are schematic diagrams showing an example of a laminate B of the present invention.

[0084] The following examples will further illustrate the present invention, but the present invention is not limited to these examples.

[0085] (1) Production of Silsesquioxane (Resin A) 65.4 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 33.0 g of a colorless solid (DD-ONa).

[0086] A 300 ml three-neck flask equipped with a dropping funnel, reflux condenser, and thermometer was charged with 11.6 g of compound (DD-ONs), 100 g of tetrahydrofuran, and 3.0 g of triethylamine, and the flask was sealed with dry nitrogen. While stirring with a magnetic stirrer, 4.5 g (30 mmol) of methyltrichlorosilane was added dropwise at room temperature. Stirring was then continued at room temperature for 3 hours. 50 g of water was added to the reaction solution to dissolve the generated sodium chloride and hydrolyze unreacted methyltrichlorosilane. The reaction mixture thus obtained was separated, and the organic layer was washed once with 1 N hydrochloric acid, once with a saturated aqueous sodium bicarbonate solution, and then three times with ion-exchanged water. The washed organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure using a rotary evaporator to obtain 7.1 g of a white powdery solid (DD(Me)-OH).

[0087] A 100 mL flask was equipped with a condenser, mechanical stirrer, Dean-Stark tube, oil bath, and thermometer protection tube, and the atmosphere inside the flask was replaced with nitrogen. 5.0 g of DD(Me)-OH, 11.6 g of octamethylcyclotetrasiloxane (D4), 3.9 g of sulfuric acid, 52 g of toluene, and 13 g of 4-methyltetrahydropyran were placed in the flask. After stirring at 100°C for 5 hours, water was poured into the reaction mixture, and the aqueous layer was extracted with toluene. The combined organic layer was washed with water, aqueous sodium bicarbonate, and saturated saline, and then dried over anhydrous sodium sulfate. This solution was concentrated under reduced pressure, and the residue was reprecipitated in a solution of 2-propanol:ethyl acetate = 50:7 (weight ratio), purified, and dried to obtain a silsesquioxane (Resin A, weight average molecular weight: 36,000) having the structure shown in structural formula (8) below, in which m is 27 and n is an average of 4.

[0088]

[0089] (2) Production of Resin B A 100 mL flask was equipped with a condenser, mechanical stirrer, Dean-Stark tube, oil bath, and thermometer protection tube, and the interior of the flask was purged with nitrogen. 5.0 g of DD(Me)-OH, 11.2 g of octamethylcyclotetrasiloxane (D4), 3.9 g of sulfuric acid, 52.0 g of toluene, and 13.0 g of 4-methyltetrahydropyran were placed in the flask. After stirring at 100°C for 5 hours, water was poured into the reaction mixture, and the aqueous layer was extracted with toluene. The combined organic layer was washed with water, aqueous sodium bicarbonate, and saturated saline, and then dried over anhydrous sodium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by reprecipitation in a solution of 2-propanol:ethyl acetate = 50:7 (weight ratio), followed by drying to obtain an organosilicon compound (Resin B, weight average molecular weight 46,000) having the structure of the above formula (8), m = 36, and n (number of DMS chains) = 3 on average.

[0090] (3) Preparation of Resin C SST-3PM2 manufactured by Gelest was used as Resin C.

[0091] (4) Preparation of Heat-Resistant Resin (Resin D) A 100 mL flask was equipped with a condenser, mechanical stirrer, Dean-Stark tube, oil bath, and thermometer protection tube. 11.1 g of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) (manufactured by Daikin Corporation), 7.8 g of bisaminopropyltetramethyldisiloxane (PAM-E, manufactured by Shin-Etsu Silicones Co., Ltd.), and 92.1 g of anisole were added to the flask and stirred. The flask was heated at 100°C for 1 hour and then refluxed in a 170°C oil bath for 1 hour. The solution was cooled to room temperature, and 1.3 g of citraconic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. The mixture was stirred at 120°C for 10 minutes and then refluxed in a 170°C oil bath for 1 hour to obtain a heat-resistant resin (Resin D, weight average molecular weight: 9900) having the structure shown below in structural formula (9). In the following structural formula (9), l represents the number of repeating units.

[0092]

[0093] (5) Production of Resin E A 100 mL flask was equipped with a condenser, mechanical stirrer, Dean-Stark tube, oil bath, and thermometer protection tube, and the atmosphere inside the flask was replaced with nitrogen. 5.0 g of DD(Me)-OH, 11.6 g of octamethylcyclotetrasiloxane (D4), 3.9 g of sulfuric acid, 52 g of toluene, and 13 g of 4-methyltetrahydropyran were placed in the flask. After stirring at 100°C for 5 hours, water was poured into the reaction mixture, and the aqueous layer was extracted with toluene. The combined organic layer was washed with water, aqueous sodium bicarbonate, and saturated saline, and then dried over anhydrous sodium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by reprecipitation in a solution of 2-propanol:ethyl acetate = 50:7 (weight ratio), followed by drying to obtain an organosilicon compound (Resin E, weight average molecular weight 100,000) having the structure of the above structural formula (8), m = 70, and n (number of DMS chains) = 4 on average.

