Resin composition, cured film, laminate, imaging device, semiconductor device, method for producing laminate, and method for producing element having bonded electrode

Abstract

The purpose of the present invention is to provide: a resin composition which has excellent heat resistance and flexibility, is capable of planarizing a connection surface even if the element surface has irregularities, and is capable of imparting high electrical connection reliability between elements; a cured film using the resin composition; a laminate having the cured film; an imaging device and a semiconductor device each having the laminate; a method for producing the laminate; and a method for producing an element having a bonded electrode, which is used in the production of the laminate. The present invention relates to a resin composition which contains an organosilicon compound and a modifier, and which has a thermal loss of 10% or less before and after holding at 400 DEG C for 3 hours when the modifier is individually heated in air from room temperature to 300 DEG C at a heating rate of 10 DEG C / min and then held for 1 hour, then heated to 400 DEG C at a heating rate of 10 DEG C / min and held at 400 DEG C for 3 hours. A sample having a viscosity of 45 cP at 25 DEG C is prepared by adding the organosilicon compound and 1 part by weight of the modifier per 100 parts by weight of the organosilicon compound to ethyl benzoate, and when the sample is dropped onto a silicon wafer, the contact angle of the sample with respect to the silicon wafer is 9-20 DEG.

Description

Technical Field

[0001] The present invention relates to a resin composition, a cured film using the resin composition, a laminate having the cured film, an imaging device and a semiconductor device having the laminate, a method for manufacturing the laminate, and a method for manufacturing a component having a bonding electrode used in the manufacture of the laminate. Background Art

[0002] With the high performance of semiconductor devices, the three-dimensionalization of stacking multiple semiconductor chips is being promoted. In the manufacture of such a laminate in which multiple semiconductor chips are stacked, first, on the electrode surfaces of components each having two electrodes, a bonding surface in which a bonding electrode containing copper is surrounded by an insulating film is formed by an embedding method. Then, two components are overlapped such that the bonding electrodes of the bonding surfaces face each other, and heat treatment is performed, thereby manufacturing a laminate (Patent Document 1).

[0003] Prior Art Documents

[0004] Patent Documents

[0005] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2006-191081 Summary of the Invention

[0006] Problems to be Solved by the Invention

[0007] In the manufacture of the above laminate, high-temperature treatment such as 400°C for 4 hours is performed during the bonding of the electrodes, and thus high heat resistance is required for the insulating layer used to form the above bonding surface. Therefore, in conventional laminates, insulating inorganic materials such as SiN and SiO2 are used as the insulating layer. However, an insulating layer formed of an inorganic material is likely to cause warping in a component, and if warping occurs in the component, the connection position of the electrodes shifts or electrode breakage occurs when the laminate is manufactured, and thus the connection reliability of the laminate sometimes becomes low. In addition, in recent years, with the high performance of semiconductor devices, the components have become larger and thinner, and thus warping of the components is more likely to occur.

[0008] In addition, in recent years, with the multi-functionality of components, unevenness of several μm to more than ten μm is sometimes formed on the surface of the component on which the insulating layer is formed. In the case of directly bonding components having unevenness, from the viewpoint of the connection reliability between the electrodes, it is necessary to fill the surface of the wafer on which the component is formed with an insulating layer to flatten the connection surface and then perform the connection. Therefore, a material capable of forming an insulating layer having excellent heat resistance, flexibility, and planarization property of the component is required.

[0009] An object of the present invention is to provide: a resin composition having excellent heat resistance and flexibility, capable of flattening a connection surface even when the surface of an element has irregularities, and capable of imparting high electrical connection reliability between elements; a cured film using the resin composition; a laminate having the cured film; an imaging device and a semiconductor device having the laminate; a method for manufacturing the laminate; and a method for manufacturing an element having a bonding electrode used in the manufacture of the laminate.

[0010] Means for solving the problems

[0011] The present invention includes the following disclosures 1 to 23. Hereinafter, the present invention will be described in detail.

[0012] [Disclosure 1]

[0013] A resin composition containing a silicone compound and a modifier,

[0014] When the above-mentioned modifier is heated alone in air from room temperature to 300 °C at a heating rate of 10 °C / min and then held for 1 hour, and then heated to 400 °C at a heating rate of 10 °C / min and held at 400 °C for 3 hours, the thermal weight loss before and after holding at 400 °C for 3 hours is 10% or less.

[0015] The above-mentioned silicone compound and 1 part by weight of the above-mentioned modifier relative to 100 parts by weight of the above-mentioned silicone compound are added to ethyl benzoate to prepare a sample having a viscosity of 45 cP at 25 °C. When the above-mentioned sample is dropped onto a silicon wafer, the contact angle of the above-mentioned sample with respect to the silicon wafer is 9° or more and 20° or less.

[0016] [Disclosure 2]

[0017] According to the resin composition described in Disclosure 1, it further contains a solvent. The resin composition is made into a solution having a viscosity of 1200 cP using the above-mentioned solvent, and the above-mentioned solution is spin-coated on a silicon wafer at 1500 rpm for 10 seconds. After the solvent is dried, it is cured at 300 °C for 1 hour to form a resin cured film having a thickness of 10 μm or more. At this time, the surface free energy of the above-mentioned resin cured film is 27 mJ / m 2 or more.

[0018] [Disclosure 3]

[0019] According to the resin composition described in Disclosure 1 or 2, it contains a metal catalyst, a crosslinking agent, and a heat-resistant additive.

[0020] [Disclosure 4]

[0021] According to the resin composition described in any one of Disclosures 1 to 3, the above-mentioned silicone compound has a structure represented by the following general formula (1).

[0022] [Chemical Formula 1]

[0023]

[0024] Here, R 0 , R 1 and R 2 each independently represents a linear, branched or cyclic aliphatic group, aromatic group or hydrogen. The above-mentioned aliphatic group and the above-mentioned aromatic group may or may not have substituents. m and n each represent an integer of 1 or more.

[0025] [Publication 5]

[0026] The resin composition according to any one of Publications 1 to 4, wherein the modifier has a polyether-modified group.

[0027] [Publication 6]

[0028] The resin composition according to any one of Publications 1 to 5, wherein the content of the modifier is 0.01 parts by weight or more and 10 parts by weight or less with respect to 100 parts by weight of the organosilicon compound.

[0029] [Publication 7]

[0030] The resin composition according to any one of Publications 1 to 6, wherein the weight average molecular weight of the modifier is 4000 or more and 30000 or less.

[0031] [Publication 8]

[0032] The resin composition according to Publication 2, wherein the 1% weight loss temperature of the cured product obtained by drying the solvent and curing at 300 °C for 1 hour is 460 °C or more.

[0033] [Publication 9]

[0034] The resin composition according to any one of Publications 1 to 8, which is used for forming an insulating layer on the uneven surface of a component having unevenness on the surface.

[0035] [Publication 10]

[0036] A resin composition containing an organosilicon compound and a modifier,

[0037] The organosilicon compound has a structure represented by the following general formula (1),

[0038] The modifier has a polyether-modified group.

[0039] [Chemical Formula 2]

[0040]

[0041] Here, R 0 , R 1 and R 2 each independently represents a linear, branched or cyclic aliphatic group, aromatic group or hydrogen. The above-mentioned aliphatic group and the above-mentioned aromatic group may or may not have a substituent. m and n each represent an integer of 1 or more.

[0042] [Publication 11]

[0043] A cured film formed by using the resin composition described in any one of Publications 1 to 10.

[0044] [Publication 12]

[0045] A laminate having the cured film described in Publication 11 between a first element having an electrode and a second element having an electrode, wherein the electrode of the first element and the electrode of the second element are electrically connected through a through hole penetrating the cured film.

[0046] [Publication 13]

[0047] According to the laminate described in Publication 12, an inorganic layer is provided between the first element and the second element.

[0048] [Publication 14]

[0049] According to the laminate described in Publication 12 or 13, a barrier metal layer is provided on the surface of the through hole.

[0050] [Publication 15]

[0051] An imaging device having the laminate described in any one of Publications 12 to 14.

[0052] [Publication 16]

[0053] A semiconductor device having the laminate described in any one of Publications 12 to 14.

[0054] [Publication 17]

[0055] A method for manufacturing a laminate, comprising:

[0056] A step of forming a resin composition described in any one of Publications 1 to 10 on the electrode-formed surfaces of a first element having an electrode and a second element having an electrode, and curing it to form a cured film;

[0057] A step of forming a through hole in each of the above-mentioned cured films;

[0058] The step of filling each of the above through-holes with a conductive material;

[0059] The step of grinding the surfaces of the first and second elements on the side filled with the conductive material to form bonding electrodes; and

[0060] The step of bonding the first element having the above bonding electrode and the second element having the above bonding electrode together in such a way that the bonding electrodes are in contact with each other.

[0061] [Publication 18]

[0062] A method for manufacturing an element having a bonding electrode, comprising:

[0063] The step of forming a resin composition described in any one of Publications 1 to 10 into a film on the surface of an element having an electrode where the electrode is formed, and curing it to form a cured film;

[0064] The step of forming through-holes in the above cured film;

[0065] The step of filling the above through-holes with a conductive material; and

[0066] The step of grinding the surface of the above element having an electrode on the side filled with the above conductive material to form a bonding electrode.

