WO2025009514A1 - Curable resin composition, cured film, multilayer object, imaging device, semiconductor device, and method for producing multilayer object - Google Patents

Abstract

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

Description

CURABLE RESIN COMPOSITION, CURED FILM, LAMINATE, IMAGING DEVICE, SEMICONDUCTOR DEVICE, AND METHOD FOR PRODUCING LAMINATE

The present invention relates to a curable resin composition, a cured film, a laminate, an imaging device, a semiconductor device, and a method for manufacturing a laminate.

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

JP 2006-191081 A

In the manufacture of the semiconductor device, a high-temperature treatment of 400°C for 4 hours is performed when bonding the electrodes, so the insulating layer used to form the bonding surface is required to have high heat resistance. For this reason, in conventional semiconductor devices, insulating inorganic materials such as SiN and _SiO2 are used as the insulating layer. However, insulating layers made of inorganic materials are prone to warping of the substrate, and if the substrate is warped, the connection position of the electrodes may shift or the electrodes may crack when stacked, which may reduce the connection reliability of the semiconductor device. In addition, in recent years, the performance of semiconductor devices has improved, and substrates have become larger and thinner, making substrate warping more likely to occur, and the substrate may crack, especially when the substrate is thin.

In order to prevent warping and cracking of the substrate due to high-temperature processing, it has been considered to use an organic compound, which has more flexibility than inorganic materials, as an organic layer in the insulating layer. However, insulating layers made of organic compounds are vulnerable to heat, and outgassing generated by thermal decomposition can easily cause the insulating layer to crack. In response, the use of heat-resistant resins in the insulating layer has been considered, but resins are easily permeable to moisture and are therefore vulnerable to high humidity environments. If moisture penetrates the electrodes in a high humidity environment, the reliability of the semiconductor device can be reduced.

As a method for solving such moisture resistance problems, it has been proposed to laminate a thin inorganic layer made of an inorganic material on the organic layer. Since inorganic materials have high moisture resistance, covering the organic layer with an inorganic layer can increase moisture resistance. Furthermore, by making the inorganic layer thin, the effect of the organic layer in suppressing warping and cracking of the substrate due to high-temperature processing is not hindered.

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

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

構造式（Ａ）、（Ｂ）中、Ｒ^Ａ、Ｒ^Ｂはそれぞれ独立して脂肪族基、芳香族基又は水素を表す。ｊ、ｋはそれぞれ１以上の整数を表す。
［開示４］
シルセスキオキサンは下記構造式（１）で表される構造を有する、開示１～３のいずれかに記載の硬化性樹脂組成物。

構造式（１）中、Ｒ^０、Ｒ^１及びＲ^２はそれぞれ独立して直鎖状、分岐鎖状若しくは環状の脂肪族基、芳香族基又は水素を表す。前記脂肪族基及び前記芳香族基は置換基を有していても有していなくてもよい。ｍ、ｎはそれぞれ１以上の整数を表す。
［開示５］
シリカフィラーの含有量が、シルセスキオキサン１００重量部に対して１５重量部以上４０重量部以下である、開示１～４のいずれかに記載の硬化性樹脂組成物。
［開示６］
溶剤は沸点が１３０℃以上２５０℃以下である、開示１～５のいずれかに記載の硬化性樹脂組成物。
［開示７］
熱硬化させた硬化物の上に無機層を積層させて用いられる、開示１～６のいずれかに記載の硬化性樹脂組成物。
［開示８］
開示１～６のいずれかに記載の硬化性樹脂組成物を熱硬化させた硬化膜。
［開示９］
第１の基板上に開示８記載の硬化膜からなる有機層、前記有機層上に無機層が積層された積層体であって、
前記第１の基板は複数のチップを有する第１面とその反対面となる第２面を有し、前記第１面側に前記有機層及び前記無機層を有する積層体。
［開示１０］
無機層上に支持基板が積層されている、開示９記載の積層体。
［開示１１］
第１の基板の第２面上に更に第２の基板を有し、前記第１の基板と前記第２の基板が電気的に接続されている、開示９又は１０記載の積層体。
［開示１２］
電極を有する第３の基板と、電極を有する第４の基板との間に開示８記載の硬化膜からなる有機層と無機層とを有する積層体であって、
前記第３の基板の電極と前記第４の基板の電極とが、前記有機層及び前記無機層を貫通する貫通孔を介して電気的に接続されている、積層体。
［開示１３］
貫通孔の表面にバリアメタル層を有する、開示１２記載の積層体。
［開示１４］
開示９～１３のいずれかに記載の積層体を有する、撮像装置。
［開示１５］
開示９～１３のいずれかに記載の積層体を有する、半導体装置。
［開示１６］
複数のチップを有する第１面とその反対面となる第２面を有する第１の基板の前記第１面上に開示１～６のいずれかに記載の硬化性樹脂組成物を塗布し、溶剤乾燥、熱硬化することで有機層を形成する工程と、
前記有機層上に無機層を形成する工程を有する積層体の製造方法。
［開示１７］
電極を有する第３の基板及び電極を有する第４の基板の前記電極を有する面上に開示１～６のいずれかに記載の硬化性樹脂組成物を塗布し、溶剤乾燥、熱硬化することで有機層を形成する工程と、
前記有機層上に無機層を形成する工程と、
各前記有機層及び前記無機層に貫通孔を形成する工程と、
各前記貫通孔を導電性材料で充填する工程と、
前記電極を有する第３の基板及び前記電極を有する第４の基板の前記導電性材料を充填した側の表面を研磨して接合電極を形成する工程と、
前記電極を有する第３の基板及び前記電極を有する第４の基板の前記接合電極同士が接合するように貼り合せる工程を有する積層体の製造方法。 The present invention includes the following Disclosures 1 to 17. The present invention will be described in detail below.
[Disclosure 1]
A curable resin composition comprising silsesquioxane, a solvent, and a silica filler as an inorganic filler, the solvent being dried at 125°C for 10 minutes, and the composition being thermally cured by heat treatment at 300°C for 1 hour, the cured product having an elastic modulus at 300°C of 0.2 MPa or more.
[Disclosure 2]
The curable resin composition according to Disclosure 1, wherein the solvent is dried under conditions of 125°C for 10 minutes, and the cured product is heat-cured by heat treatment at 300°C for 1 hour, and the cured product has a coefficient of linear expansion (CTE) of 500 ppm/°C or less in the range of -40°C to 100°C.
[Disclosure 3]
The curable resin composition according to Disclosure 1 or 2, wherein the silsesquioxane has structures represented by the following structural formulas (A) and (B) in one molecule.