[0094] Example 1 (1) Production of Curable Resin Composition A curable resin composition was obtained by adding and mixing 100 parts by weight of the obtained silsesquioxane, 1 part by weight of the obtained heat-resistant resin, 0.1 parts by weight of the catalyst, and 30 parts by weight of the silica filler so that the solvent content was 65% by weight. The details of each raw material used are as follows: Catalyst: ZC-162, an acetylacetonate complex having a zirconium central metal, manufactured by Matsumoto Fine Chemical Co., Ltd. Silica filler: MT-10, manufactured by Tokuyama Corporation, bulk density: 0.05 g / cm ３ , Shape: Powdered Solvent: N-methyl-2-pyrrolidone (referred to as NMP in the table)

[0095] (2) Measurement of coefficient of linear expansion (CTE) The curable resin composition applied to a sheet using an applicator was dried at 125°C for 10 minutes, and then heated at 300°C for 1 hour to obtain a film of the cured product of the curable resin composition having a thickness of 300 μm. The obtained film sample was punched out to a size of 4 mm x 22 mm to prepare a measurement sample. The obtained measurement sample was measured for linear thermal expansion when cooled to -70°C and then heated to 400°C at a heating rate of 5°C / min using a thermomechanical analyzer (TMA7100, manufactured by Hitachi High-Tech Science Corporation), and the coefficient of linear expansion in the range of -40°C to 100°C was calculated.

[0096] (3) Measurement of Elastic Modulus The curable resin composition applied to a sheet using an applicator was dried at 125°C for 10 minutes, and then heated at 300°C for 1 hour to obtain a film of the cured product of the curable resin composition having a thickness of 500 μm. The obtained film sample was punched out to a size of 5 mm x 35 mm to prepare a measurement sample. The elastic modulus of the obtained measurement sample at 300°C was measured using a dynamic viscoelasticity measuring device (manufactured by IT Measurement Control Co., Ltd., DVA-200) under conditions of a constant temperature rise tensile mode, a temperature rise rate of 5°C / min, and a frequency of 1 Hz.

[0097] (4) Production of Laminate 10 g of the obtained curable resin composition was ejected onto the center of an 8-inch silicon wafer (surface roughness <0.1 μm). Next, using a spin coater (ACT-400II; manufactured by ACTIVE Corporation), spin coating was performed at a rotation speed of 1500 rpm for 10 seconds. Subsequently, the spin-coated silicon wafer was dried for 10 minutes in an oven at 125°C to remove the solvent, and then heat-treated at 300°C for 1 hour to obtain an organic layer. The obtained silicon wafer with the organic layer was heat-treated at 400°C for 1 hour in a nitrogen atmosphere using a vacuum process high-speed heating furnace (VPO-650, manufactured by Unitemp Corporation). Next, inorganic film formation by CVD was performed using a PE-CVD (product number MPD-220NL, manufactured by Samco Corporation), and SiO was deposited on the organic layer. ２ A laminate was obtained by forming an inorganic layer having a thickness of 400 nm.

[0098] (Examples 2 to 16, Comparative Examples 1 to 5) Laminates were obtained under the same conditions as in Example 1, except that the compositions and thicknesses of the organic and inorganic layers were as shown in Tables 1 and 2, and measurements were carried out. The details of the raw materials in the tables are as follows: QSG-100: Silica filler, manufactured by Shin-Etsu Silicones Co., Ltd., shape: spherical NSS-3N: Silica filler, manufactured by Tokuyama Corporation, shape: spherical Sciqas 0.1 μm: Silica filler, manufactured by Sakai Chemical Industry Co., Ltd., shape: spherical MS-51: Silica oligomer, manufactured by Mitsubishi Chemical Corporation Ethyl silicate 48: Silica oligomer, manufactured by Colcoat Co., Ltd. GBL: γ-butyrolactone

[0099] <Evaluation> The laminates obtained in the examples and comparative examples were evaluated as follows. The results are shown in Tables 1 and 2.

[0100] (Evaluation of Surface Roughness) The surface of the inorganic layer of the obtained laminate was observed with a laser microscope to measure the surface roughness of the laminate (inorganic layer). Specifically, observation was performed using a laser microscope (OLS4100, manufactured by Olympus Corporation) at 20 magnifications in an observation area of ​​643 μm square, and the surface roughness Sa value was calculated.