[0067] [Publication 19]

[0068] A laminate having a cured film described in Publication 11 between a support substrate and a third element,

[0069] The above third element has a first surface and a second surface, and the first surface has a plurality of chips,

[0070] The above cured film is laminated on the first surface side.

[0071] [Publication 20]

[0072] According to the laminate described in Publication 19, wherein an inorganic layer is provided between the support substrate and the cured film.

[0073] [Publication 21]

[0074] According to the laminate described in Publication 19 or 20, wherein a fourth element is further provided on the second surface of the above third element, and the above third element is electrically connected to the above fourth element.

[0075] [Publication 22]

[0076] An imaging device having a laminate described in any one of Publications 19 to 21.

[0077] [Publication 23]

[0078] A semiconductor device having a laminate described in any one of Publications 19 to 21.

[0079] The resin composition of the present invention contains a silicone compound.

[0080] When the resin composition of the present invention is used for an insulating layer of a laminate on which elements are laminated, by making the insulating layer a cured film of a resin composition of an organic substance, the flexibility of the insulating layer is improved, warping of the elements can be suppressed, and the electrical connection reliability can be improved. In addition, by using a silicone compound in the resin composition, an insulating layer excellent in heat resistance and element planarization can be formed.

[0081] The above silicone compound is preferably a silsesquioxane.

[0082] Silsesquioxane has flexibility comparable to that of an organic compound and high heat resistance. Therefore, by using a cured film mainly composed of silsesquioxane as the insulating layer of the laminate, warping and cracking of the substrate can be suppressed, and the electrical connection reliability can be improved. The above silsesquioxane is not particularly limited as long as it is thermosetting. From the aspect of further suppressing warping and cracking of the substrate, it preferably has structures represented by the following structural formulas (A) and (B) in one molecule.

[0083] [Chemical formula 3]

[0084]

[0085] 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, each representing an integer of 1 or more.

[0086] The above silicone compound more preferably has a structure represented by the following general formula (1). By making the silicone compound have the structure of the following general formula (1), the heat resistance is further improved, and when used for the insulating layer of the laminate, electrode shift and cracking can be further suppressed, and the electrical connection reliability can be improved. In addition, the silicone compound represented by the following general formula (1) can be combined with a modifier described later. Therefore, the modifier can be dispersed throughout the resin composition. Therefore, when used for the insulating layer of the laminate, the planarization of the elements can be further improved. In addition, it can easily satisfy the contact angle with respect to a silicon wafer described later.

[0087] [Chemical formula 4]

[0088]

[0089] Here, R 0 , R1 and R 2 each independently represents a linear, branched or cyclic aliphatic group, aromatic group or hydrogen. The above aliphatic group and the above aromatic group may or may not have substituents. m and n each represent an integer of 1 or more.

[0090] In the above general formula (1), R 0 each independently represents a linear, branched or cyclic aliphatic group, aromatic group or hydrogen. The above aliphatic group and the above aromatic group may or may not have substituents. The above R 0 is preferably a phenyl group, an alkyl group having 1 to 20 carbon atoms or an arylalkyl group, more preferably a phenyl group. By making R 0 be a phenyl group, an alkyl group having 1 to 20 carbon atoms or an arylalkyl group, higher heat resistance can be exhibited.

[0091] In the above general formula (1), R 1 and R 2 each independently represents a linear, branched or cyclic aliphatic group, aromatic group or hydrogen. The above aliphatic group and the above aromatic group may or may not have substituents. The above R 1 and R 2 are preferably a phenyl group, an alkyl group having 1 to 20 carbon atoms or an arylalkyl group, more preferably a phenyl group or a methyl group. By making R 1 and R 2 be a phenyl group, an alkyl group having 1 to 20 carbon atoms or an arylalkyl group, higher heat resistance can be exhibited.

[0092] In the above general formula (1), m and n are each an integer of 1 or more, representing the number of repeating units. The above m is preferably 30 or more, more preferably 50 or more, and preferably 100 or less. The above n is preferably 1 or more, more preferably 3 or more, further preferably 4 or more, preferably 8 or less, more preferably 6 or less.

[0093] The above silicone compound preferably has a reactive site.

[0094] By using a silicone compound having a reactive site as the curable resin of the resin composition, warping of the element and displacement and cracking of the electrode can be further suppressed when used for the insulating layer of the laminate. In addition, since the silicone compound has excellent heat resistance, decomposition of the cured film caused by high-temperature treatment performed during the manufacture of electronic components can be further suppressed. Examples of the above reactive site include a hydroxyl group, an alkoxy group, etc. Examples of the above silicone compound having a reactive site include the silicone compound represented by the above general formula (1).

[0095] In 100 parts by weight of the solid content (the amount of components other than the solvent) in the above resin composition, the content of the above silicone compound is preferably 80 parts by weight or more, more preferably 90 parts by weight or more, and still more preferably 95 parts by weight or more. In 100 parts by weight of the solid content in the above resin composition, the content of the above silicone compound is preferably less than 100 parts by weight, and more preferably 98 parts by weight or less.

[0096] The weight average molecular weight of the above silicone compound is not particularly limited, and is preferably 5,000 or more and 150,000 or less. By making the molecular weight of the silicone compound within the above range, the film forming property during coating is improved, the planarization performance is further improved, and when used for the insulating layer of the laminate, warping of the element and displacement and cracking of the electrode can be further suppressed. The molecular weight of the above silicone compound is more preferably 10,000 or more, still more preferably 30,000 or more, more preferably 100,000 or less, and still more preferably 70,000 or less.

[0097] It should be noted that the weight average molecular weight of the above silicone compound is measured by gel permeation chromatography (GPC) in terms of the molecular weight converted to polystyrene. The elution solvent can be set as THF, and as the column, Time-MB-M6.0×150 mm (manufactured by Waters Corporation) or its equivalent is used, and it is calculated by the polystyrene standard.

[0098] From the viewpoints of improving the film forming property during coating, further improving the planarization performance, and further suppressing warping of the element and displacement and cracking of the electrode when used for the insulating layer of the laminate, the above silicone compound is preferably dissolved in the resin composition and preferably does not exist in a dispersed state having a specific shape such as particles.

[0099] The resin composition of the present invention contains a modifier.

[0100] By selecting a modifier having a thermal weight loss described below and satisfying the contact angle with respect to the silicon wafer described below when used in combination with the above silicone compound, the connection surface can be planarized even when used on an element having irregularities on the surface, and high electrical connection reliability can be imparted between the elements. It should be noted that in order to planarize the connection surface, it is required to stably form a film even at high temperatures. Therefore, when using a modifier only in a flexible silicone compound, film cracking sometimes occurs and the planarization property of the connection surface is lacking.

[0101] When the above modifier is heated from room temperature to 300 °C at a heating rate of 10 °C / min in air and then held for 1 hour, and then heated to 400 °C at a heating rate of 10 °C / min and held at 400 °C for 3 hours, the thermal weight loss before and after holding at 400 °C for 3 hours is 10% or less.

[0102] By making the thermal weight loss of the modifier within the above range under the above conditions, it is possible to suppress the thermal decomposition of the modifier and the film breakage of the insulating layer caused thereby even after high-temperature treatment, and to sufficiently fill the unevenness on the surface of the component when used on the component. From the viewpoint of further improving the heat resistance of the cured product of the resin composition, the above thermal weight loss is preferably 8% or less, more preferably 5% or less.

[0103] It should be noted that the above thermal weight loss can be adjusted by the molecular weight and the type of functional group. In addition, the above thermal weight loss can be measured by using a differential thermal-thermogravimetric simultaneous measurement device (TG-DTA; STA7200, manufactured by Hitachi High-Tech Science Corporation or equivalent), and specifically, it can be measured by the following method.

[0104] Using a differential thermal-thermogravimetric simultaneous measurement device (TG-DTA; STA7200, manufactured by Hitachi High-Tech Science Corporation or equivalent), the modifier is heated from 25°C to 300°C in air at a heating rate of 10°C / min and held for 1 hour. After holding for 1 hour, it is further heated to 400°C at a heating rate of 10°C / min and held for 3 hours after reaching 400°C. Among the weights at each temperature, the thermal weight loss is calculated based on the weight at the initial arrival at 400°C and the weight after 3 hours at 400°C.

[0105] The above modifier is not particularly limited as long as it satisfies the above thermal weight loss and the contact angle with respect to the silicon wafer described below. As compounds that easily satisfy them, for example, polyether-based compounds, aralkyl-based compounds, polyester-based compounds, organosilicon-based compounds, etc. can be cited. Among them, from the aspect of easily satisfying the above thermal weight loss and the contact angle with respect to the silicon wafer described below and being able to planarize the joint surface even when used on a component having unevenness on the surface, the above modifier preferably has a polyether modification group, and more preferably is an organosilicon-based compound having a polyether modification group.

[0106] The content of the above modifier is not particularly limited. From the aspect of being able to further planarize the joint surface of the component, with respect to 100 parts by weight of the above organosilicon compound, it is preferably 0.01 part by weight or more, more preferably 0.1 part by weight or more, further preferably 0.3 part by weight or more, preferably 10 parts by weight or less, more preferably 1 part by weight or less, and further preferably 0.7 part by weight or less.

