Curable resin composition, cured film, multilayer object, and semiconductor device

Abstract

The purpose of the present invention is to provide: a curable resin composition that has a low foreign matter content and can give a cured object which, even when an inorganic layer is formed thereon, inhibits the inorganic layer from creasing and thereby suppresses process abnormalities; a cured film formed from the curable resin composition; a multilayer object including the cured film; and a semiconductor device including the multilayer object. This curable resin composition comprises a solvent and a silicone resin having a silanol group, and contains an alkoxysilane and has a filler content of 2 wt% or less. A cured object obtained by subjecting the curable resin composition to the drying of the solvent under the condition of 125°C for 10 minutes and then to a heat treatment at 300°C for 1 hour to thermally cure the curable resin composition has a tensile modulus at 300°C of 0.7 MPa or greater.

Description

Curable resin composition, cured film, laminate and semiconductor device

[0001] The present invention relates to a curable resin composition, a cured film, a laminate, and a semiconductor device.

[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] In order to prevent warping and cracking of the substrate due to high-temperature treatment, it is conceivable to use a heat-resistant organic compound that is more flexible than inorganic materials as an organic insulating layer. However, resins are easily permeable to moisture and are therefore vulnerable to high-humidity environments. If moisture penetrates into 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] To address this problem, a method has been proposed in which a filler is added to the curable resin composition that is the base material for the organic layer. Adding a filler to the curable resin composition makes it less likely for wrinkles to form in the inorganic layer, thereby reducing alignment defects. However, when a filler is added to the curable resin composition, the curable resin composition aggregates, making it impossible to perform a filtration step for removing foreign matter when producing the curable resin composition. When a semiconductor device is manufactured using a curable resin composition that contains foreign matter without performing a filtration step, the curable resin composition may not be applied evenly to the wafer, which can lead to process abnormalities.

[0009] The present invention aims to provide a curable resin composition that is less likely to contain foreign matter, 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; and a semiconductor device having the laminate.

[0010] The present invention includes the following Disclosures 1 to 17. The present invention is described in detail below. [Disclosure 1] A curable resin composition containing a silicone resin having a silanol group and a solvent, wherein the curable resin composition contains an alkoxysilane, and the curable resin composition has a filler content of 2% by weight or less. The curable resin composition is obtained by drying the solvent at 125°C for 10 minutes and then heat-curing the composition by heat-treating at 300°C for 1 hour, and the cured product has a tensile modulus at 300°C of 0.7 MPa or more. [Disclosure 2] The curable resin composition according to Disclosure 1, wherein an inorganic layer is laminated on the cured product of the curable resin composition. [Disclosure 3] The curable resin composition according to Disclosure 1 or 2, wherein the curable resin composition is obtained by drying the solvent at 125°C for 10 minutes and then heat-curing the composition by heat-treating at 300°C for 1 hour, and the cured product has a first-scan coefficient of linear expansion (CTE) in the range of 25°C to 350°C of 200 ppm / °C or less. [Disclosure 4] The curable resin composition according to any one of Disclosures 1 to 3, further comprising a catalyst and a heat-resistant additive. [Disclosure 5] The curable resin composition according to any one of Disclosures 1 to 4, wherein the silicone resin has a structure represented by the following structural formula (1): In structural formula (1), m represents an integer of 1 or more, and n represents 3 or 4. [Disclosure 6] The curable resin composition according to any one of Disclosures 1 to 5, wherein the alkoxysilane has a weight-average molecular weight of 579 or more. [Disclosure 7] The curable resin composition according to any one of Disclosures 1 to 6, wherein the alkoxysilane has three or more alkoxyl groups. [Disclosure 8] The curable resin composition according to any one of Disclosures 1 to 7, wherein the alkoxysilane is branched or linear, and the alkoxyl group has two or more carbon atoms. [Disclosure 9] The curable resin composition according to any one of Disclosures 1 to 8, wherein the alkoxysilane does not have a silanol group. [Disclosure 10] The curable resin composition according to any one of Disclosures 1 to 9, wherein the content of the alkoxysilane is 5 parts by weight or more and 50 parts by weight or less, relative to 100 parts by weight of the silicone resin. [Disclosure 11] A cured film obtained by thermally curing the curable resin composition according to any one of Disclosures 1 to 10. [Disclosure 12] A laminate comprising an organic layer made of the cured film according to Disclosure 11 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 13] The laminate according to Disclosure 12, wherein a support substrate is laminated on the inorganic layer. [Disclosure 14] The laminate according to Disclosure 12 or 13, 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 15] A laminate comprising an organic layer made of the cured film according to Disclosure 11 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 16] The laminate according to Disclosure 15, wherein a barrier metal layer is provided on the surface of the through hole. [Disclosure 17] A semiconductor device having the laminate according to Disclosure 12 or 15.

