TW202328296A - Semiconductor device and method of manufacturing the same - Google Patents

Abstract

The subject of the present invention is to provide a semiconductor device having an excellent adhesion between a sealing material and an interlayer insulating film in a rewiring layer, and a manufacturing method thereof. The semiconductor device (1) of the present invention comprises: a semiconductor chip (2); a sealing material (3) covering the semiconductor chip; and a rewiring layer (4) having an area larger than the semiconductor chip in a top view, wherein i-ray transmittance of the interlayer insulating film (6) of the rewiring layer is 80% or less. According to the present invention, provided are the semiconductor device having an excellent adhesion between the sealing material and the interlayer insulating film in the rewiring layer, and the manufacturing method thereof.

Description

Semiconductor device, and manufacturing method thereof

The present invention relates to a semiconductor device and a manufacturing method thereof.

There are various methods of semiconductor packaging methods for semiconductor devices. As a semiconductor packaging method, for example, there is a packaging method in which an element sealing material is formed by covering a semiconductor chip with a sealing material (molding resin), and then a rewiring layer electrically connected to the semiconductor chip is formed. Among the semiconductor packaging methods, in recent years, the fan-out (Fan-Out) semiconductor packaging method has become the mainstream.

In a fan-out semiconductor package, a semiconductor chip is covered with a sealing material to form a chip sealing body whose chip size is larger than that of the semiconductor chip. Furthermore, a rewiring layer is formed up to the region of the semiconductor wafer and the sealing material. The redistribution layer is formed with a relatively thin film thickness. Also, the rewiring layer can be formed up to the area of the sealing material, so the number of external connection terminals can be increased.

For example, the following patent document 1 is known as a fan-out type semiconductor device. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2011-129767

[Problem to be solved by the invention]

In fan-out semiconductor devices, high adhesion between the interlayer insulating film and the sealing material in the rewiring layer is required. However, the adhesion between the interlayer insulating film and the sealing material in the rewiring layer of the conventional fan-out semiconductor device is not sufficient.

The present invention was made in view of this point, and an object of the present invention is to provide a semiconductor device having excellent adhesion between an interlayer insulating film in a rewiring layer and a sealing material, and a method for manufacturing the same. [Technical means to solve the problem]

The semiconductor device of the present invention is characterized in that it comprises: a semiconductor chip, a sealing material covering the above-mentioned semiconductor chip, and a rewiring layer having a larger area in plan view than the above-mentioned semiconductor chip, and the i-ray transmittance of the interlayer insulating film of the above-mentioned rewiring layer is determined by a thickness of 10 The μm conversion is less than 80%.

In the present invention, it is preferable that the sealing material is in direct contact with the interlayer insulating film.

In the present invention, preferably, the sealing material includes epoxy resin.

In the present invention, it is preferable that the interlayer insulating film includes at least one selected from polyimide, polybenzoxazole, and a polymer having a phenolic hydroxyl group.

In the present invention, it is preferable that the interlayer insulating film includes polyimide having a structure of the following general formula (1). [chemical 1] (In the general formula (1), ^X1 is a tetravalent organic group, ^Y1 is a divalent organic group, and m is an integer of 1 or more)

In the present invention, it is preferable that ^X1 in the above general formula (1) is a tetravalent organic group containing an aromatic ring, and ^Y1 in the above general formula (1) is a divalent organic group containing an aromatic ring.

In the present invention, it is preferable that X ¹ in the above general formula (1) includes at least one structure represented by the following general formulas (2) to (4). [Chem 2] [Chem 3] [chemical 4] (In the general formula (4), R ₉ is an oxygen atom, a sulfur atom, or a divalent organic group)

In the present invention, it is preferable that X ¹ in the above general formula (1) includes a structure represented by the following general formula (5). [chemical 5]

In the present invention, Y ¹ in the above general formula (1) preferably includes at least one structure represented by the following general formulas (6) to (8). [chemical 6] (R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are a hydrogen atom, a monovalent aliphatic group with 1 to 5 carbons or a hydroxyl group, which may be the same or different) [Chemical 7] (R ₁₄ to R ₂₁ are a hydrogen atom, a halogen atom, a monovalent organic group with 1 to 5 carbons, or a hydroxyl group, which may be different or the same) [Chem. 8] (R ₂₂ is a divalent organic group, R ₂₃ to R ₃₀ are hydrogen atoms, halogen atoms, monovalent aliphatic groups with 1 to 5 carbons or hydroxyl groups, which may be the same or different)