[0107] The weight average molecular weight of the above-mentioned modifier is preferably 4000 or more and 30000 or less. By making the polymerization average molecular weight of the modifier within the above range, the connection surface of the element can be further flattened. The weight average molecular weight of the above-mentioned modifier is more preferably 15000 or more, more preferably 20000 or more, more preferably 30000 or less, and more preferably 25000 or less. It should be noted that the weight average molecular weight of the above-mentioned modifier can be measured by the same method as the weight average molecular weight of the above-mentioned organosilicon compound.

[0108] The resin composition of the present invention preferably contains a solvent.

[0109] By including a solvent in the resin composition, the above-mentioned organosilicon compound can be easily adjusted to a viscosity that can be applied to the element, and when used on the element, the surface irregularities of the element can be filled to make it flatter. The above-mentioned solvent can be composed of a single component or a mixture of multiple components.

[0110] The solvent is not particularly limited, and examples thereof include ketone solvents such as cyclopentanone, ester solvents such as ethyl benzoate, lactone solvents, lactam solvents, glycol ether solvents, etc. Among them, cyclopentanone is preferred because it can further planarize the connection surface of the element.

[0111] The boiling point of the solvent is preferably 150° C. or higher and 250° C. or lower.

[0112] By making the boiling point of the above-mentioned solvent within the above-mentioned range, the flattening performance can be further improved. In addition, by making the boiling point of the above-mentioned solvent meet the above-mentioned lower limit, it is possible to suppress the abnormal foreign matter caused by the solvent volatilizing into a rope-like shape (Japanese original: ひも状) during spin coating and adhering to the coating film. The boiling point of the above-mentioned solvent is more preferably above 170°C, more preferably above 180°C, more preferably below 230°C, and more preferably below 220°C. As solvents having a boiling point in the above-mentioned range, aromatic organic solvents, lactam organic solvents, and lactone organic solvents can be cited. Lactam organic solvents refer to organic solvents of heterocyclic compounds having -C(=O)NR- in the ring, and lactone organic solvents refer to organic solvents of heterocyclic compounds having -C(=O)- in the ring. It should be noted that 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.).

[0113] The content of the above solvent in the above resin composition is preferably 50% by weight or less.

[0114] By making the content of the above solvent in the resin composition within the above range, the shrinkage caused by the volatilization of the solvent during curing becomes smaller. Therefore, the resulting cured film is less likely to have irregularities, and the joint surface can be made flat. As a result, the bonding reliability of the components is improved, and the electrical connection reliability can also be improved. The content of the above solvent is preferably 45% by weight or less, more preferably 40% by weight or less, and further preferably 35% by weight or less. The lower limit of the content of the above solvent is not particularly limited, and from the viewpoint of further improving the planarization performance, it is preferably 30% by weight or more.

[0115] With respect to 100 parts by weight of the above silicone compound, the content of the above solvent is preferably 50 parts by weight or more and 100 parts by weight or less.

[0116] By making the content of the above solvent relative to the above silicone compound within the above range, the planarization performance of the component surface can be further improved. The content of the above solvent relative to the above silicone compound is more preferably 55 parts by weight or more, further preferably 60 parts by weight or more, more preferably 80 parts by weight or less, and further preferably 70 parts by weight or less.

[0117] The resin composition of the present invention preferably contains a metal catalyst that promotes the curing reaction.

[0118] By making the resin composition have a metal catalyst, the resin composition can be cured more completely, and the decomposition of the cured film caused by high-temperature treatment can be further suppressed.

[0119] Examples of the above metal catalyst include: organotin compounds such as dibutyltin dilaurate and stannous acetate, metal carboxylates such as zinc naphthenate, zirconium oxide compounds such as zirconium acetylacetonate, and titanium compounds. Among them, from the aspect of being able to further promote the curing of the resin composition, zirconium acetylacetonate and dibutyltin dilaurate are preferred.

[0120] The above metal catalyst also exists after the resin composition is cured. That is, the cured film formed by curing the resin composition of the present invention preferably contains a metal catalyst that promotes the curing reaction.

[0121] The content of the above catalyst is not particularly limited, and with respect to 100 parts by weight of the silicone compound in the above resin composition, it is preferably 0.01 part by weight or more and 10 parts by weight or less. By making the content of the catalyst within the above range, the curing of the resin composition can be further promoted. The content of the above catalyst is more preferably 0.1 part by weight or more, further preferably 0.2 part by weight or more, more preferably 7 parts by weight or less, and further preferably 5 parts by weight or less.

[0122] The resin composition of the present invention preferably contains a crosslinking agent.

[0123] The crosslinking agent capable of reacting with the reactive site of the organosilicon compound crosslinks between the polymers of the organosilicon compound having the reactive site, whereby the crosslinking density of the cured product increases, and the decomposition at high temperature is further suppressed. As a result, the generation of voids caused by the generation of decomposition gas during high-temperature treatment when used as an insulating layer for a laminate can be further suppressed, and thus the shift of the electrode during connection and the reduction of electrical connection reliability can be suppressed. As the above crosslinking agent, for example, when the reactive site is a silanol group, 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 can be mentioned. Among them, silicate oligomers are preferred from the viewpoints of increasing the crosslinking density and improving the heat resistance. Examples of alkoxysilane compounds include dimethyldimethoxysilane, trimethoxymethylsilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, etc. Examples of silicate oligomers include Silicate MS51, MS56, MS57, MS56S (all manufactured by Mitsubishi Chemical Corporation), Ethyl Silicate 40, Ethyl Silicate 48, EMS485 (all manufactured by COLCOAT Corporation), etc.

[0124] The content of the above crosslinking agent is not particularly limited, and is preferably 1 part by weight or more and 50 parts by weight or less with respect to 100 parts by weight of the organosilicon compound in the resin composition. By setting the content of the crosslinking agent within the above range, the crosslinking density of the cured film can be set to a suitable range. The content of the crosslinking agent is more preferably 3 parts by weight or more, further preferably 3.2 parts by weight or more, more preferably 30 parts by weight or less, and further preferably 20 parts by weight or less.

[0125] The resin composition of the present invention preferably contains a heat-resistant additive.

[0126] By using a heat-resistant additive in the resin composition, the heat resistance of the cured product of the resin composition can be made more excellent. As the above heat-resistant additive, for example, polyimide resin, epoxy resin, silicone resin, benzoxazine resin, cyanate ester resin, phenolic resin, etc. can be mentioned. Among them, polyimide resin is preferred particularly from the aspect of being able to improve the heat resistance.

[0127] The molecular weight and weight-average molecular weight of the above heat-resistant additive are not particularly limited, and are preferably 5,000 or more and 150,000 or less. By making the weight-average molecular weight of the heat-resistant additive within the above range, it is possible to easily adjust the viscosity and solid content concentration of the resin composition to the range of the present invention. The molecular weight of the above heat-resistant additive is more preferably 10,000 or more, further preferably 30,000 or more, more preferably 100,000 or less, and further preferably 70,000 or less.

[0128] The content of the above heat-resistant additive is not particularly limited. From the viewpoint of further improving heat resistance, it is preferably 0.1 part by weight or more, more preferably 0.5 part by weight or more, preferably 10 parts by weight or less, and more preferably 5 parts by weight or less based on 100 parts by weight of the above silicone compound.

[0129] When the above heat-resistant additive is polyimide, the above polyimide preferably has a siloxane bond.

[0130] By making the above polyimide have a siloxane bond, the compatibility with the silicone compound contained in the resin composition is improved, and thus it is possible to further suppress the unevenness (surface roughness) caused by the precipitation of polyimide during coating.

[0131] When the above polyimide has a siloxane bond, the ratio of carbon atoms to silicon atoms C / Si in the main chain structure of the above polyimide is preferably 17 or less.

[0132] By making the ratio of carbon atoms to silicon atoms in the main chain structure of the polyimide within the above range, the compatibility with the silicone compound contained in the resin composition is further improved, and thus surface roughness can be further suppressed during coating. The above C / Si is more preferably 16.5 or less, and further preferably 16 or less. The lower limit of the above C / Si is not particularly limited, and from the viewpoints of practical use and further improving the heat resistance at 400 °C, it is preferably 4 or more. It should be noted that the ratio of carbon atoms to silicon atoms C / Si in the main chain structure of the above polyimide is the ratio of C and Si within the repeating unit, excluding C and Si at both ends. In addition, the above C / Si can be obtained by using 1 H-NMR, 13 C-NMR and 29 Si-NMR to obtain the structure of the above polyimide, and calculating the number of C atoms and Si atoms from the repeating unit of the main chain.

[0133] The above polyimide preferably has a plurality of aromatic rings.

[0134] By making the above polyimide have a plurality of aromatic rings, it is possible to form a cured film that is not easily broken during high-temperature treatment under various conditions even when a cured film with a thickness is formed.

[0135] The above polyimide preferably has an oxazine ring or an imide ring structure at at least one end, and more preferably has an oxazine ring or an imide ring structure at both ends.

[0136] By making the above polyimide have an oxazine ring or an imide ring structure at the end, the surface roughness when forming a thick film can be further suppressed. It should be noted that the above oxazine ring and imide ring structures may have substituents.