In structural formulae (A) and (B), R ^A and R ^B each independently represent an aliphatic group, an aromatic group, or hydrogen, and j and k each represent an integer of 1 or more.
[Disclosure 4]
The curable resin composition according to any one of Disclosures 1 to 3, wherein the silsesquioxane has a structure represented by the following structural formula (1):

In the structural formula (1), R ⁰ , R ¹ and R ² each independently represent a linear, branched or cyclic aliphatic group, an aromatic group or hydrogen. The aliphatic group and the aromatic group may or may not have a substituent. m and n each represent an integer of 1 or more.
[Disclosure 5]
The curable resin composition according to any one of Disclosures 1 to 4, wherein the content of the silica filler is 15 parts by weight or more and 40 parts by weight or less with respect to 100 parts by weight of the silsesquioxane.
[Disclosure 6]
The curable resin composition according to any one of Disclosures 1 to 5, wherein the solvent has a boiling point of 130° C. or higher and 250° C. or lower.
[Disclosure 7]
The curable resin composition according to any one of Disclosures 1 to 6, which is used by laminating an inorganic layer on a heat-cured product.
[Disclosure 8]
A cured film obtained by thermally curing the curable resin composition according to any one of Disclosures 1 to 6.
[Disclosure 9]
A laminate comprising an organic layer formed of the cured film according to Disclosure 8 on a first substrate, and an inorganic layer laminated on the organic layer,
The first substrate has a first surface having a plurality of chips and a second surface opposite thereto, and the organic layer and the inorganic layer are disposed on the first surface side of the first substrate.
[Disclosure 10]
Disclosure 10. The laminate according to Disclosure 9, wherein a supporting substrate is laminated on the inorganic layer.
[Disclosure 11]
The laminate according to Disclosure 9 or 10, further comprising a second substrate on the second surface of the first substrate, the first substrate and the second substrate being electrically connected to each other.
[Disclosure 12]
A laminate having an organic layer and an inorganic layer, each of which is made of the cured film according to Disclosure 8, between a third substrate having an electrode and a fourth substrate having an electrode,
a laminate in which the electrode of the third substrate and the electrode of the fourth substrate are electrically connected via a through hole penetrating the organic layer and the inorganic layer.
[Disclosure 13]
13. The laminate according to Disclosure 12, having a barrier metal layer on the surface of the through hole.
[Disclosure 14]
An imaging device having the laminate according to any one of Disclosures 9 to 13.
[Disclosure 15]
A semiconductor device comprising the laminate according to any one of Disclosures 9 to 13.
[Disclosure 16]
A step of applying a curable resin composition according to any one of Disclosures 1 to 6 onto a first surface of a first substrate having a first surface having a plurality of chips and a second surface opposite the first surface, and then drying the composition with a solvent and thermally curing the composition to form an organic layer;
A method for producing a laminate, comprising the step of forming an inorganic layer on the organic layer.
[Disclosure 17]
A step of applying the curable resin composition according to any one of Disclosures 1 to 6 onto a surface of a third substrate having an electrode and a fourth substrate having an electrode, and then drying the composition and thermally curing the composition to form an organic layer;
forming an inorganic layer on the organic layer;
forming through holes in each of the organic layer and the inorganic layer;
filling each of the through holes with a conductive material;
a step of polishing the surfaces of the third substrate having the electrode and the fourth substrate having the electrode, the surfaces being filled with the conductive material, to form bonding electrodes;
A method for manufacturing a laminate, comprising a step of bonding a third substrate having the electrode and a fourth substrate having the electrode together so that the bonding electrodes of the third substrate and the fourth substrate are bonded to each other.

The curable resin composition of the present invention contains a silsesquioxane.
Silsesquioxane has high heat resistance while having the same degree of flexibility as organic compounds, so that by using a cured film mainly composed of silsesquioxane as the insulating layer of a laminate, it is possible to suppress warping and cracking of the substrate and improve the reliability of electrical connection. The above-mentioned silsesquioxane is not particularly limited as long as it is thermosetting, but it is preferable that one molecule has a structure represented by the following structural formulas (A) and (B) in order to further suppress warping and cracking of the substrate.

構造式（Ａ）、（Ｂ）中、Ｒ^Ａ、Ｒ^Ｂはそれぞれ独立して脂肪族基、芳香族基又は水素を表す。ｊ、ｋは繰り返し単位であり、それぞれ１以上の整数を表す。

In structural formulae (A) and (B), R ^A and R ^B each independently represent an aliphatic group, an aromatic group, or hydrogen, and j and k each represent a repeating unit and an integer of 1 or more.

The silsesquioxane preferably has a reactive site.
By using silsesquioxane having a reactive site as the curable resin of the curable resin composition, warping and cracking of the element can be further suppressed. In addition, since silsesquioxane has excellent heat resistance, decomposition of the organic layer due to high-temperature treatment performed during the manufacture of a semiconductor device having multiple laminates can be further suppressed. Examples of the reactive site include a hydroxyl group and an alkoxy group.