In the present invention, Y ¹ in the above general formula (1) preferably includes a structure represented by the following general formula (9). [chemical 9]

In the present invention, it is preferable that the above-mentioned polybenzoxazole includes a polybenzoxazole having a structure of the following general formula (10). [chemical 10] (In general formula (10), U and V are divalent organic groups)

In the present invention, U in the general formula (10) is preferably a divalent organic group having 1 to 30 carbon atoms.

In the present invention, U in the above general formula (10) is preferably a chain alkylene group having 1 to 8 carbon atoms and part or all of hydrogen atoms substituted with fluorine atoms.

In the present invention, V in the above general formula (10) is preferably a divalent organic group containing an aromatic group.

In the present invention, it is preferable that V in the above general formula (10) includes at least one structure represented by the following general formulas (6) to (8). [chemical 11] (R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are a hydrogen atom and a monovalent aliphatic group with 1 to 5 carbon atoms, which may be the same or different) [Chem. 12] (R ₁₄ to R ₂₁ are a hydrogen atom, a halogen atom, or a monovalent organic group with 1 to 5 carbon atoms, which may be different or the same) [Chem. 13] (R ₂₂ is a divalent organic group, and R ₂₃ to R ₃₀ are hydrogen atoms, halogen atoms, and monovalent aliphatic groups with 1 to 5 carbon atoms, which may be the same or different)

In the present invention, V of the general formula (10) above preferably includes a structure represented by the following general formula (9). [chemical 14]

In the present invention, V in the general formula (10) is preferably a divalent organic group having 1 to 40 carbon atoms.

In the present invention, V in the general formula (10) is preferably a divalent chain aliphatic group having 1 to 20 carbon atoms.

In the present invention, it is preferable that the above-mentioned polymer having a phenolic hydroxyl group contains a novolak-type phenolic resin.

In the present invention, it is preferable that the above-mentioned polymer having a phenolic hydroxyl group includes a phenol resin not having an unsaturated hydrocarbon group and a modified phenol resin having an unsaturated hydrocarbon group.

In the present invention, it is preferable that when the redistribution layer is observed in section, the redistribution layer includes: a first interlayer insulating film layer; a second interlayer insulating film layer; The insulating film layer is a different layer from the second interlayer insulating film layer, and is provided between the first interlayer insulating film layer and the second interlayer insulating film layer.

In the present invention, preferably, the first interlayer insulating film layer is in contact with the sealing material, and the i-ray transmittance of the first interlayer insulating film layer is 80% or less in terms of a thickness of 10 μm.

In the present invention, it is preferable that the composition of the second interlayer insulating film layer is different from that of the first interlayer insulating film layer.

In the present invention, it is preferable that the i-ray transmittance of the second interlayer insulating film layer is different from the i-ray transmittance of the first interlayer insulating film layer.

In the present invention, it is preferable that the above-mentioned semiconductor device is a fan-out WLCS semiconductor device.

In the present invention, the i-ray transmittance of the interlayer insulating film of the rewiring layer is preferably 70% or less in terms of a thickness of 10 μm.

In the present invention, the i-ray transmittance of the interlayer insulating film of the rewiring layer is preferably 60% or less in terms of a thickness of 10 μm.

In the present invention, the i-ray transmittance of the interlayer insulating film of the rewiring layer is preferably 50% or less in terms of a thickness of 10 μm.

In the present invention, the i-ray transmittance of the interlayer insulating film of the rewiring layer is preferably 40% or less in terms of a thickness of 10 μm.

In the present invention, the i-ray transmittance of the interlayer insulating film of the rewiring layer is preferably 30% or less in terms of a thickness of 10 μm.

In the present invention, it is preferable that the i-ray transmittance of the interlayer insulating film of the rewiring layer is 5% or more in terms of a thickness of 10 μm.

In the present invention, the i-ray transmittance of the interlayer insulating film of the rewiring layer may be 10% or more in terms of a thickness of 10 μm.