[0137] Among them, it is further preferred that the above polyimide has any one of the following structures (2) to (7) at at least one end, and particularly preferably has any one of the following structures (2) to (7) at both ends. It should be noted that " " in the following formula represents the bonding site with the part other than the end of the above polyimide.

[0138] [Chemical formula 5]

[0139]

[0140] The weight average molecular weight of the above polyimide is preferably 1000 or more and 50000 or less.

[0141] By making the weight average molecular weight of the above polyimide within the above range, the compatibility with the silicone compound is improved, and the processability can be further improved. The weight average molecular weight is more preferably 2000 or more, further preferably 3000 or more, more preferably 35000 or less, and further preferably 30000 or less.

[0142] It should be noted that the weight average molecular weight of the above polyimide is measured in the form of a polystyrene-equivalent molecular weight by gel permeation chromatography (GPC). The elution solvent can be set as THF, and Time-MB-M6.0×150mm (manufactured by Waters Corporation) or its equivalent can be used as the column, and it is calculated by a polystyrene standard.

[0143] Relative to 100 parts by weight of the above silicone compound, the content of the above polyimide is preferably 0.5 parts by weight or more and 50 parts by weight or less.

[0144] By making the content of the polyimide within the above range, even when forming a cured film with a thickness, a cured film that is less likely to cause film rupture during high-temperature treatment can be formed.

[0145] Relative to 100 parts by weight of the silicone compound, the content of the above polyimide is preferably 0.7 parts by weight or more, more preferably 0.75 parts by weight or more, further preferably 1 part by weight or more, preferably 20 parts by weight or less, more preferably 10 parts by weight or less, and further preferably 5 parts by weight or less.

[0146] The resin composition of the present invention may contain other additives such as a viscosity modifier, a filler, an adhesion-imparting agent, etc. as needed. However, from the viewpoint of suppressing the amount of thermal decomposition at high temperatures and improving heat resistance, it is preferably free of a fluorescent agent.

[0147] Regarding the resin composition of the present invention, the above-mentioned silicone compound and 1 part by weight of the above-mentioned modifier with respect to 100 parts by weight of the above-mentioned silicone compound are added to ethyl benzoate to prepare a sample having a viscosity of 45 cP at 25°C. When the above-mentioned sample is dropped onto a silicon wafer, the contact angle of the above-mentioned sample with respect to the silicon wafer is 9° or more and 20° or less.

[0148] By making the above-mentioned silicone compound and a specific amount of the modifier into an ethyl benzoate solution having a specific viscosity so that the contact angle when dropped onto a silicon wafer is within the above range, the resin composition can be spread over the bottom surface of the recess to make the joint surface flat.

[0149] From the viewpoint of making the joint surface of the element flatter, the above contact angle is preferably 12° or more, more preferably 14° or more, preferably 18° or less, and more preferably 15° or less. The above contact angle can be adjusted by the combination of the types of the above-mentioned silicone compound and the above-mentioned modifier. More specifically, for example, when a compound having the structure shown in the above general formula (1) is used as the silicone compound and a compound having a polyether-modified group is used as the modifier, the contact angle can be easily adjusted to the above range.

[0150] It should be noted that the viscosity at 25°C can be measured by using an E-type viscometer (TVE100H, manufactured by Toki Sangyo Co., Ltd., or its equivalent) to measure the kinematic viscosity at 25°C and a shear rate of 10.0 rpm. In addition, the above contact angle can be measured by the method according to JIS R3257. Specifically, it can be measured by the following method.

[0151] The above-mentioned silicone compound and 1 part by weight of the modifier with respect to 100 parts by weight of the above-mentioned silicone compound are added to ethyl benzoate to prepare a sample having a viscosity of 45 cP at 25°C. The obtained sample is dropped onto a silicon wafer using a contact angle measuring device (fully automatic contact angle meter DMo-702, manufactured by Kyowa Interface Science Co., Ltd., or its equivalent), and the contact angle of the sample with respect to the silicon wafer is measured.

[0152] Preferably, the resin composition of the present invention further contains a solvent, and the resin composition is made into a solution having a viscosity of 1200 cP at 25° C. using the solvent, and the solution is spin-coated on a silicon wafer at 1500 rpm for 10 seconds, and after the solvent is dried, it is cured at 300° C. for 1 hour to form a resin cured film with a thickness of 10 μm or more, and the surface free energy of the resin cured film at this time is 27 mJ / m 2 above.

[0153] If the surface free energy of the cured resin film is within the above range, wettability to the Si wafer can be reduced and outflow of the resin composition can be suppressed. Therefore, even when used on an element with an uneven surface, the connection surface can be flattened. From the viewpoint of making the connection surface of the element flatter, the surface free energy of the cured resin film is more preferably 30 mJ / m 2 More preferably, 33 mJ / m 2 More preferably, 38 mJ / m 2 Below, more preferably 35mJ / m 2 the following.

[0154] The surface free energy of the above-mentioned resin cured film can be adjusted by the type and content of the above-mentioned organic silicon compound, the type and content of the above-mentioned modifier, the type and content of the above-mentioned catalyst, the type and content of the above-mentioned cross-linking agent, the type and content of the above-mentioned heat-resistant additive, the type of solvent (Japanese original: solvent), etc. It should be noted that the surface energy of the above-mentioned resin cured film can be measured using a contact angle meter (fully automatic contact angle meter DMo-702, manufactured by Kyowa Interface Science Co., Ltd. or its equivalent), and specifically, it can be measured by the following method. In addition, as the above-mentioned solvent, there is no particular limitation as long as it can be set to the above-mentioned viscosity and is completely volatilized when the resin cured film is made. For example, the same solvent as the above-mentioned solvent can be used.

[0155] A solvent is added to the resin composition to prepare a solution with a viscosity of 1200 cP at 25°C. At room temperature, the solution is dripped onto the center of an 8-inch silicon wafer, and the resin composition is applied to the silicon wafer using a spin coater (ACT-400II, manufactured by ACTIVE or equivalent) at 1500 rpm for 10 seconds. The wafer coated with the solution is heated at 125°C for 10 minutes to dry the solvent. Then, it is heated at 300°C for 1 hour to obtain a resin cured film with a thickness of more than 10 μm. For the obtained resin cured film, water and diiodomethane are added using a contact angle meter (fully automatic contact angle meter DMo-702, manufactured by Kyowa Interface Science Co., Ltd. or its equivalent), and the contact angle of each liquid relative to the resin cured film is measured, thereby measuring the dispersion energy γ d , interaction energy γ h, the surface free energy γ is calculated based on their sum.

[0156] The resin composition of the present invention preferably has a 1% weight loss temperature of 440 °C or higher for a cured product obtained by drying the above solvent and curing at 300 °C for 1 hour.

[0157] By making the weight loss rate of the cured product within the above range, elements can be joined more reliably, and the generation of bubbles, cracks at the interface, and peeling at the interface caused by the cured product decomposed during electrode bonding can be further suppressed. The above weight loss temperature is more preferably 450 °C or higher, and further preferably 460 °C or higher. The upper limit of the above weight loss temperature is not particularly limited, and the higher the better, but it is limited to about 480 °C in terms of manufacturing technology.

[0158] The above weight loss temperature can be adjusted by the composition of the resin composition, the types of resin raw materials constituting the resin composition, the curing conditions of the resin composition, etc.

[0159] Specifically, for example, by using a resin raw material with high heat resistance, an inorganic component, increasing the content of a crosslinking agent, etc. in the resin composition, the above weight loss temperature can be increased.

[0160] In addition, by using a resin with high heat resistance (for example, a resin with a large molecular weight, a resin having a main chain and substituents with high heat resistance) as the type of resin raw material, the above weight loss temperature can be increased.

[0161] Specifically, the weight loss temperature of the cured product of the above resin composition can be measured by the following method.

[0162] The resin composition coated in a sheet shape using an applicator or the like is heated at 125 °C for 10 minutes to be dried, and then further heated at 300 °C for 1 hour to obtain a film (cured film) of the cured product of the resin composition with a thickness of 35 μm. Weigh about 3 - 10 mg of the obtained film, and use a differential thermal - thermogravimetric simultaneous measurement device (TG - DTA; STA7200, manufactured by Hitachi High - Tech Science Corporation, or its equivalent), and heat it at a heating rate of 10 °C / min in a nitrogen gas stream (50 mL / min), and measure the temperature when the weight loss rate reaches 1% at this time.

[0163] The manufacturing method of the resin composition of the present invention is not particularly limited. For example, it can be manufactured by mixing the above silicone compound, the above modifier, and additives such as the above catalyst and the above crosslinking agent as needed.

[0164] The resin composition of the present invention contains a silicone compound and a modifier. The above-mentioned modifier satisfies the above weight reduction amount and the contact angle with respect to the above silicon wafer, and thus has excellent heat resistance and flexibility. Moreover, even when the surface of the component has irregularities, it can flatten the connection surface and can impart high electrical connection reliability between components. On the other hand, when the above silicone compound is the silicone compound represented by the above general formula (1), by making the above modifier have a polyether-modified group, the effects of the present invention can be exerted.

[0165] A resin composition containing a silicone compound and a modifier, wherein the above silicone compound has a structure represented by the following general formula (1) and the above modifier has a polyether-modified group is also one of the present inventions. It should be noted that the details of the above silicone compound, the above modifier, other additives, and various physical properties are the same as those above.