[0101] (Evaluation of Wrinkles in Inorganic Layer) The inorganic layer of the obtained laminate was visually observed, and the wrinkling of the inorganic layer was evaluated as follows: "Good" if no wrinkles occurred on the entire surface; "Good" if there were a mixture of wrinkle-free and wrinkled areas on the wafer surface; and "Poor" if wrinkles occurred on the entire surface.

[0102]

[0103]

[0104] According to the present invention, it is possible to provide a curable resin composition that is less likely to cause wrinkles in an inorganic layer even when an inorganic layer is formed on the cured product, and that can suppress process abnormalities; a cured film of the curable resin composition; a laminate using the cured film; an imaging device and a semiconductor device that have the laminate; and a method for manufacturing the laminate.

[0105] REFERENCE SIGNS LIST 1 First substrate 2 Chip 3 Organic layer 4 Inorganic layer 5 Support substrate 6 Second substrate 7 Third substrate 8 Electrode 9 Fourth substrate 10 Through hole 11 Barrier metal layer

Claims

1. A curable resin composition containing silsesquioxane, a solvent, and silica filler as an inorganic filler, wherein the solvent is dried at 125°C for 10 minutes, and the cured product after heat treatment at 300°C for 1 hour has an elastic modulus of 0.2 MPa or more at 300°C.

2. The curable resin composition according to claim 1, wherein the cured product, after drying the solvent at 125°C for 10 minutes and heat-curing it by heat treatment at 300°C for 1 hour, has a coefficient of linear expansion (CTE) of 500 ppm / °C or less in the range of -40°C to 100°C.

3. The curable resin composition according to claim 1, wherein silsesquioxane has structures represented by the following structural formulas (A) and (B) within a single molecule. 【Chemistry 1】 In structural formulas (A) and (B), R Ａ , R Ｂ Each of these independently represents an aliphatic group, an aromatic group, or a hydrogen atom. j and k each represent an integer of 1 or greater.

4. The curable resin composition according to claim 1, wherein silsesquioxane has a structure represented by the following structural formula (1). 【Chemistry 2】 In structural formula (1), R ０ , R １ and R ２ Each of these independently represents a linear, branched, or cyclic aliphatic group, aromatic group, or hydrogen atom. The aliphatic group and the aromatic group may or may not have substituents. m and n each represent an integer of 1 or more.

5. The curable resin composition according to claim 1, wherein the silica filler content is 15 parts by weight or more and 40 parts by weight or less per 100 parts by weight of silsesquioxane.

6. The curable resin composition according to claim 1, wherein the solvent has a boiling point of 130°C or higher and 250°C or lower.

7. The curable resin composition according to claim 1, which is used by laminating an inorganic layer on top of a heat-cured product.

8. A cured film obtained by thermosetting the curable resin composition according to Claim 1.

9. A laminate comprising an organic layer made of a cured film according to claim 8 on a first substrate, and an inorganic layer laminated on the organic layer, The first substrate is a laminate having a first surface with a plurality of chips and a second surface opposite to it, with the organic layer and the inorganic layer on the first surface side.

10. The laminate according to claim 9, wherein a support substrate is laminated on an inorganic layer.

11. The laminate according to claim 9, further comprising a second substrate on the second surface of a first substrate, wherein the first substrate and the second substrate are electrically connected.

12. A laminate comprising an organic layer and an inorganic layer made of the cured film described in claim 8, between a third substrate having electrodes and a fourth substrate having electrodes, A laminate in which the electrodes of the third substrate and the electrodes of the fourth substrate are electrically connected via through-holes that penetrate the organic layer and the inorganic layer.

13. The laminate according to claim 12, having a barrier metal layer on the surface of the through hole.

14. An imaging device having a laminate according to any one of claims 9 to 13.

15. A semiconductor device having a laminate according to any one of claims 9 to 13.

16. A step of forming an organic layer by applying a curable resin composition according to any one of claims 1 to 6 onto the first surface of a first substrate having a first surface with multiple chips and a second surface opposite to it, and then solvent drying and heat curing, A method for manufacturing a laminate, comprising the step of forming an inorganic layer on the organic layer.

17. A step of forming an organic layer by applying the curable resin composition according to any one of claims 1 to 6 onto the electrode-bearing surfaces of a third substrate having electrodes and a fourth substrate having electrodes, followed by solvent drying and heat curing, The step of forming an inorganic layer on the organic layer, A step of forming through holes in each of the organic and inorganic layers, A step of filling each of the aforementioned through holes with a conductive material, A step of forming a bonded electrode by polishing the surface of the side of the third substrate having the electrode and the fourth substrate having the electrode that is filled with the conductive material, A method for manufacturing a laminate, comprising the step of bonding a third substrate having the electrodes and a fourth substrate having the electrodes together such that the bonding electrodes of the substrates are bonded to each other.

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