[0011] The curable resin composition of the present invention contains a silicone resin having silanol groups (hereinafter simply referred to as silicone resin). Silicone resins have high heat resistance while maintaining flexibility comparable to that of organic compounds. Therefore, by using a cured film containing silicone resin as the insulating layer of a laminate, warping and cracking of the substrate can be suppressed, thereby improving the reliability of electrical connection. The silicone resin is not particularly limited as long as it has silanol groups and is thermosetting, but it is preferable that the silicone resin have a structure represented by the following structural formula (2) in order to further suppress warping and cracking of the substrate.

[0012] In structural formula (2), 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.

[0013] In the above structural formula (2), 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.

[0014] In the above structural formula (2), 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 R ２When 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.

[0015] In the structural formula (2), m and n each represent an integer of 1 or greater and represent the number of repeating units. The m is preferably 30 or greater, more preferably 50 or greater, and preferably 100 or less. The n is preferably 1 or greater, more preferably 3 or greater, even more preferably 4 or greater, and preferably 8 or less.

[0016] More specifically, the silicone resin preferably has a structure represented by the following structural formula (1). By using a silicone resin having such a structure, warping of an element and misalignment or cracking of an electrode can be further suppressed when used in an insulating layer of a laminate. Furthermore, since silicone resins have excellent heat resistance, decomposition of a cured film due to high-temperature treatment performed during the manufacture of electronic components can be further suppressed.

[0017] In structural formula (1), m represents an integer of 1 or more, and n represents 3 or 4.

[0018] The content of the silicone resin 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 (components other than the solvent) in the curable resin composition. The content of the silicone resin 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.

[0019] The weight-average molecular weight of the silicone resin is not particularly limited, but is preferably 1,000 or more and 150,000 or less. Having a weight-average molecular weight of the silicone resin within this range improves film-forming properties during application, further enhancing planarization performance and further suppressing warping and cracking of elements. The weight-average molecular weight of the silicone resin is more preferably 1,100 or more, even more preferably 1,400 or more, even more preferably 5,000 or more, very preferably 10,000 or more, particularly preferably 30,000 or more, more preferably 100,000 or less, even more preferably 70,000 or less, even more preferably 50,000 or less, and very preferably 40,000 or less. The weight-average molecular weight of the silicone resin 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.

[0020] The content of the silicone resin is preferably 65% ​​by weight or more and 99% by weight or less based on 100% by weight of the solid components (components other than the solvent) of the curable resin composition. By having the content of the silicone resin in the curable resin composition within the above range, warping and cracking of the element can be suppressed, and electrical connection reliability can be further improved. The content of the silicone resin 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, even more preferably 97% by weight or less, and even more preferably 90% 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 silicone resin can be made to have a viscosity sufficient to be applied to a substrate, and unevenness 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 of the solvent within the above range allows the components in the curable resin composition to be uniformly dispersed. The boiling point of the solvent is more preferably 150°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, 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 product and allowing the connection surface to be flat. As a result, the bonding reliability of the substrates can be 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 silicone resin. By having the content of the solvent relative to the silicone resin in the above range, the planarization performance of the substrate surface can be further improved. The content of the solvent relative to the silicone resin 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 an alkoxysilane. By using an alkoxysilane in the curable resin composition and using a filler in an amount not greater than the amount described below, the filterability of the curable resin composition is improved, and foreign matter can be removed by performing a filtration process. As a result, the curable resin composition can be applied more reliably and evenly, thereby suppressing process abnormalities caused by application of the curable resin composition. Furthermore, by crosslinking the silicone resin during curing with the alkoxysilane, when an inorganic layer is formed on a cured product of the curable resin composition, the occurrence of wrinkles in the inorganic layer can be suppressed, and process abnormalities such as alignment abnormalities can also be suppressed.