[0166] [Chemical formula 6]

[0167]

[0168] Here, R 0 , R 1 and R 2 each independently represent a linear, branched or cyclic aliphatic group, aromatic group or hydrogen. The above aliphatic group and the above aromatic group may or may not have substituents. m and n each represent an integer of 1 or more.

[0169] The use of the resin composition of the present invention is not particularly limited. Since it has excellent performance in flattening due to filling irregularities and the cured film has heat resistance and flexibility, it can be suitably used for: the use of forming an insulating layer on the uneven surface of a component having unevenness on the surface; an insulating layer when manufacturing a laminate by electrically connecting the electrodes between two components having electrodes.

[0170] The resin composition of the present invention used in the use of forming an insulating layer on the uneven surface of such a component having unevenness on the surface, and the cured film formed using the resin composition of the present invention are also one of the present inventions.

[0171] As the above component, for example, there can be mentioned: a sensor circuit component provided with a pixel portion (pixel region), a circuit component equipped with a peripheral circuit portion such as a logic circuit that performs various signal processes related to the operation of a solid-state imaging device, etc.

[0172] The 1% weight reduction temperature of the cured film of the present invention is preferably 440 °C or higher.

[0173] By making the weight reduction rate of the cured film after heating nitrogen within the above range, it is possible to more reliably bond the elements and further suppress the generation of bubbles, cracks at the interface, and peeling at the interface caused by the cured product decomposed during electrode bonding. The above weight reduction temperature is more preferably 450 °C or higher, and further preferably 460 °C or higher. The upper limit of the above weight reduction temperature is not particularly limited, and the higher the better, but in terms of manufacturing technology, it is limited to around 480 °C.

[0174] The above weight reduction temperature can be adjusted by the composition of the resin composition, the type of resin raw material constituting the resin composition, the curing conditions of the resin composition, etc.

[0175] Specifically, for example, by using a resin raw material with high heat resistance, an inorganic component, increasing the content of the crosslinking agent, etc. in the resin composition, the above weight reduction temperature can be increased.

[0176] In addition, by using a resin with high heat resistance (such as a resin with a large molecular weight, a resin with a main chain and substituents with high heat resistance) as the type of resin raw material constituting the cured film, or by setting the curing conditions of the resin composition as the raw material of the cured film to a high temperature where curing is sufficient or setting the curing time to a long time, the above weight reduction temperature can be increased.

[0177] The weight reduction temperature of the above cured film can be specifically measured by the following method.

[0178] Weigh about 3 - 10 mg of the cured film, use a differential thermal - thermogravimetric simultaneous measurement device (TG - DTA; STA7200, manufactured by Hitachi High - Tech Science Corporation, or its equivalent), and heat it at a heating rate of 10 °C / min under a nitrogen gas flow (50 mL / min), and measure the temperature when the weight reduction rate reaches 1%.

[0179] In addition, a laminate in which the cured film of the present invention is provided between a first element having an electrode and a second element having an electrode, and the electrode of the first element and the electrode of the second element are electrically connected via a through - hole penetrating the cured film is also one of the present inventions. (Hereinafter, it is also referred to as laminate A) Hereinafter, the laminate of the present invention will be described.

[0180] The laminate A of the present invention has the cured film of the present invention between a first element having an electrode and a second element having an electrode, and the electrode of the first element and the electrode of the second element are electrically connected via a through - hole penetrating the cured film.

[0181] A cured film provided between an electrode of a first element (hereinafter also referred to as the first electrode) and an electrode of a second element (hereinafter also referred to as the second electrode) functions as an insulating layer, thereby being able to suppress a short circuit of current. Conventional insulating layers use hard inorganic materials such as SiN and SiO2. Therefore, when warpage occurs during the formation of the insulating layer or the laminate, the warpage cannot be eliminated by stress relaxation. As a result, warpage of the elements and displacement and breakage of the electrodes caused thereby are likely to occur. In the present invention, by using a cured film containing a resin having a higher flexibility than inorganic materials as the insulating layer, high electrical connection reliability can be achieved. In particular, the resin composition of the present invention that is the source of the above-mentioned cured film can fill unevenness and flatten the bonding surface even when the element has unevenness, so that a laminate having high electrical connection reliability can be produced. In addition, conventional insulating layers are formed by vapor deposition, so the formation takes time. However, the cured film of the laminate of the present invention can be formed, for example, by coating and curing a resin composition, so that the production efficiency can be improved.

[0182] It should be noted that here, electrical connection means a state in which the first electrode and the second electrode are connected by using a conductive material filled in the above-mentioned through hole or the like.

[0183] The above-mentioned first element and second element are not particularly limited, and circuit elements formed with elements, wirings, and electrodes can be used. For example, a sensor circuit element provided with a pixel portion (pixel region), a circuit element equipped with a peripheral circuit portion such as a logic circuit that performs various signal processes related to the operation of a solid-state imaging device, etc. can be used.

[0184] The materials of the electrodes of the above-mentioned first element and second element and the above-mentioned conductive material are not particularly limited, and conventionally known electrode materials such as gold, copper, and aluminum can be used.

[0185] The thickness of the above-mentioned cured film is not particularly limited, and it is preferably 10 μm or more and 300 μm or less.

[0186] By making the thickness of the cured film within the above range, the function as an insulating layer can be further exerted, and displacement and breakage of the electrodes can be further suppressed. The thickness of the above-mentioned cured film is more preferably 20 μm or more, further preferably 30 μm or more, more preferably 200 μm or less, and further preferably 100 μm or less.

[0187] The laminate A of the present invention preferably has an inorganic layer between the above-mentioned first element and the above-mentioned second element.

[0188] By providing an inorganic layer between the first element and the second element, the insulation property is improved, and a laminate with more excellent connection reliability can be produced. It should be noted that in the conventional laminate, since an insulating layer containing an inorganic material with a thickness of about 10 to 20 μm was used, warpage of the element and the laminate could not be eliminated, which became a cause of reduced connection reliability. However, in the present invention, since the insulating layer is mainly the above-mentioned cured film, if the thickness of the inorganic layer is reduced, the effect of the inorganic layer can be exerted, and warpage generated in the element and the laminate can also be eliminated.

[0189] The material of the inorganic layer is not particularly limited, and examples thereof include SiN, SiO2, Al2O3, etc. Among them, SiN and SiO2 are preferred from the viewpoints of excellent insulation property and heat resistance.

[0190] From the viewpoint of further improving the connection reliability of the laminate, the thickness of the inorganic layer is preferably 1 nm or more, more preferably 5 nm or more, further preferably 10 nm or more, preferably 1 μm or less, more preferably 500 nm or less, and further preferably 100 nm or less.

[0191] The laminate A of the present invention preferably has a barrier metal layer on the surface of the through-hole.

[0192] The barrier metal layer has the function of preventing the conductive material filled in the through-hole (for example, Cu atoms in the case of a Cu electrode) from diffusing into the cured film. By providing a barrier metal layer on the surface of the through-hole, the conductive material filling the through-hole is covered by the barrier metal layer except for the surface in contact with the electrode, so that short circuits and conduction failures caused by the diffusion of the conductive material into the cured film can be further suppressed. As the material of the barrier metal layer, known materials such as tantalum, tantalum nitride, titanium nitride, silicon oxide, and silicon nitride can be used.

[0193] The thickness of the barrier metal layer is not particularly limited. From the viewpoint of further improving the connection reliability of the laminate, it is more preferably 1 nm or more, further preferably 10 nm or more, more preferably 100 nm or less, and further preferably 50 nm or less.

[0194] Here, a diagram schematically showing one mode of the laminate A of the present invention is shown in Figure 1 . As Figure 1As shown, the laminate A of the present invention has the following structure: The first element 1 having the electrode 3 and the second element 2 are bonded by the cured film 4, and the electrodes 3 on the first element 1 and the second element 2 are electrically connected by the conductive material filled in the through holes 5 provided in the cured film 4. In the conventional laminate, the portion of the cured film 4 corresponding to the insulating layer is a hard inorganic material. Therefore, when warping occurs in the element or the laminate, the warping cannot be eliminated by stress relaxation, and electrode displacement and breakage are likely to occur. By using a flexible organic compound in the insulating layer in the present invention, the warping of the element and the laminate can be eliminated, so that electrode displacement and breakage can be suppressed.

[0195] In Figure 2 shows a diagram schematically showing one mode of the laminate A of the present invention. In Figure 2 's mode, an inorganic layer 6 is provided between the cured films 4, and the insulation is further improved. It should be noted that the thickness of the inorganic layer 6 of the present invention can be significantly thinner than the insulating layer of the conventional laminate, so it will not become an obstacle when eliminating the warping of the element and the laminate. In addition, in Figure 2 , the inorganic layer 6 is provided between the cured films 4, but it can also be provided on the first element 1 and the second element 2. In addition, in Figure 2 , the inorganic layer 6 is provided on the cured films 4 on the first element 1 side and the second element 2 side respectively, but it can also be provided only on either one. In addition, in Figure 2 's mode, a barrier metal layer 7 is provided on the surface of the through hole 5. By forming the barrier metal layer 7 on the surface of the through hole 5, the conductive material filled in the through hole 5 is less likely to diffuse into the cured film 4, so that short circuit and conduction failure can be further suppressed.