In the present invention, the i-ray transmittance of the interlayer insulating film of the rewiring layer may be 20% or more in terms of a thickness of 10 μm.

The method for manufacturing a semiconductor device in the present invention is characterized in that it includes: a step of covering the semiconductor wafer with a sealing material, and a step of forming a rewiring layer having an area larger than the semiconductor wafer in plan view and including an interlayer insulating film, and the interlayer insulating film The i-ray transmittance is less than 80% based on the conversion of a thickness of 10 μm.

In the present invention, it is preferable to form an interlayer insulating film including forming the above-mentioned interlayer insulating film using a photosensitive resin composition that can form at least one compound of polyimide, polybenzoxazole, or a polymer having a phenolic hydroxyl group. step.

In the present invention, it is preferable that the forming step of the above-mentioned interlayer insulating film includes forming the above-mentioned photosensitive resin composition with additives adjusted so that the i-ray transmittance of the above-mentioned interlayer insulating film becomes 80% or less in conversion of a thickness of 10 μm. interlayer insulating film step.

One aspect of the semiconductor device of this embodiment is characterized by comprising: a semiconductor wafer, a sealing material covering the semiconductor wafer, and a rewiring layer having a larger area in plan view than the semiconductor wafer, and 5% of the interlayer insulating film of the rewiring layer The weight reduction temperature is 300°C or lower.

In one aspect of the semiconductor device of the present invention, it is preferable that the sealing material is in direct contact with the interlayer insulating film.

In one aspect of the semiconductor device of the present invention, it is preferable that the sealing material includes an epoxy resin.

In one aspect of the semiconductor device of the present invention, it is preferable that the interlayer insulating film includes at least one selected from polyimide, polybenzoxazole, and a polymer having a phenolic hydroxyl group.

In one aspect of the semiconductor device of the present invention, it is preferable that the interlayer insulating film includes polyimide having a structure of the following general formula (1).

[chemical 15] (In the general formula (1), ^X1 is a tetravalent organic group, ^Y1 is a divalent organic group, and m is an integer of 1 or more)

In one aspect of the semiconductor device of the present invention, it is preferable that X in the above general formula ( ¹ ) is a tetravalent organic group containing an aromatic ring, and Y in the above general formula ( ¹ ) is a tetravalent organic group containing an aromatic ring. The divalent organic group of the ring.

In one aspect of the semiconductor device of the present invention, it is preferable that X ¹ in the above general formula (1) includes at least one structure represented by the following general formulas (2) to (4).

[chemical 16] [chemical 17] [chemical 18] (In the general formula (4), R ₉ is an oxygen atom, a sulfur atom, or a divalent organic group)

In one aspect of the semiconductor device of the present invention, it is preferable that X ¹ in the above general formula (1) includes a structure represented by the following general formula (5).

[chemical 19]

In one aspect of the semiconductor device of the present invention, Y ¹ in the above general formula (1) preferably includes at least one structure represented by the following general formulas (6) to (8).

[chemical 20] (R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are a hydrogen atom, a monovalent aliphatic group with 1 to 5 carbons or a hydroxyl group, which may be the same or different) [Chem. 21] (R ₁₄ to R ₂₁ are a hydrogen atom, a halogen atom, a monovalent organic group with 1 to 5 carbons, or a hydroxyl group, which may be different from each other or the same) [Chemical 22] (R ₂₂ is a divalent group, R ₂₃ to R ₃₀ are a hydrogen atom, a halogen atom, a monovalent aliphatic group with 1 to 5 carbons or a hydroxyl group, which may be the same or different)

In one aspect of the semiconductor device of the present invention, Y ¹ in the above-mentioned general formula (1) preferably includes a structure represented by the following general formula (9).

[chem 23]

In one aspect of the semiconductor device of the present invention, it is preferable that the interlayer insulating film includes polybenzoxazole having a structure of the following general formula (10).

[chem 24] (In general formula (10), U and V are divalent organic groups)

In one aspect of the semiconductor device of the present invention, U in the general formula (10) is preferably a divalent organic group having 1 to 30 carbon atoms.