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

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

構造式（１）中、Ｒ^０、Ｒ^１及びＲ^２はそれぞれ独立して直鎖状、分岐鎖状若しくは環状の脂肪族基、芳香族基又は水素を表す。上記脂肪族基及び上記芳香族基は置換基を有していても有していなくてもよい。ｍ、ｎはそれぞれ１以上の整数を表す。

In the structural formula (1), R ⁰ , R ¹ and R ² each independently represent a linear, branched or cyclic aliphatic group, an aromatic group or hydrogen. The aliphatic group and the aromatic group may or may not have a substituent. m and n each represent an integer of 1 or more.

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

In the structural formula (1), R ¹ and R ² each independently represent a linear, branched or cyclic aliphatic group, an aromatic group, or hydrogen. The aliphatic group and the aromatic group may or may not have a substituent. R ¹ and R ² are preferably a phenyl group, an alkyl group having 1 to 20 carbon atoms, or an arylalkyl group, and more preferably a phenyl group or a methyl group. By R ¹ and R ² being a phenyl group, an alkyl group having 1 to 20 carbon atoms, or an arylalkyl group, higher heat resistance can be exhibited.

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

The weight average molecular weight of the silsesquioxane is not particularly limited, but is preferably 5000 to 150000. When the weight average molecular weight of the silsesquioxane is in the above range, the film-forming property during application is improved, the flattening performance is further improved, and warping and cracking of the element can be further suppressed. The weight average molecular weight of the silsesquioxane is more preferably 10000 or more, even more preferably 30000 or more, more preferably 100000 or less, and even more preferably 70000 or less.
The weight average molecular weight of the silsesquioxane is measured as a polystyrene-equivalent molecular weight by gel permeation chromatography (GPC) using THF as an elution solvent and a Time-MB-M6.0×150 mm (manufactured by Waters Corporation) or an equivalent column, and can be calculated with a polystyrene standard.

The content of the silsesquioxane is preferably 65% by weight or more and 99% by weight or less based on 100% by weight of the solid components of the curable resin composition.
By setting the content of silsesquioxane in the curable resin composition within the above range, it is possible to suppress warping or cracking of the element and further improve the reliability of electrical connection. The content of silsesquioxane in 100% by weight of the solid component of the curable resin composition is more preferably 70% by weight or more, even more preferably 75% by weight or more, more preferably 98% by weight or less, and even more preferably 97% by weight or less.

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

The solvent in the curable resin composition preferably has a boiling point of 130° C. or higher and 250° C. or lower.
By having the boiling point of the solvent in the above range, the aggregation of the silica filler due to the evaporation of the solvent can be suppressed, and the silica filler can be uniformly dispersed in the resin composition. The boiling point of the solvent is more preferably 150°C or higher, even more preferably 180°C or higher, more preferably 230°C or lower, and even more preferably 220°C or lower. Examples of solvents having a boiling point in the above range include aromatic organic solvents, ketone organic solvents, lactam organic solvents, and lactone organic solvents. A lactam organic solvent is an organic solvent of a heterocyclic compound having -C(=O)NR- in the ring, and a lactone organic solvent is an organic solvent of a heterocyclic compound having -C(=O)- in the ring. Here, R represents a hydrocarbon. Specific examples of the compound include cyclopentanone (boiling point: 131° C.), propylene glycol monomethyl ether acetate (boiling point: 146° C.), anisole (boiling point: 154° C.), ethyl benzoate (boiling point: 211 to 213° C.), N-methyl-2-pyrrolidone (boiling point: 202° C.), 2-piperidone (boiling point: 256° C.), 2-pyrrolidone (boiling point: 245° C.), γ-butyrolactone (boiling point: 204° C.), and γ-valerolactone (boiling point: 207° C.).

The content of the solvent in the curable resin composition is preferably 50% by weight or less.
By the content of the solvent in the curable resin composition being within the above range, shrinkage due to the volatilization of the solvent during curing is reduced, so that the resulting cured film is less likely to have unevenness, and the connection surface can be made flat. As a result, the bonding reliability of the substrate is improved, and the electrical connection reliability can also be improved. The content of the solvent is more preferably 45% by weight or less, even more preferably 40% by weight or less, and even more preferably 35% by weight or less. The lower limit of the content of the solvent is not particularly limited, but is preferably 30% by weight or more from the viewpoint of further improving the flattening performance.

The content of the solvent is preferably 50 parts by weight or more and 100 parts by weight or less based on 100 parts by weight of the silsesquioxane.
The content of the solvent relative to the silsesquioxane in the above range can further improve the planarization performance of the substrate surface. The content of the solvent relative to the silsesquioxane is more preferably 55 parts by weight or more, even more preferably 60 parts by weight or more, more preferably 80 parts by weight or less, and even more preferably 70 parts by weight or less.

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

The silica filler is preferably not spherical in shape.
The elastic modulus is increased by the silica filler having a shape other than a perfect sphere, and the elastic modulus described later can be more easily satisfied. In addition, by using a silica filler having a shape other than a perfect sphere, it is possible to control the elastic modulus without using a crosslinking agent, and it is possible to avoid the increase in storage stability and viscosity caused by the use of a crosslinking agent in combination. The reason why the elastic modulus is increased by the silica filler having a shape other than a perfect sphere is not clear, but it is thought that this is because the contact area with other fillers is small when the silica filler is a perfect sphere, making it difficult to interact with other fillers. Examples of the shape of the silica filler other than a perfect sphere include needles, pulverized, and fibrous. Note that even when a perfect spherical silica filler is used, it is possible to adjust the elastic modulus to the range described later by combining it with a crosslinking agent.