[0196] As a method for manufacturing the laminate A of the present invention, for example, a method for manufacturing a laminate having the following steps can be cited: a step of forming the resin composition of the present invention on the surfaces of the first element having the electrode and the second element having the electrode where the electrodes are formed, and curing it to form a cured film; a step of forming through holes in each of the above cured films; a step of filling each of the above through holes with a conductive material; a step of grinding the surfaces of the first element and the second element on the side filled with the conductive material to form bonding electrodes; a step of bonding the first element having the above bonding electrode and the second element having the above bonding electrode in a manner that the bonding electrodes are bonded to each other. Such a method for manufacturing a laminate is also one of the present inventions.

[0197] The method for manufacturing the laminate of the present invention first performs the following steps: a step of forming the resin composition of the present invention on the surfaces of the first element having the electrode and the second element having the electrode where the electrodes are formed, and curing it to form a cured film.

[0198] The above-described first and second elements having electrodes, and the resin composition may use the same substances as the first and second elements having electrodes of the laminate of the present invention, and the resin composition of the present invention. Further, when the resin composition of the present invention contains a solvent, the step of forming the cured film is performed after the resin composition of the present invention is formed into a film and the solvent is dried.

[0199] The method of forming the above film is not particularly limited, and a conventionally known method such as a spin coating method can be used.

[0200] The solvent drying conditions are not particularly limited. From the viewpoint of reducing the residual solvent and improving the heat resistance of the cured film, preferably, heating is performed 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, for example, 30 minutes, and more preferably about 1 hour.

[0201] The curing conditions are not particularly limited. From the viewpoint of allowing the curing reaction to proceed sufficiently and further improving the heat resistance, preferably, heating is performed 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, for example, 1 hour or more, and more preferably about 2 hours or more. The upper limit of the heating time is not particularly limited, and preferably 3 hours or less from the viewpoint of suppressing the thermal decomposition of the cured film.

[0202] Next, in the method for manufacturing the laminate of the present invention, a step of forming through holes in each of the above cured films is performed.

[0203] The above through holes can be patterned. The method of forming the above through holes is not particularly limited, and can be formed by laser irradiation such as CO2 laser, etching, etc. It should be noted that when other layers are formed on the electrode surface of the element, the above through holes are formed so as to also penetrate the other layers and expose the electrode surface of the element.

[0204] Next, in the method for manufacturing the laminate of the present invention, a step of forming an inorganic layer and / or a barrier metal layer is performed as needed.

[0205] The above inorganic layer and barrier metal layer may use the same inorganic layer and barrier metal layer as the laminate of the present invention. The above inorganic layer and barrier metal layer can be formed by sputtering, evaporation, etc.

[0206] The step of forming the above inorganic layer is preferably performed before and / or after the step of forming the above cured film. The formation of the above barrier metal layer is preferably performed after the step of forming the above through holes.

[0207] Next, in the method for manufacturing the laminate of the present invention, a step of filling each of the above through holes with a conductive material is performed. As a method of filling the above conductive material, plating, etc. can be used.

[0208] The above-mentioned conductive material can use the same conductive material as the conductive material of the laminate of the present invention.

[0209] Next, in the manufacturing method of the laminate of the present invention, a step of forming a bonding electrode by grinding the surfaces of the first element and the second element on the side filled with the conductive material is performed.

[0210] The above-mentioned conductive material formed in the unnecessary part is removed by grinding, thereby forming a bonding electrode for connecting the electrodes formed between the two elements. The above-mentioned grinding preferably flattens and removes the layer formed of the conductive material until the cured film is exposed, or until the inorganic layer is exposed when the above-mentioned inorganic layer exists.

[0211] The above-mentioned grinding method is not particularly limited, and for example, a chemical mechanical polishing method or the like can be used.

[0212] Such a manufacturing method of an element having a bonding electrode is also one of the present inventions. The manufacturing method includes: a step of forming a film of the resin composition of the present invention on the surface of the element having an electrode and curing it to form a cured film; a step of forming a through-hole in the above-mentioned cured film; a step of filling the above-mentioned through-hole with a conductive material; and a step of grinding the surface of the above-mentioned element to form a bonding electrode.

[0213] The above-mentioned element having a bonding electrode is a member for forming a laminate by bonding the bonding electrodes between the elements to each other. Regarding the above-mentioned element, cured film, resin composition and other configurations and each step, they are the same as the descriptions of the resin composition, laminate and manufacturing method of the laminate of the present invention.

[0214] Next, in the manufacturing method of the laminate of the present invention, a step of bonding the first element having the above-mentioned bonding electrode and the second element having the above-mentioned bonding electrode in such a manner that the above-mentioned bonding electrodes are bonded to each other is performed.

[0215] Even when the surface of the element has irregularities, the resin composition of the present invention can fill the irregularities. Therefore, the bonding surface of the obtained cured film becomes flat, and reliable bonding can be performed, so that the electrical connection reliability can be improved.

[0216] As a method of bonding the first element and the second element, a method of connecting by melting the electrode and the bonding electrode by heat treatment can be cited. The above-mentioned heat treatment is usually about 400 °C for 4 hours.

[0217] The use of the laminate of the present invention is not particularly limited. It has high electrical connection reliability. In particular, even when thin elements are joined to each other, warping and cracking of the elements and the laminate can be suppressed. Therefore, it can be suitably used for laminates constituting semiconductor devices and imaging devices.

[0218] Such semiconductor devices and imaging devices having the laminate of the present invention are also one of the present inventions.

[0219] The cured film of the present invention can be suitably used as an insulating layer of a laminate having a structure such as the above-mentioned laminate A, and can also be suitably used as an insulating layer of a laminate having a structure in which a support substrate is laminated on the chip-bearing surface of an element having a plurality of chips.

[0220] Such a laminate having the cured film of the present invention between the support substrate and the third element, wherein the third element has a first surface and a second surface, the first surface has a plurality of chips, and the cured film is laminated on the first surface side is also one of the present inventions. (Hereinafter, it is also referred to as laminate B)

[0221] The laminate B of the present invention has the cured film of the present invention between the support substrate and the third element.

[0222] Examples of the support substrate include glass and single crystal silicon. The third element is the same as the first and second elements. In addition, regarding the cured film, it is as described above.

[0223] The third element has a first surface and a second surface, the first surface has a plurality of chips, and the cured film is laminated on the first surface side.

[0224] The surface of the third element having a plurality of chips has larger irregularities due to the chips. In the present invention, even if the surface of the resin composition that is the source of the cured film has large irregularities, the gaps can be sufficiently filled to make the connection surface flat. Therefore, the connection reliability with the support substrate can be improved, and warping and cracking of the element can be suppressed. It should be noted that the number of the above chips is not particularly limited as long as it is two or more.

[0225] The laminate B of the present invention preferably has an inorganic layer between the support substrate and the cured film.

[0226] By further providing an inorganic layer between the support substrate and the cured film, the insulation can be further improved. Regarding the inorganic layer, the same inorganic layer as the inorganic layer of the laminate A can be used.

[0227] The laminate B of the present invention preferably further has a fourth element on the second surface of the third element, and the third element is electrically connected to the fourth element.

[0228] The laminate B of the present invention has large irregularities on its surface due to the chips, but is sufficiently adhered to the support substrate by the cured film of the present invention. Therefore, warping and cracking of the third element can be suppressed, and warping and cracking of the fourth element laminated on the third element can also be suppressed. As a result, displacement and cracking of the inter-element electrodes can also be suppressed, so that the electrical connection reliability can be improved.

[0229] The above-mentioned fourth element can use the same elements as the above-mentioned first to third elements.

[0230] Here, a diagram schematically showing one mode of the laminate B of the present invention is shown in Figure 3 . As Figure 3 shown, the laminate B of the present invention has the following structure: a plurality of chips 9 electrically connected to the third element 8 are laminated on the first surface of the third element 8, and a fourth element 10 electrically connected to the third element 8 is laminated on the second surface, which is the opposite surface of the first surface, of the third element 8. In addition, the first surface of the third element 8 and the support substrate 11 are laminated with the cured film 4 interposed therebetween. In the laminate B of the present invention, by using the cured film of the resin composition of the present invention for the cured film, the irregularities between the chip 9 and the support substrate 11 can be sufficiently filled to flatten the connection surface, and warping and poor adhesion of the elements and chips can be eliminated. Therefore, high electrical connection reliability can be imparted between the elements.

[0231] In Figure 4 , a diagram schematically showing one mode of the laminate B of the present invention is shown. In Figure 4 's mode, in addition to Figure 3 's mode, an inorganic layer 6 is provided between the cured film 4 and the support substrate 11, and the insulation is further improved. It should be noted that the thickness of the inorganic layer 6 of the present invention can be extremely thinner than the insulation layer of the conventional laminate, so it will not become an obstacle when eliminating the warping of the elements and the laminate.

[0232] The use of the laminate B of the present invention is not particularly limited, and it is similarly suitable for a photographing device and a semiconductor device as the above-mentioned laminate A.

[0233] Such a photographing device and a semiconductor device having the laminate B of the present invention are also one of the present inventions.