[0026] The alkoxysilane preferably has three or more alkoxyl groups. When the alkoxysilane has three or more alkoxyl groups, the crosslinking reactivity can be further increased, and the 300°C tensile modulus of the cured product of the curable resin composition can be set within a suitable range. The alkoxysilane more preferably has six or more alkoxyl groups, and even more preferably has nine or more alkoxyl groups. The upper limit of the alkoxyl groups in the alkoxysilane is not particularly limited, but is preferably 30 or less from the viewpoint of viscosity storage stability.

[0027] The alkoxysilane is preferably branched or linear and the alkoxyl group has two or more carbon atoms. When the alkoxysilane structure is branched or linear and the alkoxyl group has two or more carbon atoms, the reactivity of the alkoxysilane is appropriately reduced, and the storage stability of the resulting curable resin composition can be further improved. From the viewpoint of the balance between reactivity and storage stability, when the alkoxysilane is linear, the number of carbon atoms in the alkoxyl group is preferably four or less, and more preferably three or less. Here, the term "branched" refers to a structure in which an alkoxyl group is bonded to each main chain or side chain of a branched siloxane bond, or a structure in which a silicon atom bonded to an alkoxyl group is bonded to an atom constituting a dendrimer structure or a cyclic structure, and the like, in which a silicon atom bonded to an alkoxyl group is branched.

[0028] The alkoxysilane preferably does not have a silanol group, which can suppress intramolecular bonding of the alkoxysilane, thereby further suppressing cracking of the element.

[0029] Specific examples of the alkoxysilane include tetraalkoxysilanes, trialkoxysilanes, dialkoxysilanes, etc. Specific examples include tetraethoxysilane, 2,4,6,8-tetramethyl-2,4,6,8-tetrakis[2-(triethoxysilyl)ethyl]cyclotetrasiloxane, tetrakis[[[2-(trimethoxysilyl)ethyl]dimethylsilyl]oxy]silane, 1,2-bis(triethoxysilyl)ethane, dimethoxydimethylsilane, etc. Among these, trialkoxysilanes are preferred because they can further improve the filterability of the resulting curable resin composition, thereby further suppressing the inclusion of foreign matter, and further suppressing wrinkling of the inorganic layer when an inorganic layer is formed on the cured product.

[0030] The weight-average molecular weight of the alkoxysilane is preferably 579 or more. By having the weight-average molecular weight of the alkoxysilane be 579 or more, the silicone resin can be more reliably crosslinked, thereby further suppressing wrinkles in the inorganic layer. The weight-average molecular weight of the alkoxysilane is more preferably 600 or more, and even more preferably 700 or more. From the viewpoint of compatibility with the resin composition, the upper limit of the weight-average molecular weight of the alkoxysilane is preferably 100,000 or less, and more preferably 10,000 or less. The weight-average molecular weight of the alkoxysilane 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.

[0031] The content of the alkoxysilane is preferably 5 parts by weight or more and 50 parts by weight or less relative to 100 parts by weight of the silicone resin. By having the content of the alkoxysilane relative to 100 parts by weight of the curable resin composition within the above range, the tensile modulus of the obtained curable resin composition at 300 ° C. can be further increased, and when an inorganic layer is formed on the cured product of the obtained curable resin composition, wrinkles in the inorganic layer can be further suppressed. The content of the alkoxysilane relative to 100 parts by weight of the silicone resin is preferably 10 parts by weight or more, more preferably 13 parts by weight or more, even more preferably 14 parts by weight or more, even more preferably 15 parts by weight or more, preferably 40 parts by weight or less, more preferably 30 parts by weight or less, and even more preferably 20 parts by weight or less.