The silica filler preferably has a bulk density of 0.01 g/cm ³ or more and 0.2 g/cm ³ or less.
When the bulk density of the silica filler is in the above range, it is easier to satisfy the elastic modulus described below. The bulk density of the silica filler is more preferably 0.05 g/ ^cm3 or more and more preferably 0.1 g/cm3 or ^less .

The content of the silica filler is preferably 15 parts by weight or more and 40 parts by weight or less based on 100 parts by weight of the silsesquioxane.
By setting the content of the silica filler within the above range, it is possible to suppress warping and cracking of the substrate and to more easily satisfy the elastic modulus described below. The content of the silica filler is more preferably 20 parts by weight or more, more preferably 25 parts by weight or more, more preferably 35 parts by weight or less, and even more preferably 30 parts by weight or less, relative to 100 parts by weight of the silsesquioxane.

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

The content of the catalyst is not particularly limited, but is preferably 0.01 parts by weight or more and 10 parts by weight or less per 100 parts by weight of the silsesquioxane. By setting the content of the catalyst within the above range, curing can be further promoted and decomposition of the cured film due to high-temperature treatment can be further suppressed. The content of the catalyst is more preferably 0.1 parts by weight or more, even more preferably 0.2 parts by weight or more, more preferably 7 parts by weight or less, and even more preferably 5 parts by weight or less per 100 parts by weight of the silsesquioxane.

The curable resin composition may contain a crosslinking agent.
When the curable resin composition contains a crosslinking agent, the crosslinking agent crosslinks between the curable resins, increasing the crosslink density of the cured product, and further suppressing decomposition at high temperatures. As a result, the warping and cracking of the substrate can be suppressed, and the connection reliability can be further improved. In addition, the elastic modulus described below can be controlled by adjusting the blending amount and structure of the crosslinking agent. Furthermore, by containing a crosslinking agent, the elastic modulus described below can be controlled even if the shape of the silica filler is spherical. Examples of the crosslinking agent include alkoxysilane compounds such as dimethoxysilane compounds, trimethoxysilane compounds, diethoxysilane compounds, and triethoxysilane compounds, or silicate oligomers obtained by condensation of tetramethoxysilane compounds and tetraethoxysilane compounds. Among them, polyalkoxysilane is preferable from the viewpoint of improving the crosslink density and improving the heat resistance.

The content of the crosslinking agent is not particularly limited, but is preferably 1 part by weight or more and 50 parts by weight or less per 100 parts by weight of the silsesquioxane. By setting the content of the crosslinking agent within the above range, the crosslink density of the cured product can be controlled, and by combining it with the silica filler described above, it is possible to easily adjust the elastic modulus to the range described below. The content of the crosslinking agent is more preferably 3 parts by weight or more, even more preferably 3.2 parts by weight or more, more preferably 30 parts by weight or less, and even more preferably 20 parts by weight or less per 100 parts by weight of the silsesquioxane.

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

The heat-resistant resins include polyimide, epoxy resin, silicone resin, benzoxazine resin, cyanate resin, phenolic resin, etc., and polyimide is particularly preferred from the viewpoint of heat resistance.

The molecular weight of the heat-resistant resin is not particularly limited, but is preferably 5,000 or more and 150,000 or less. By having the weight-average molecular weight of the heat-resistant resin in the above range, it is possible to obtain a cured film that is less likely to crack during high-temperature treatment, even if the cured film is thick. The molecular weight of the heat-resistant resin is more preferably 10,000 or more, even more preferably 30,000 or more, more preferably 100,000 or less, and even more preferably 70,000 or less.

The content of the heat-resistant resin is preferably 0.5 parts by weight or more and 50 parts by weight or less based on 100 parts by weight of the silsesquioxane.
By making the content of heat-resistant resin within the above range, even if it is made into a thick cured film, it can be made into a cured film that is less likely to crack when treated at high temperature.The content of the heat-resistant resin is more preferably 0.7 parts by weight or more, more preferably 0.75 parts by weight or more, particularly preferably 1 part by weight or more, more preferably 20 parts by weight or less, more preferably 10 parts by weight or less, particularly preferably 5 parts by weight or less, based on 100 parts by weight of the silsesquioxane.

When the heat-resistant resin is a polyimide, the polyimide preferably has a siloxane bond.
When the polyimide has a siloxane bond, the compatibility with the silsesquioxane is increased, so that unevenness (surface roughness) caused by precipitation of the polyimide during application can be further suppressed.

When the polyimide has a siloxane bond, the polyimide preferably has a ratio of carbon atoms to silicon atoms in the main chain structure, C/Si, of 17 or less.
When the ratio of carbon atoms to silicon atoms in the main chain structure of the polyimide falls within the above range, the compatibility with the silsesquioxane is further increased, so that surface roughness can be further suppressed during application. The C/Si is more preferably 16.5 or less, and even more preferably 16 or less. The lower limit of the C/Si is not particularly limited, but is preferably 4 or more from the viewpoint of practical use and further increasing the heat resistance at 400°C. The ratio C/Si of carbon atoms to silicon atoms in the main chain structure of the polyimide is the ratio of C and Si in the repeating unit, and does not include C and Si at both ends. The C/Si can be obtained by obtaining the structure of the polyimide by ¹ H-NMR, ¹³ C-NMR, and ²⁹ Si-NMR, and measuring the number of C atoms and Si atoms from the repeating unit of the main chain.

The polyimide preferably has an oxazine ring or imide ring structure at least at one of its terminals, and more preferably has an oxazine ring or imide ring structure at both terminals.
By having an oxazine ring or imide ring structure at the terminal of the polyimide, surface roughness can be further suppressed when the polyimide is made into a thick film. The oxazine ring and imide ring structures may have a substituent.
Among them, it is more preferable that the polyimide has any one of the structures represented by the following structural formulas (2) to (7) at at least one terminal, and it is particularly preferable that both terminals have any one of the structures represented by the following structural formulas (2) to (7). Note that "*" in the structural formulas below represents a bonding site with a portion other than the terminal of the polyimide.