[0234] Advantages of the Invention

[0235] According to the present invention, it is possible to provide: a resin composition having excellent heat resistance and flexibility, capable of flattening the connection surface even when the surface of the element has irregularities, and capable of imparting high electrical connection reliability between elements; a cured film using the resin composition; a laminate having the cured film; a photographing device and a semiconductor device having the laminate; a manufacturing method of the laminate; and a manufacturing method of an element having a bonding electrode used in the manufacturing of the laminate. BRIEF DESCRIPTION OF THE DRAWINGS

[0236] Figure 1 FIG. is a diagram schematically showing one mode of the laminate of the present invention.

[0237] Figure 2 FIG. is a diagram schematically showing one mode of the laminate of the present invention.

[0238] Figure 3 FIG. is a diagram schematically showing one mode of the laminate of the present invention.

[0239] Figure 4 FIG. is a diagram schematically showing one mode of the laminate of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0240] Hereinafter, examples are listed to explain the mode of the present invention in more detail, but the present invention is not limited to these examples.

[0241] (1) Production of organosilicon compound a

[0242] 320 g of phenyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 198.29), 8.8 g of sodium hydroxide, 6.6 g of water, and 263 mL of 2-propanol were added to a reaction vessel equipped with a reflux condenser, a thermometer, and a dropping funnel. While stirring, heating was started under a nitrogen stream. After continuing stirring for 6 hours from the start of reflux, the mixture was allowed to stand at room temperature overnight. Then, the reaction mixture was transferred to a filter and filtered under nitrogen pressure. The obtained solid was washed once with 2-propanol, filtered, and dried under reduced pressure at 80 ° C to obtain 330 g of a colorless solid (DD-ONa).

[0243] Next, 20 g of cyclopentyl methyl ether, 2.4 g of 2-propanol, 14 g of ion-exchanged water, and 7.25 g of trichloromethylsilane (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 149.48) were added to a reaction vessel equipped with a reflux condenser, a thermometer, and a dropping funnel, and stirred at room temperature under a nitrogen atmosphere. Then, 8 g of the above-obtained compound (DD-ONa) and 20 g of cyclopentyl methyl ether were added to the dropping funnel to form a slurry, which was added dropwise to the reactor over 30 minutes. After the addition was completed, stirring was continued for 30 minutes. After the reaction, stirring was stopped and the mixture was allowed to stand, separating into an organic layer and an aqueous layer. The obtained organic layer was made neutral by washing with water, the waste was removed using a membrane filter, and the mixture was concentrated under reduced pressure at 60 ° C using a rotary evaporator to obtain 9.5 g of a colorless solid. The colorless solid was washed with 10 g of methyl acetate and dried under reduced pressure to obtain 6.2 g of a colorless powdery solid (DD(Me)-OH).

[0244] A condenser, a mechanical stirrer, a Dean-Stark tube, an oil bath, and a thermometer protection tube were installed on a 100 mL flask, and the inside of the flask was purged with nitrogen. 5.0 g of (DD(Me)-OH), 2.5 g of octamethylcyclotetrasiloxane (D4), 0.5 g of RCP-160M (strong acidic cation exchange resin, manufactured by Mitsubishi Chemical Corporation: water content 23.4 mass%), and 51.0 mL of dehydrated toluene were added to the flask. Reflux was carried out for 1 hour, and 22.4 mL of toluene and 0.12 g of water (23.4 mass% contained in RCP-160M) were distilled off. After the reflux was completed, the mixture was cooled to 80 °C, 0.55 g of pure water was added, and curing was carried out at 80 °C. As a result, equilibrium was reached in 5 hours. After cooling to room temperature, RCP-160M was separated by filtration, and the obtained filtrate was washed with water once. Then, the solvent and low-boiling components of the filtrate were removed by distillation, and the obtained crude product was reprecipitated with heptane for purification, whereby a silicone compound (silicone compound a, weight-average molecular weight 36,000) having the structure of the following formula (8) with m = 30 and an average of n (number of DMS chains) = 4 was obtained.

[0245] [Chemical formula 7]

[0246]

[0247] (2) Preparation of silicone compound b

[0248] SST-3PM4 manufactured by Gelest was used as silicone compound b. It should be noted that SST-3PM4 is a silicone compound that does not satisfy the above general formula (1).

[0249] (3) Manufacture of resin A (heat-resistant additive)

[0250] In a reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen inlet, 10.00 g of tetracarboxylic dianhydride 4,4’-(hexafluoroisopropylidene) diphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 444.24) and 92.72 g of anisole were added, and the solution in the reaction vessel was heated to 60 °C. Next, 7.573 g of aromatic diamine PAM-E (manufactured by Shin-Etsu Chemical Co., Ltd., molecular weight 280.51) was added to the reaction vessel. A Dean-Stark separator and a condenser were installed on the flask, and the mixture was heated under reflux at 100 °C for 1 hour and further at 170 °C for 4 hours to obtain an imide compound with amine groups at both ends. After cooling, citraconic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 112.08) was added, and the mixture was stirred while heating at 120 °C for 10 minutes and further at 170 °C for 20 minutes to obtain a compound having an imide structure with the structure of the following formula (9) (resin A, weight average molecular weight 9000).

[0251] [Chemical formula 8]

[0252]

[0253] Here, l represents the number of repeating units.

[0254] (4) Preparation of modifier

[0255] As the modifier, the following compounds were prepared.

[0256] Modifier A (BYK-320, manufactured by BYK Chemie): Polymethylalkylsiloxane having a polyether-modified group, molecular weight 22000

[0257] Modifier B (BYK-325N, manufactured by BYK Chemie): Polymethylalkylsiloxane having a polyether-modified group, molecular weight 17000

[0258] Modifier C (KP-341, manufactured by Shin-Etsu Chemical Co., Ltd.): Organosilicon compound having a polyether-modified group, molecular weight 18000

[0259] Modifier D (KP-112, manufactured by Shin-Etsu Chemical Co., Ltd.): Organosilicon compound having a polyether-modified group, molecular weight 20000

[0260] Modifier E (BYK-326, manufactured by BYK Chemie): Polymethylalkylsiloxane having a polyether-modified group, molecular weight 25000

[0261] Modifier F (BYK-307, manufactured by BYK Chemie): Polydimethylsiloxane with a polyether-modified group, molecular weight 31000

[0262] Modifier G (BYK-330, manufactured by BYK Chemie): Polydimethylsiloxane with a polyether-modified group, molecular weight 19000

[0263] Modifier H (BYK-327, manufactured by BYK Chemie): Polydimethylsiloxane with a polyether-modified group, molecular weight 6700

[0264] Modifier I (BYK-310, manufactured by BYK Chemie): Polymethylalkylsiloxane with a polyether-modified group, molecular weight 4400

[0265] Modifier J (BYK-322, manufactured by BYK Chemie): Polymethylalkylsiloxane with an arylalkyl-modified group, molecular weight 12000

[0266] Modifier K (BYK-323, manufactured by BYK Chemie): Polymethylalkylsiloxane with an arylalkyl-modified group, molecular weight 27000

[0267] Modifier L (KF-96-100cs, manufactured by Shin-Etsu Chemical Co., Ltd.): Silicone oil, molecular weight 12000

[0268] Modifier M (KF-96-1000cs, manufactured by Shin-Etsu Chemical Co., Ltd.): Silicone oil, molecular weight 34000

[0269] Modifier N: Fluorine-based surfactant, molecular weight 14000

[0270] Modifier O (BYK-394, manufactured by BYK Chemie): Polyacrylate-based surface conditioner, molecular weight 7000

[0271] (5) Determination of the thermal weight loss of the modifier

[0272] Using a differential thermal-thermogravimetric simultaneous measurement device (TG-DTA; STA7200, manufactured by Hitachi High-Tech Science Corporation), each modifier was heated from 25°C to 300°C in air at a heating rate of 10°C / min and held for 1 hour. After holding for 1 hour, it was further heated to 400°C at a heating rate of 10°C / min and held for 3 hours after reaching 400°C. Among the weights at each temperature, the thermal weight loss was calculated based on the weight at the initial arrival at 400°C and the weight after passing through 400°C for 3 hours.

[0273] (Example 1)

[0274] To 100 parts by weight of a silicone compound, 0.5 part by weight of modifier A, 3.2 parts by weight of a crosslinking agent (Silicate MS-51, manufactured by Mitsubishi Chemical Corporation), 0.2 part by weight of a catalyst (ZC-162, manufactured by Matsumoto Fine Chemical Co., Ltd.), and 1.0 part by weight of resin A (heat-resistant additive), cyclopentanone as a solvent was added to make the viscosity of the resulting composition 1200 cP, obtaining a resin composition.

[0275] (Examples 2 to 12, Comparative Examples 1 to 8)

[0276] The types and compounding amounts of the silicone compound, modifier, and solvent were changed to achieve the compositions shown in Tables 1 and 2, and otherwise, the operation was the same as in Example 1, obtaining a resin composition.

[0277] It should be noted that the viscosities of the resin compositions in the examples and comparative examples were all 1200 cP.

[0278] <Physical properties>

[0279] The following measurements were performed on the obtained resin composition. The results are shown in Tables 1 and 2.