[0032] The curable resin composition of the present invention preferably contains a catalyst. The catalyst serves to accelerate the curing reaction of the silicone resin. 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 cured product due to high-temperature treatment can be further suppressed, and the elastic modulus can be easily controlled. 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 accelerate 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 product obtained by curing the curable resin composition.

[0033] 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 relative to 100 parts by weight of the silicone resin. By setting the content of the catalyst within this range, curing can be further promoted and decomposition of the cured product due to high-temperature treatment can be further suppressed. The content of the catalyst is more preferably 0.05 parts by weight or more, even 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 relative to 100 parts by weight of the silicone resin.

[0034] The curable resin composition preferably contains a heat-resistant additive. By using the heat-resistant additive in the curable resin composition, it is possible to obtain a cured product that is less likely to crack when subjected to high-temperature treatment, even when the cured product has a large thickness.

[0035] Examples of the heat-resistant additive include polyimide, epoxy resin, silicone resin, benzoxazine resin, cyanate resin, and phenolic resin, with polyimide being particularly preferred from the viewpoint of heat resistance.

[0036] The weight average 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, even if a thick cured product is obtained, the cured product is less likely to crack when treated at high temperatures. The weight average 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.

[0037] The content of the heat-resistant additive is preferably 0.5 parts by weight or more and 50 parts by weight or less relative to 100 parts by weight of the silicone resin.By making the content of the heat-resistant additive within the above range, even if a thick cured product is obtained, it is possible to make a cured product that is less likely to cause film cracking during high-temperature treatment.The content of the heat-resistant additive is more preferably 0.7 parts by weight or more relative to 100 parts by weight of the silicone resin, more preferably 0.75 parts by weight or more, even more preferably 1 part by weight or more, more preferably 20 parts by weight or less, even more preferably 10 parts by weight or less, and particularly preferably 5 parts by weight or less.

[0038] When the heat-resistant additive is a polyimide, the polyimide preferably has a siloxane bond, which enhances compatibility with the silicone resin, thereby further suppressing surface roughness caused by precipitation of the polyimide during application.

[0039] 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 silicone resin 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 carbon atoms and silicon atoms is measured from the repeating unit of the main chain, whereby the number of carbon atoms and silicon atoms can be determined.

[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 one of the structures represented by the following structural formulas (3) to (8) at at least one terminal, and particularly preferably has one of the structures represented by the following structural formulas (3) to (8) at both terminals. In the structural formulas below, "*" represents the bonding site with 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 the silicone resin, 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.

[0043] 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 silicone resin.By setting the content of polyimide within the above range, even if a thick cured product is obtained, it is possible to obtain a cured product 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 silicone resin, more preferably 0.75 parts by weight or more, and even more preferably 1 part by weight or more, and 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 curable resin composition of the present invention contains 2 parts by weight or less of a filler relative to 100 parts by weight of the silicone resin. Conventional curable resin compositions containing a filler can prevent wrinkles in an inorganic layer even when an inorganic layer is formed on the cured product. However, due to the filler agglomeration, the filterability is poor, and the filtration process for removing foreign matter during the production of the curable resin composition cannot be performed sufficiently, resulting in contamination with foreign matter. A curable resin composition containing foreign matter may not be applied evenly to a wafer or the like, which may cause new process abnormalities. By reducing the filler content, which causes reduced filterability, the curable resin composition of the present invention can perform a filtration process during production and prevent the introduction of foreign matter. As a result, the curable resin composition can be applied evenly, and process abnormalities caused by application can be suppressed. Furthermore, by reducing the filler content and using the alkoxysilane, the occurrence of wrinkles in the inorganic layer when an inorganic layer is formed on a cured product of the curable resin composition can be suppressed, thereby suppressing process abnormalities such as alignment abnormalities. The content of the filler is preferably as small as possible, and more preferably 0 parts by weight, that is, no filler is contained. As described above, the content of the filler is preferably 0 parts by weight, but the lower limit when a filler is contained is, for example, 0.001 parts by weight. Here, the filler refers to an additive added to improve the tensile modulus of the cured product of the curable resin composition, particularly the tensile modulus at high temperatures, and examples thereof include inorganic fillers such as silica filler. The content of the filler can be measured by a conventionally known method.