The polyimide preferably has a weight average molecular weight of 1,000 or more and 50,000 or less.
When the weight average molecular weight of the polyimide is within the above range, the compatibility with the silsesquioxane is improved, and the handleability can be further improved. The weight average molecular weight is more preferably 2000 or more, even more preferably 3000 or more, more preferably 35000 or less, and even more preferably 30000 or less.
The weight average molecular weight of the polyimide is measured as a polystyrene-equivalent molecular weight by gel permeation chromatography (GPC) using THF as an elution solvent and a Time-MB-M 6.0×150 mm (manufactured by Waters Corporation) or an equivalent column, and can be calculated with a polystyrene standard.

The content of the polyimide is preferably 0.5 parts by weight or more and 50 parts by weight or less based on 100 parts by weight of the silsesquioxane.
By making the polyimide content within the above range, even if it is made into a thick cured film, it can be made into a cured film that is less likely to crack when treated at high temperature.The content of the polyimide is preferably 0.7 parts by weight or more, more preferably 0.75 parts by weight or more, and even more preferably 1 part by weight or more, and is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, and even more preferably 5 parts by weight or less, based on 100 parts by weight of the silsesquioxane.

The curable resin composition of the present invention may contain other additives such as viscosity modifiers, fillers other than silica fillers, and adhesion promoters as necessary, within the scope of the invention.

The curable resin composition of the present invention has an elastic modulus at 300° C. of 0.2 MPa or more for a cured product after drying the solvent at 125° C. for 10 minutes and heat-curing by heat treatment at 300° C. for 1 hour.
By setting the elastic modulus of the cured product at 300°C within the above range, it is possible to suppress the occurrence of wrinkles in the inorganic layer, and to suppress process abnormalities caused by wrinkles in the inorganic layer. The elastic modulus of the cured product at 300°C is preferably 0.2 MPa or more, more preferably 0.5 MPa or more, and even more preferably 1 MPa or more. The upper limit of the elastic modulus of the cured product at 300°C is not particularly limited, but is preferably 100 MPa or less, more preferably 50 MPa or less, from the viewpoint of further suppressing warping and cracking of the substrate. The elastic modulus can be adjusted by the type of the silsesquioxane, the type, shape and amount of the silica filler, the crosslinking structure, etc.
The elastic modulus can be specifically measured by the following method.

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

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

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

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

The curable resin composition of the present invention is preferably used as an insulating layer in a laminate consisting of multiple substrates in which the heat-cured cured product is used in semiconductor devices, image sensors, etc., and more preferably used by laminating an inorganic layer on the heat-cured cured product. By forming such an insulating layer, it is possible to exhibit high moisture resistance while suppressing warping and cracking of the substrate, and further, wrinkles are less likely to occur in the inorganic layer, thereby suppressing process abnormalities caused by wrinkles in the inorganic layer.

Such a cured film obtained by thermally curing the curable resin composition of the present invention also constitutes the present invention.
Furthermore, a laminate using the cured film of the present invention, that is, a laminate in which an organic layer made of the cured film of the present invention is laminated on a first substrate, and an inorganic layer is laminated on the organic layer, the first substrate has a first surface having a plurality of chips and a second surface which is the opposite surface, and the organic layer and the inorganic layer are on the first surface side (hereinafter also referred to as laminate A). is also one aspect of the present invention.

The laminate A of the present invention is a laminate in which an organic layer is laminated on a first element, and an inorganic layer is laminated on the organic layer.
The organic layer and inorganic layer serve as an insulating layer between each element and substrate in a semiconductor device in which a plurality of elements and substrates are laminated. Conventional insulating layers use hard inorganic materials to withstand high-temperature treatment during manufacturing, so that when the substrate is deformed, the stress cannot be relieved and the substrate is prone to warping and cracking. In the laminate of the present invention, by using an organic compound having flexibility capable of relieving stress as the insulating layer, the substrate is less likely to warp or crack, and as a result, the electrode misalignment and cracking caused by the substrate warping and cracking can be suppressed, thereby improving the connection reliability between the substrates. In addition, by providing an inorganic layer as an auxiliary insulating layer on the organic layer, moisture in the atmosphere is less likely to permeate than the organic layer alone, so that high connection reliability can be achieved even under high temperature and high humidity. Furthermore, since the organic layer is made of a cured film of the curable resin composition of the present invention, wrinkles are less likely to occur in the inorganic layer even when the inorganic layer is laminated. As a result, process abnormalities such as alignment defects caused by wrinkles in the inorganic layer can be suppressed. In addition, since the inorganic layer of the laminate of the present invention is thin, the organic layer does not hinder the elimination of the warping of the substrate.

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

The first substrate has a first surface having a plurality of chips and a second surface opposite thereto, and has the organic layer and the inorganic layer on the first surface side.
When a plurality of chips are arranged on the first substrate and an insulating layer is formed on the surface of the first substrate on which the chips are arranged, the chips form unevenness, so that the connection surface is not flat and the connection reliability is likely to decrease. In the laminate of the present invention, even in the case of a substrate having such unevenness, the organic layer fills the unevenness to make the connection surface flat, so that warping and cracking of the first substrate and the chips can be suppressed. In addition, by forming a thin inorganic layer on the organic layer, it is possible to improve the connection reliability under high temperature and high humidity while eliminating the warping of the substrate. In addition, since the connection reliability under high temperature and high humidity is improved, it is preferable that the inorganic layer covers the entire exposed surface of the organic layer.