[0280] (Measurement of contact angle)

[0281] The above silicone compound and 1 part by weight of the above modifier relative to 100 parts by weight of the above silicone compound were added to ethyl benzoate to prepare a sample having a viscosity of 45 cP at 25°C. Using a contact angle measuring device (fully automatic contact angle meter DMo-702, manufactured by Kyowa Interface Science Co., Ltd.), the above sample was dropped onto a silicon wafer, and the contact angle of the above sample with respect to the silicon wafer was measured. It should be noted that for Comparative Examples 4 and 5, since the modifier was insoluble in the solvent, the measurement of the contact angle and the following measurements and evaluations were not performed.

[0282] (Measurement of surface free energy)

[0283] Using the resin compositions described in Tables 1 and 2 as solutions, the following measurements were carried out. At room temperature, 6 g of the solution was dropped onto the central part of an 8-inch silicon wafer, and the resin composition was coated on the silicon wafer (surface roughness < 0.1 μm) using a spin coater (ACT-400II, manufactured by ACTIVE Corporation) under the conditions of 1500 rpm for 10 seconds. The wafer coated with the solution was heated at 125 °C for 10 minutes to dry the solvent. Then, it was heated at 300 °C for 1 hour to obtain a resin cured film with a thickness of 35 μm. For the obtained resin cured film, a contact angle measuring device (fully automatic contact angle meter DMo-702, manufactured by Kyowa Interface Science Co., Ltd.) was used to drop water and diiodomethane, and the contact angles of each liquid with respect to the resin cured film were measured, and thus the dispersion energy γ d , interaction energy γ h were calculated, and the surface free energy γ was calculated from their sum.

[0284] <Evaluation>

[0285] The following evaluations were carried out on the resin compositions obtained in the examples and comparative examples. The results are shown in Tables 1 and 2.

[0286] (Evaluation of film cracking)

[0287] At room temperature, 6 g of the solution obtained by the same method as the above measurement of surface free energy was dropped onto the central part of an 8-inch silicon wafer, and the resin composition was coated on the silicon wafer (surface roughness < 0.1 μm) using a spin coater (ACT-400II, manufactured by ACTIVE Corporation) under the conditions of 1500 rpm for 10 seconds. The wafer coated with the solution was heated at 125 °C for 10 minutes to dry the solvent. At this time, the rotation time of spin coating was adjusted so that the thickness of the dried resin composition became 35 μm. Then, it was further heated at 300 °C for 1 hour to cure the resin composition. After cooling to room temperature, the coated surface (surface) of the cured film was observed to evaluate the presence or absence of film cracking.

[0288] (Evaluation of 1% thermal weight loss temperature)

[0289] A cured film was prepared by the same method as the evaluation of film cracking. For the obtained cured film, a differential thermal-thermogravimetric simultaneous measurement device (TG-DTA; STA7200, manufactured by Hitachi High-Tech Science Corporation) was used to heat it at a heating rate of 10 °C / min under a nitrogen gas flow of 200 mL / min, and the temperature at which the weight loss rate reached 1% was measured.

[0290] (Evaluation of groove filling property)

[0291] At the center of an 8-inch silicon wafer with grooves having a depth of 10 μm and a width of 300 μm dug at 40 mm intervals, 6 g of a solution obtained by the same method as the measurement of the above surface free energy was dropped, and a film was formed on the silicon wafer (the surface roughness outside the groove part < 0.1 μm) using a spin coater (ACT-400II, manufactured by ACTIVE Corporation). The wafer coated with the solution was heated at 125°C for 10 minutes to dry the solvent. At this time, the rotation time of spin coating was adjusted so that the thickness of the dried resin composition became 35 μm. Then, it was further heated at 300°C for 1 hour to cure the resin composition. The groove part of the silicon wafer on the surface of the cured product after heat curing was observed using a laser microscope (OLS4100; manufactured by Olympus Corporation), and the depth of the groove part was measured. The ratio obtained by dividing the depth of the groove measured with the laser microscope by the original depth of the groove of the wafer, which is 10 μm (the value represented by the following formula), was used as the amount of depression (%), and the groove filling property (planarization property) was evaluated according to the following criteria. Note that the values in the table are the values of the amount of depression (%).

[0292] Amount of depression (%) = (Depth of groove (μm) after coating and curing the resin composition) / 10 (μm) × 100

[0293] 〇: Depression is less than 7%

[0294] △: Depression is 7% or more and less than 10%

[0295] ×: Depression is 10% or more

[0296] [Table 1]

[0297]

[0298] [Table 2]

[0299]

[0300] Industrial applicability

[0301] According to the present invention, it is possible to provide: a resin composition having excellent heat resistance and flexibility, and capable of planarizing the connection surface even when the surface of the element has irregularities and capable of imparting high electrical connection reliability between elements; a cured film using the resin composition; a laminate having the cured film; an imaging device and a semiconductor device having the laminate; a method for manufacturing the laminate; and a method for manufacturing an element having a bonding electrode used in the manufacture of the laminate.

[0302] Explanation of reference numerals

[0303] 1 First element

[0304] 2 Second element

[0305] 3 electrodes

[0306] 4 cured film

[0307] 5 through-hole

[0308] 6 inorganic layer

[0309] 7 barrier metal layer

[0310] 8 third element

[0311] 9 chip

[0312] 10 fourth element

[0313] 11 support substrate

Claims

1. A resin composition comprising a silicone compound and a modifier, The modifier is heated alone in air from room temperature to 300 °C at a heating rate of 10 °C / min and then held for 1 hour, and then heated to 400 °C at a heating rate of 10 °C / min and held at 400 °C for 3 hours. The thermal weight loss before and after holding at 400 °C for 3 hours is 10% or less. The silicone compound and 1 part by weight of the modifier relative to 100 parts by weight of the silicone compound are added to ethyl benzoate to prepare a sample having a viscosity of 45 cP at 25 °C. When the sample is dropped onto a silicon wafer, the contact angle of the sample with respect to the silicon wafer is 9° or more and 20° or less.

2. The resin composition according to claim 1 further contains a solvent. The resin composition is made into a solution with a viscosity of 1200 cP using the solvent, and the solution is spin-coated on a silicon wafer at 1500 rpm for 10 seconds. After the solvent is dried, it is cured at 300 °C for 1 hour to form a resin cured film with a thickness of 10 μm or more. At this time, the surface free energy of the resin cured film is 27 mJ / m 2 or more.

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

4. The resin composition according to any one of claims 1 to 3, wherein The silicone compound has a structure represented by the following general formula (1), Here, R 0 , R 1 and R 2 each independently represents a linear, branched or cyclic aliphatic group, aromatic group or hydrogen; 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 resin composition according to any one of claims 1 to 4, wherein, The modifier has a polyether-modified group.

6. The resin composition according to any one of claims 1 to 5, wherein, The content of the modifier is 0.01 part by weight or more and 10 parts by weight or less relative to 100 parts by weight of the silicone compound.

7. The resin composition according to any one of claims 1 to 6, wherein, The weight-average molecular weight of the modifier is 4000 or more and 30000 or less.

8. The resin composition according to claim 2, wherein, The 1% weight loss temperature of the cured product obtained by drying the solvent and curing at 300 °C for 1 hour of the resin composition is 460 °C or higher.

9. The resin composition according to any one of claims 1 to 8, for use in forming an insulating layer on the uneven surface of a component having unevenness on its surface.

10. A resin composition comprising a silicone compound and a modifier, The silicone compound has a structure represented by the following general formula (1), The modifier has a polyether-modified group, Here, R 0 , R 1 and R 2 each independently represents a linear, branched or cyclic aliphatic group, aromatic group or hydrogen; the aliphatic group and the aromatic group may or may not have substituents; m and n each represent an integer of 1 or more.

11. A cured film formed using the resin composition according to any one of claims 1 to 10.

12. A laminate having the cured film according to claim 11 between a first component having an electrode and a second component having an electrode, wherein the electrode of the first component and the electrode of the second component are electrically connected via a through-hole penetrating the cured film.

13. The laminate according to claim 12, having an inorganic layer between the first component and the second component.

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

15. An imaging device having the laminate according to any one of claims 12 to 14.

16. A semiconductor device having the laminate according to any one of claims 12 to 14.

17. A method for manufacturing a laminate, comprising: A step of forming the resin composition according to any one of claims 1 to 10 on the electrode-formed surfaces of a first component having an electrode and a second component having an electrode, and curing it to form a cured film; A step of forming through-holes in each of the cured films; A step of filling each of the through-holes with a conductive material; A step of polishing the surfaces of the first component and the second component on the side filled with the conductive material to form bonding electrodes; and A step of laminating a first element having the bonding electrode and a second element having the bonding electrode such that the bonding electrodes are bonded to each other.

18. A method for manufacturing an element having a bonding electrode, the method comprising: A step of forming a film of the resin composition according to any one of claims 1 to 10 on a surface of an element having an electrode, and curing the film to form a cured film; A step of forming a through hole in the cured film; A step of filling the through hole with a conductive material; and A step of polishing a surface of the element having the electrode on a side filled with the conductive material to form a bonding electrode.

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

20. The laminate according to claim 19, wherein, An inorganic layer is provided between the support substrate and the cured film.

21. The laminate according to claim 19 or 20, wherein A fourth element is further provided on the second surface of the third element, and the third element is electrically connected to the fourth element.

22. An imaging device having the laminate according to any one of claims 19 to 21.

23. A semiconductor device having the laminate according to any one of claims 19 to 21.

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