[0045] The curable resin composition of the present invention has a filler content of 2 wt% or less based on 100 wt% of the resin solids (components other than the solvent) in the curable resin composition. By ensuring that the filler content is within the above range, a filtration process can be performed during the production of the curable resin composition, thereby preventing the inclusion of foreign matter. As a result, the curable resin composition can be applied evenly, thereby preventing process defects caused by application. Furthermore, by reducing the filler content while using the alkoxysilane, the occurrence of wrinkles in the inorganic layer when an inorganic layer is formed on a cured product of the curable resin composition can be prevented, thereby preventing process defects such as alignment defects. The filler content is preferably as low as possible, and more preferably 0 wt%, i.e., no filler is contained. As described above, the filler content is preferably as low as possible, but the lower limit can be, for example, 0.001 wt%.

[0046] The curable resin composition of the present invention may contain other additives such as a viscosity modifier and an adhesion promoter, as needed, within the range that does not impair the effects of the present invention.

[0047] The curable resin composition of the present invention is thermally cured by drying the solvent at 125°C for 10 minutes and then heat-treating at 300°C for 1 hour, and the resulting cured product has a tensile modulus at 300°C of 0.7 MPa or more. Having the tensile modulus at 300°C of the cured product within the above range can prevent wrinkles from forming in the inorganic layer, thereby preventing process abnormalities caused by wrinkles in the inorganic layer. The tensile modulus at 300°C of the cured product is preferably 1 MPa or more, and more preferably 1.3 MPa or more. There is no particular upper limit to the tensile modulus at 300°C of the cured product, but from the perspective of further preventing warping and cracking of the substrate, it is preferably 100 MPa or less, and more preferably 50 MPa or less. The tensile modulus can be adjusted by the type of silicone resin, the type and amount of the alkoxysilane, etc. The tensile modulus can be measured specifically by the following method.

[0048] 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.

[0049] The curable resin composition of the present invention is preferably obtained by drying the solvent at 125°C for 10 minutes and then heat-curing the cured product at 300°C for 1 hour, and the resulting product preferably has a first scan linear expansion coefficient (CTE) in the range of 25°C to 350°C of 200 ppm / °C or less. When the curable resin composition satisfies this linear expansion coefficient, even when an inorganic layer is formed on the cured product, wrinkles are less likely to occur in the inorganic layer, thereby preventing process abnormalities caused by wrinkles in the inorganic layer. The linear expansion coefficient is more preferably 180 ppm / °C or less, and even more preferably 150 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 layer. The linear expansion coefficient can be adjusted by the type of silicone resin, the type and amount of the alkoxysilane, etc. The linear expansion coefficient can be measured by the following method.

[0050] 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 measured for linear thermal expansion when cooled to -80°C and then heated to 400°C at a heating rate of 5°C / min using a thermomechanical analyzer (Hitachi High-Tech Science Corporation, TMA7100 or equivalent), and the linear expansion coefficient in the range of 25°C to 350°C is calculated.

[0051] 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 silicone resin, the solvent, the alkoxysilane, and, if necessary, additives such as the catalyst and the heat-resistant additive with the solvent.

[0052] The curable resin composition of the present invention is preferably used as an insulating layer in a laminate of a plurality of substrates, the cured product of which is heat-cured, for use in a semiconductor device, etc., and more preferably used by laminating an inorganic layer on the cured product of the curable resin composition. By forming 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.

[0053] 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.

[0054] The laminate A of the present invention is a laminate in which an organic layer is stacked on a first element and an inorganic layer is stacked on the organic layer. The organic layer and inorganic layer serve as insulating layers in a semiconductor device in which multiple elements and substrates are stacked. 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 stacked. As a result, process abnormalities such as alignment defects 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.

[0055] 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.

[0056] 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.

[0057] 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.