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

The organic layer preferably has a thickness of 10 μm or more.
By setting the thickness of the organic layer within the above range, it can play a role as an insulating layer, and can suppress warping and cracking of the substrate to improve connection reliability. In addition, in a conventional laminate in which an inorganic layer is formed on an organic layer, cracks are particularly likely to occur in the inorganic layer when the organic layer is made into a thick film, but in the laminate of the present invention, even when the organic layer is made into a thick film, cracks are unlikely to occur in the inorganic layer, and it can exhibit high moisture resistance. The thickness of the organic layer is preferably 20 μm or more, more preferably 30 μm or more, and preferably 200 μm or less, and more preferably 100 μm or less.

The material of the inorganic layer is not particularly limited, and examples thereof include SiN, SiO ₂ , and Al ₂ O _3. Among these, SiN and SiO ₂ are preferred because of their excellent insulating properties and heat resistance.

The thickness of the inorganic layer is preferably 1 nm or more, more preferably 5 nm or more, and even more preferably 10 nm or more, from the viewpoint of further increasing the connection reliability of the laminate. Furthermore, from the viewpoint of not preventing the elimination of warpage in the substrate, the thickness is preferably 1 μm or less, more preferably 500 nm or less, and even more preferably 100 nm or less.

The laminate A of the present invention may further include a supporting substrate laminated on the inorganic layer.
By laminating a support substrate on the inorganic layer, it becomes easy to fix an electronic component including the laminate of the present invention, such as an imaging device or semiconductor device, to a housing.
The supporting substrate may be made of glass, single crystal silicon, or the like.

The laminate A of the present invention may further have a second substrate on the second surface of the first substrate, and the first substrate and the second substrate may be electrically connected to each other.
In the laminate A of the present invention, since the organic layer suppresses warping and cracking of the first substrate, warping and cracking of the second substrate further laminated on the first substrate are also suppressed, thereby improving connection reliability. The second substrate may be the same as the first substrate.

Here, a schematic diagram showing an example of the laminate A of the present invention is shown in FIG. 1. As shown in FIG. 1, the laminate A of the present invention has a structure in which an organic layer 3 and an inorganic layer 4 are laminated on the surface (first surface) of a first substrate 1 having a plurality of chips 2 on which the chips are laminated, and the organic layer 3 and the inorganic layer 4 act as insulating layers. Conventional insulating layers consisting of an organic layer and an inorganic layer exhibit excellent connection reliability by suppressing warping and cracking of the substrate with the organic layer 3 and suppressing moisture permeation with the inorganic layer 4, but wrinkles in the inorganic layer, which cause process abnormalities, tend to occur. In the laminate of the present invention, wrinkles are unlikely to occur in the inorganic layer by using the curable resin composition of the present invention as the material for the organic layer, so that process abnormalities such as alignment defects can be suppressed. In addition, the laminate A of the present invention may have a support substrate 5 laminated on the inorganic layer 4, and a second substrate 6 may be laminated on the surface (second surface) opposite to the surface on which the organic layer 3 of the first substrate 1 is laminated, and the first substrate 1 and the second substrate 6 may be electrically connected. In FIG. 1, the organic layer 3 and the inorganic layer 4 are single layers, but they may be made up of multiple layers.

A method for producing a laminate A of the present invention, which includes a step of applying a curable resin composition of the present invention to a first surface of a first substrate having a first surface with a plurality of chips and a second surface opposite the first surface, and forming an organic layer by solvent drying and thermal curing, and a step of forming an inorganic layer on the organic layer, is also one aspect of the present invention.

The method for manufacturing the laminate A of the present invention first involves applying the curable resin composition of the present invention onto the first surface of a first substrate having a first surface having a plurality of chips and a second surface opposite the first surface, followed by solvent drying and thermal curing to form an organic layer.
Conventional laminates using inorganic materials for the insulating layer have been manufactured by time-consuming methods such as chemical vapor deposition (CVD) and sputtering. Since the main component of the insulating layer of the laminate of the present invention is an organic compound, it can be manufactured by applying a solution and drying it, which not only improves connection reliability but also increases production efficiency. The first substrate and the curable resin composition are the same as the first substrate and the curable resin composition of the present invention in the laminate A of the present invention.

The method for forming the film is not particularly limited, and a conventionally known method such as spin coating can be used.
The solvent drying conditions are not particularly limited, but from the viewpoint of reducing the remaining solvent and improving the heat resistance of the organic layer, it is preferable to heat the organic layer at a temperature of preferably 70° C. or higher, more preferably 100° C. or higher, preferably 250° C. or lower, more preferably 200° C. or lower, for example, for 30 minutes, more preferably for about 1 hour.
The curing conditions are not particularly limited, but from the viewpoint of sufficiently progressing the curing reaction and further improving the heat resistance, it is preferable to heat for, for example, about 1 hour or more, more preferably 2 hours or more at a temperature of preferably 200° C. or more, more preferably 220° C. or more, preferably 400° C. or less, more preferably 300° C. or less. The upper limit of the heating time is not particularly limited, but from the viewpoint of suppressing thermal decomposition of the organic layer, it is preferably 3 hours or less.

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

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

When the laminate A of the present invention has a second substrate, the manufacturing method of the laminate A of the present invention includes a step of laminating a second substrate on the second surface of the first substrate and electrically connecting the first substrate and the second substrate.
The first and second substrates may be electrically connected by a method of melting and connecting the electrodes of the first and second substrates by heat treatment, etc. The heat treatment is usually performed at 400° C. for about 4 hours.

An example of a laminate using the cured film of the present invention is a laminate having a structure in which two substrates having electrodes are electrically connected and an insulating layer made of the cured film of the present invention and an inorganic layer is disposed between the two substrates.
Such a laminate having an organic layer and an inorganic layer made of the cured film of the present invention between a third substrate having an electrode and a fourth substrate having an electrode, in which the electrode of the third substrate and the electrode of the fourth substrate are electrically connected via a through hole penetrating the organic layer and the inorganic layer (hereinafter, also referred to as laminate B), also constitutes one aspect of the present invention.