[0058] 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.

[0059] 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.

[0060] 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.

[0061] 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.

[0062] 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.

[0063] 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.

[0064] Examples of a method for producing the laminate A of the present invention include 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, followed by solvent drying and thermal curing to form an organic layer, a step of forming an inorganic layer on the organic layer, and, if necessary, a step of further laminating the second substrate on the second surface of the first substrate and a step of laminating a support substrate on the inorganic layer.

[0065] 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.

[0066] 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.

[0067] The third and fourth substrates may be the same as the first substrate. The organic and inorganic layers may be the same as the organic and inorganic layers of the laminate A of the present invention. In order to improve connection reliability under high temperature and high humidity conditions, it is preferable that the inorganic layer covers the entire side surface of the organic layer.

[0068] 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.

[0069] 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.

[0070] 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.

[0071] 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.

[0072] Examples of a method for producing the laminate B of the present invention include a 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, 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; forming a barrier metal layer as needed; 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.

[0073] The uses of the laminates A and B of the present invention are not particularly limited, but they are suitable for 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 a semiconductor device having the laminate of the present invention also constitutes one aspect of the present invention.

[0074] According to the present invention, it is possible to provide a curable resin composition which is less likely to be contaminated with foreign matter, which is less likely to cause wrinkles in the inorganic layer even when an inorganic layer is formed on the cured product, and which can suppress process abnormalities; a cured film of the curable resin composition; a laminate using the cured film; and a semiconductor device having the laminate.

[0075] 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.

[0076] The following examples will further illustrate the present invention, but the present invention is not limited to these examples.

[0077] (1) Production of Silicone 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).

[0078] 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).

[0079] 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, 11.6 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 a silicone resin (silicone resin A, weight average molecular weight: 34,000) having the structure of the above structural formula (1) and silanol groups in which m is 23 and n is an average of 4.

[0080] (2) Preparation of Silicone Resin B 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, 11.2 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 solution, 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), and dried to obtain a silicone resin having the structure of structural formula (1) above, m being 21, and n (the number of DMS chains) being an average of 3, and having silanol groups (silicone resin B, weight average molecular weight 30,000).

[0081] (3) Preparation of Heat-Resistant Additive 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 Industries, Ltd.), 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 additive (weight average molecular weight: 9900) having the structure shown in structural formula (9) below. Note that "l" in structural formula (9) below represents the number of repeating units.

[0082]

[0083] (4) Preparation of Alkoxysilanes The following commercially available and synthetic alkoxysilanes were used. <Ethyl Silicate 48> Linear type, alkoxyl group carbon number: 2, number of alkoxyl groups: 22, no silanol groups, weight average molecular weight: 1414, manufactured by Colcoat Co., Ltd. <Ethyl Silicate 40> Linear type, alkoxyl group carbon number: 2, number of alkoxyl groups: 12, no silanol groups, weight average molecular weight: 744, manufactured by Colcoat Co., Ltd. <MS-51> Linear type, alkoxyl group carbon number: 1, no silanol groups, weight average molecular weight: 576, manufactured by Mitsubishi Chemical Corporation <1,2-bis(triethoxysilyl)ethane> Linear type, alkoxyl group carbon number: 1, number of alkoxyl groups: 6, no silanol groups, weight average molecular weight: 354, manufactured by Tokyo Chemical Industry Co., Ltd. <KR-213> Branched type, silanol group-containing, weight average molecular weight: 545, manufactured by Shin-Etsu Silicones Co., Ltd. <KR-9218> Branched type, silanol group-containing, weight average molecular weight: 635, manufactured by Shin-Etsu Silicones Co., Ltd. <KR-510> Branched type, silanol group-containing, weight average molecular weight: 1350, manufactured by Shin-Etsu Silicones Co., Ltd. <KR-401N> Branched type, silanol group-containing, weight average molecular weight: 2210, manufactured by Shin-Etsu Silicones Co., Ltd. <KBM9659> Branched type, number of carbon atoms in alkoxyl group: 3, silanol group-free, weight average molecular weight: 579, manufactured by Shin-Etsu Silicones Co., Ltd.