The laminate B of the present invention is a laminate having an organic layer and an inorganic layer composed of the cured film of the present invention between a third substrate having an electrode and a fourth substrate having an electrode, and the electrode of the third substrate and the electrode of the fourth substrate are electrically connected via a through hole penetrating the organic layer and the inorganic layer.
The cured film and inorganic layer provided between the electrode of the third substrate (hereinafter also referred to as the first electrode) and the electrode of the fourth substrate (hereinafter also referred to as the second electrode) act as an insulating layer, thereby suppressing short circuit of current. Conventional insulating layers use only hard inorganic materials such as SiN and SiO ₂ , so that when warping occurs during the formation of the insulating layer or the formation of the laminate, it is not possible to eliminate this by stress relaxation, and as a result, warping of the substrate and the resulting displacement and cracking of the electrodes are likely to occur. In the present invention, the cured film made of a curable resin composition having higher flexibility than inorganic materials is used as the main insulating layer, so that the warping of the substrate can be eliminated, thereby exhibiting high connection reliability. In addition, the moisture resistance can be increased by using a thin inorganic layer as an auxiliary insulating layer so as not to prevent the elimination of the warping of the substrate. Furthermore, the cured film of the present invention is less likely to cause wrinkles in the inorganic layer even when an inorganic layer is laminated on the cured film, so that process defects such as alignment defects can be suppressed.
Here, being electrically connected refers to a state in which the first electrode and the second electrode are connected by a conductive material or the like filled in the through hole.

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

The materials of the electrodes of the third and fourth substrates and the conductive material are not particularly limited, and conventional electrode materials such as gold, copper, and aluminum can be used.

The laminate B of the present invention preferably has a barrier metal layer on the surface of the through hole.
The barrier metal layer has a role of preventing the diffusion of the conductive material (e.g., Cu atoms in the case of a Cu electrode) filled in the through hole into the organic layer. By providing a barrier metal layer on the surface of the through hole, the conductive material filling the through hole is covered with the barrier metal layer except for the surface in contact with the electrode, so that short circuits and poor conduction caused by the diffusion of the conductive material into the organic layer can be further suppressed. The material of the barrier metal layer can be a known material such as tantalum, tantalum nitride, titanium nitride, silicon oxide, silicon nitride, etc.

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

Here, a schematic diagram showing an example of the laminate B of the present invention is shown in FIG. 2. As shown in FIG. 2, the laminate B of the present invention has a structure in which a third substrate 7 having an electrode 8 and a fourth substrate 9 are bonded via an organic layer 3 and an inorganic layer 4, and the electrodes 8 on the third substrate 7 and the fourth substrate 9 are electrically connected through a conductive material filled in a through hole 10 provided in the organic layer 3. In the conventional laminate, the organic layer 3 corresponding to the insulating layer was a hard inorganic material, so that when warping occurred in the substrate or laminate, this could not be eliminated by stress relaxation, and the electrodes were prone to misalignment and cracking. The laminate B of the present invention can eliminate warping of the substrate or laminate by using an organic layer made of the cured film of the present invention having flexibility in the insulating layer, so that the electrodes can be prevented from misaligning and cracking. In addition, the moisture resistance can be improved by using a thin inorganic layer 4 as an auxiliary insulating layer so as not to prevent the elimination of the warp of the substrate. If the inorganic layer 4 covers the entire side surface of the organic layer 3, the moisture resistance can be further improved. Furthermore, the cured film of the present invention is unlikely to cause wrinkles in the inorganic layer even when an inorganic layer is laminated on the cured film, so that process defects such as alignment defects can be suppressed. Furthermore, the laminate B of the present invention may be provided with a barrier metal layer 11 on the surface of the through hole 10. By providing the barrier metal layer 11, the conductive material filled in the through hole 10 is unlikely to diffuse into the organic layer 3, so that short circuits and conduction defects can be further suppressed. In FIG. 2, the inorganic layer 4 is provided on the organic layer 3 on the third substrate 7 side and the fourth substrate 9 side, but it may be provided on only one of them.

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

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

In the method for producing the laminate B of the present invention, a step of forming through holes in each of the organic layers and the inorganic layers is then carried out.
The through-hole may be patterned. The method for forming the through-hole is not particularly limited, and the through-hole may be formed by laser irradiation such as _CO2 laser or etching. When other layers are formed on the electrode surface of the substrate, the through-hole is formed so as to penetrate the other layers and expose the electrode surface of the substrate.

In the method for producing the laminate B of the present invention, a step of forming a barrier metal layer is then carried out as necessary.
The barrier metal layer may be the same as that of the laminate B of the present invention. The barrier metal layer may be formed by sputtering, vapor deposition or the like.

The method for producing the laminate B of the present invention then includes a step of filling each of the through holes with a conductive material. As a method for filling the through holes with the conductive material, plating or the like can be used.
The conductive material may be the same as the conductive material of the laminate B of the present invention.

The method for producing the laminate B of the present invention then includes a step of polishing the surfaces of the third substrate having the electrode and the fourth substrate having the electrode, the surfaces being filled with the conductive material, to form bonding electrodes.
The conductive material formed in the unnecessary portion is removed by grinding to form a bonding electrode connecting the electrodes formed on the two elements. The polishing is preferably performed by planarizing and removing the layer formed of the conductive material until the inorganic layer is exposed.
The polishing method is not particularly limited, and for example, a chemical mechanical polishing method can be used.