[0084] <Alkoxysilane A> 38.1 g of vinyltriethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 190.31) and 1 g of platinum(0)-1,3-divinyl-1,3-divinyl-1,1,3,3-tetramethyldisiloxane complex (manufactured by Sigma-Aldrich, molecular weight 381.48) were added to a reaction vessel equipped with a reflux condenser, a thermometer, and a dropping funnel, and the mixture was heated to 90°C with stirring. Then, 12 g of 1,3,5,7-tetramethylcyclotetrasiloxane (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., molecular weight 240.51) was slowly added dropwise using the dropping funnel. After the dropwise addition, the mixture was stirred for 6 hours while heating to 90°C. This resulted in the production of alkoxysilane A (branched type, number of carbon atoms in the alkoxyl group: 2, no silanol groups, weight average molecular weight: 1000) represented by the following structural formula (10).

[0085]

[0086] <Alkoxysilane B> 29.6 g of vinyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 148.23) and 0.04 g of a 5% solution of chloroplatinic acid in isopropanol were added to a reaction vessel equipped with a reflux condenser, a thermometer, and a dropping funnel, and the mixture was heated to 100°C with stirring. 21.9 g of tetrakis(dimethylsiloxy)silane (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 328.73) was then slowly added dropwise using a dropping funnel. After the addition, the mixture was heated at 130°C for 1 hour to obtain alkoxysilane B (branched, number of carbon atoms in the alkoxyl group: 1, no silanol groups, weight average molecular weight: 728) represented by the following structural formula (11).

[0087]

[0088] (5) Preparation of Other Raw Materials The following fillers, catalysts, and solvents were used: Filler: MT-10, manufactured by Tokuyama Corporation Catalyst: ZC-162, an acetylacetonate complex with zirconium as the central metal, manufactured by Matsumoto Fine Chemical Co., Ltd. Solvent: cyclopentanone

[0089] (Examples 1 to 5, Comparative Examples 1 to 10) The silicone resin, heat-resistant additive, catalyst, alkoxysilane, filler, and solvent shown in Tables 1 and 2 were mixed in the amounts shown in Tables 1 and 2. The resulting mixture was then passed through a filter (T100A047A, manufactured by Advantec Co., Ltd.) to obtain a curable resin composition. Note that in Comparative Example 2, the mixture could not pass through the filter, so the mixture was used as a curable resin composition as is without passing it through the filter.

[0090] <Physical Properties> The curable resin compositions obtained in the examples and comparative examples were subjected to the following measurements. The results are shown in Tables 1 and 2.

[0091] (1) Measurement of coefficient of linear expansion (CTE) A 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 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 -80°C and then heated to 420°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 25°C to 350°C was calculated.

[0092] (2) Measurement of tensile 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 500 μm thick film of the cured curable resin composition. The obtained film sample was 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 was measured using a dynamic viscoelasticity measuring device (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.

[0093] <Evaluation> The curable resin compositions obtained in the examples and comparative examples were evaluated as follows. The results are shown in Tables 1 and 2.

[0094] (Evaluation of Contamination) 0.1 g of the obtained curable resin composition was observed under an optical microscope to check for contamination with foreign matter. If foreign matter of 1 μm or more was found, it was considered to be contaminated and the contamination was evaluated.

[0095] (Evaluation of storage stability) The kinematic viscosity of the obtained curable resin composition was measured at 25°C and 20.0 rpm shear using an E-type viscometer (TVE100H, manufactured by Toki Sangyo Co., Ltd.) and recorded as the initial viscosity. Next, the curable resin composition was left to stand for 2 weeks in an environment with an air temperature of 25°C and a humidity of 50%. Thereafter, the viscosity after standing was measured under the same conditions as for the initial viscosity, and the rate of change from the initial viscosity was calculated. Storage stability was evaluated by marking a rate of change in viscosity within 10% as "good" and a rate of change in viscosity greater than 10% as "poor."

[0096] (Evaluation of Flatness) The obtained curable resin composition was ejected onto the center of an 8-inch silicon wafer (surface roughness <0.1 μm). Next, spin coating was performed at a rotation speed of 1500 rpm using a spin coater (ACT-400II; manufactured by ACTIVE Corporation). Subsequently, the spin-coated silicon wafer was solvent-dried in an oven at 125°C for 10 minutes, and then heat-treated at 300°C for 1 hour to obtain an organic layer with a thickness of 30 μm. 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 was performed by CVD using a PE-CVD (product number MPD-220NL, manufactured by Samco Corporation), and a 400 nm thick inorganic layer made of SiN was formed on the organic layer to obtain a laminate. The surface roughness of the laminate (inorganic layer) was measured by observing the inorganic layer surface of the obtained laminate with a laser microscope. Specifically, a laser microscope (OLS4100, manufactured by Olympus Corporation) was used to observe the sample at 20 magnification in an observation range of 643 μm square, and the surface roughness Sa value was calculated.

[0097] (Evaluation of Wrinkles in Inorganic Layer) The inorganic layer of the laminate obtained in the above evaluation of flatness was visually observed, and the wrinkling of the inorganic layer was evaluated by marking "O" when no wrinkles were present and marking "X" when wrinkles were present.

[0098]

[0099]

[0100] According to the present invention, it is possible to provide a curable resin composition which is less likely to be contaminated with foreign matter, which is less likely to cause wrinkles in the inorganic layer even when an inorganic layer is formed on the cured product, and which can suppress process abnormalities; a cured film of the curable resin composition; a laminate using the cured film; and a semiconductor device having the laminate.

[0101] 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 a silicone resin having a silanol group and a solvent, wherein the curable resin composition contains an alkoxysilane, the curable resin composition has a filler content of 2% by weight or less, and the curable resin composition is heat-cured by drying the solvent under conditions of 125°C for 10 minutes and then heat-treating the curable resin composition at 300°C for 1 hour, and the cured product has a tensile modulus of elasticity at 300°C of 0.7 MPa or more.

2. The curable resin composition according to claim 1, which is used by laminating an inorganic layer on the cured product of the curable resin composition.

3. A curable resin composition according to claim 1 or 2, in which the solvent is dried off from the curable resin composition at 125°C for 10 minutes, and then the cured product is heat-cured at 300°C for 1 hour, and the first scan linear expansion coefficient (CTE) in the range of 25°C to 350°C is 200 ppm / °C or less.

4. The curable resin composition according to claim 1 or 2, further comprising a catalyst and a heat resistance additive.

5. The curable resin composition according to claim 1 or 2, wherein the silicone resin has a structure represented by the following structural formula (1): In structural formula (1), m represents an integer of 1 or more, and n represents 3 or 4.

6. The curable resin composition according to claim 1 or 2, wherein the alkoxysilane has a weight average molecular weight of 579 or more.

7. The curable resin composition according to claim 1 or 2, wherein the alkoxysilane has three or more alkoxyl groups.

8. The curable resin composition according to claim 1 or 2, wherein the alkoxysilane is a branched or linear alkoxysilane having 2 or more carbon atoms in the alkoxyl group.

9. The curable resin composition according to claim 1 or 2, wherein the alkoxysilane does not have a silanol group.

10. The curable resin composition according to claim 1 or 2, wherein the content of the alkoxysilane is 5 parts by weight or more and 50 parts by weight or less per 100 parts by weight of the silicone resin.

11. A cured film obtained by thermally curing the curable resin composition according to claim 1.

12. A laminate comprising an organic layer made of the cured film according to claim 11 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.

13. The laminate according to claim 12, wherein a supporting substrate is laminated on the inorganic layer.

14. The laminate according to claim 12 or 13, further comprising a second substrate on the second surface of the first substrate, the first substrate and the second substrate being electrically connected.

15. A laminate having an organic layer and an inorganic layer, each of which is made of the cured film according to claim 11, 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.

16. The laminate according to claim 15, further comprising a barrier metal layer on the surface of the through hole.

17. A semiconductor device comprising the laminate according to claim 12 or 15.

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