The method for producing laminate B of the present invention then carries out a step of bonding the third substrate having the electrode and the fourth substrate having the electrode together so that the bonding electrodes of the third substrate having the electrode are bonded to each other.
The third substrate and the fourth substrate may be bonded to each other by a method of melting and connecting the electrodes and the connecting electrodes by heat treatment, etc. The heat treatment is usually performed at 400° C. for about 4 hours.

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

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

FIG. 1 is a schematic diagram showing an example of a laminate A of the present invention. FIG. 2 is a schematic diagram showing an example of a laminate B of the present invention.

The following examples further illustrate aspects of the present invention, but the present invention is not limited to these examples.

(1) Production of silsesquioxane (resin A) 65.4 g of phenyltrimethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd., molecular weight 198.29), 8.8 g of sodium hydroxide, 6.6 g of water, and 263 mL of 2-propanol were added to a reaction vessel equipped with a reflux condenser, a thermometer, and a dropping funnel. Heating was started with stirring under a nitrogen stream. Stirring was continued for 6 hours from the start of reflux, and then the mixture was allowed to stand overnight at room temperature. The reaction mixture was then transferred to a filter, pressurized with nitrogen gas, and filtered. The obtained solid was washed once with 2-propyl alcohol, filtered, and then dried under reduced pressure at 80°C to obtain 33.0 g of a colorless solid (DD-ONa).

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

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

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

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

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

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

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

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

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

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

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

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

(Evaluation of surface roughness)
The surface of the inorganic layer of the obtained laminate was observed with a laser microscope to measure the surface roughness of the laminate (inorganic layer). Specifically, a laser microscope (OLS4100, manufactured by Olympus Corporation) was used to observe the surface at 20 times magnification in an observation range of 643 μm square, and the surface roughness Sa value was calculated.

(Evaluation of Wrinkles in Inorganic Layer)
The inorganic layer of the obtained laminate was visually observed, and wrinkles in the inorganic layer were evaluated as follows: "O" if no wrinkles occurred over the entire surface, "△" if there was a mixture of wrinkle-free and wrinkled areas within the wafer surface, and "X" if wrinkles occurred over the entire surface.

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

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

Claims (17)

A curable resin composition containing silsesquioxane, a solvent, and silica filler as an inorganic filler, in which the solvent is dried at 125°C for 10 minutes, and the cured product is thermally cured by heat treatment at 300°C for 1 hour, and the cured product has an elastic modulus at 300°C of 0.2 MPa or more. The curable resin composition according to claim 1, in which the solvent is dried at 125°C for 10 minutes, and the cured product is heat-cured by heat treatment at 300°C for 1 hour, and the coefficient of linear expansion (CTE) in the range of -40°C to 100°C is 500 ppm/°C or less. The curable resin composition according to claim 1 or 2, wherein the silsesquioxane has structures represented by the following structural formulas (A) and (B) in one molecule.

In structural formulae (A) and (B), R ^A and R ^B each independently represent an aliphatic group, an aromatic group, or hydrogen, and j and k each represent an integer of 1 or more. The curable resin composition according to any one of claims 1 to 3, wherein the silsesquioxane has a structure represented by the following structural formula (1):

In the structural formula (1), R ⁰ , R ¹ and R ² each independently represent a linear, branched or cyclic aliphatic group, an aromatic group or hydrogen. The aliphatic group and the aromatic group may or may not have a substituent. m and n each represent an integer of 1 or more. The curable resin composition according to any one of claims 1 to 4, wherein the content of the silica filler is 15 parts by weight or more and 40 parts by weight or less per 100 parts by weight of the silsesquioxane. The curable resin composition according to any one of claims 1 to 5, wherein the solvent has a boiling point of 130°C or higher and 250°C or lower. The curable resin composition according to any one of claims 1 to 6, which is used by laminating an inorganic layer on a heat-cured product. A cured film obtained by thermally curing the curable resin composition according to any one of claims 1 to 6. A laminate comprising an organic layer formed of the cured film according to claim 8 on a first substrate, and an inorganic layer laminated on the organic layer,
The first substrate has a first surface having a plurality of chips and a second surface opposite thereto, and the organic layer and the inorganic layer are disposed on the first surface side of the first substrate. The laminate according to claim 9, in which a support substrate is laminated on the inorganic layer. The laminate according to claim 9 or 10, further comprising a second substrate on the second surface of the first substrate, the first substrate and the second substrate being electrically connected. A laminate having an organic layer and an inorganic layer, each of which is made of the cured film according to claim 8, between a third substrate having an electrode and a fourth substrate having an electrode,
A laminate in which the electrode of the third substrate and the electrode of the fourth substrate are electrically connected via a through hole penetrating the organic layer and the inorganic layer. The laminate according to claim 12, having a barrier metal layer on the surface of the through hole. An imaging device having a laminate according to any one of claims 9 to 13. A semiconductor device having a laminate according to any one of claims 9 to 13. A step of applying the curable resin composition according to any one of claims 1 to 6 onto a first surface of a first substrate having a first surface having a plurality of chips and a second surface opposite to the first surface, and then drying the composition with a solvent and thermally curing the composition to form an organic layer;
A method for producing a laminate, comprising the step of forming an inorganic layer on the organic layer. A step of applying the curable resin composition according to any one of claims 1 to 6 onto a surface of a third substrate having an electrode and a fourth substrate having an electrode, and then drying the composition with a solvent and thermally curing the composition to form an organic layer;
forming an inorganic layer on the organic layer;
forming through holes in each of the organic layer and the inorganic layer;
filling each of the through holes with a conductive material;
a step of polishing the surfaces of the third substrate having the electrode and the fourth substrate having the electrode, the surfaces being filled with the conductive material, to form bonding electrodes;
A method for manufacturing a laminate, comprising a step of bonding a third substrate having the electrode and a fourth substrate having the electrode together so that the bonding electrodes of the third substrate and the fourth substrate are bonded to each other.

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