In one aspect of the semiconductor device of the present invention, U in the above general formula (10) is preferably a chain alkylene group having 1 to 8 carbon atoms and a part or all of the hydrogen atoms are substituted with fluorine atoms.

In one aspect of the semiconductor device of the present invention, it is preferable that V in the above general formula (10) is a divalent organic group containing an aromatic group.

In one aspect of the semiconductor device of the present invention, it is preferable that V in the above general formula (10) includes at least one structure represented by the following general formulas (6) to (8).

[chem 25] (R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are a hydrogen atom and a monovalent aliphatic group with 1 to 5 carbon atoms, which may be the same or different) [Chemical 26] (R ₁₄ to R ₂₁ are a hydrogen atom, a halogen atom, or a monovalent organic group with 1 to 5 carbon atoms, which may be different or the same) [Chemical 27] (R ₂₂ is a divalent group, and R ₂₃ to R ₃₀ are hydrogen atoms, halogen atoms, and monovalent aliphatic groups with 1 to 5 carbon atoms, which may be the same or different)

In one aspect of the semiconductor device of the present invention, it is preferable that V in the above general formula (10) includes a structure represented by the following general formula (9).

[chem 28]

In one aspect of the semiconductor device of the present invention, V in the general formula (10) is preferably a divalent organic group having 1 to 40 carbon atoms.

In one aspect of the semiconductor device of the present invention, V in the general formula (10) is preferably a divalent chain aliphatic group having 1 to 20 carbon atoms.

In one aspect of the semiconductor device of the present invention, it is preferable that the polymer having a phenolic hydroxyl group includes a novolak-type phenolic resin.

In one aspect of the semiconductor device of the present invention, it is preferable that the polymer having a phenolic hydroxyl group includes a phenol resin not having an unsaturated hydrocarbon group and a modified phenol resin having an unsaturated hydrocarbon group.

In one aspect of the semiconductor device of the present invention, preferably, when the rewiring layer is observed in section, the rewiring layer includes: a first interlayer insulating film layer; a second interlayer insulating film layer; and an intermediate layer, It is a layer different from the first interlayer insulating film layer and the second interlayer insulating film layer, and is provided between the first interlayer insulating film layer and the second interlayer insulating film layer.

In one aspect of the semiconductor device of the present invention, preferably, the first interlayer insulating film layer is in contact with the sealing material, and the 5% weight loss temperature of the first interlayer insulating film layer is 300° C. or lower.

In one aspect of the semiconductor device of the present invention, preferably, the composition of the second interlayer insulating film layer is different from that of the first interlayer insulating film layer.

In one aspect of the semiconductor device of the present invention, it is preferable that the 5% weight loss temperature of the second interlayer insulating film layer is different from the 5% weight loss temperature of the first interlayer insulating film layer.

In one aspect of the semiconductor device of the present invention, it is preferable that the semiconductor device is a fan-out wafer-level chip size package semiconductor device.

In one aspect of the semiconductor device of the present invention, it is preferable that the 5% weight reduction temperature of the interlayer insulating film of the rewiring layer is 280° C. or lower.

In one aspect of the semiconductor device of the present invention, it is preferable that the 5% weight reduction temperature of the interlayer insulating film of the rewiring layer is 260° C. or lower.

In one aspect of the semiconductor device of the present invention, it is preferable that the 5% weight reduction temperature of the interlayer insulating film of the rewiring layer is 240° C. or lower.

In one aspect of the semiconductor device of the present invention, it is preferable that the 5% weight reduction temperature of the interlayer insulating film of the rewiring layer is 220° C. or lower.

In one aspect of the semiconductor device of the present invention, it is preferable that the 5% weight loss temperature of the interlayer insulating film of the rewiring layer is 200° C. or lower.

In one aspect of the semiconductor device of the present invention, it is preferable that the 5% weight reduction temperature of the interlayer insulating film of the rewiring layer is 80° C. or higher.

In one aspect of the semiconductor device of the present invention, it is preferable that the 5% weight reduction temperature of the interlayer insulating film of the rewiring layer is 100° C. or lower.

In one aspect of the semiconductor device of the present invention, it is preferable that the 5% weight loss temperature of the interlayer insulating film of the rewiring layer is 150° C. or lower.

In one aspect of the method for manufacturing a semiconductor device according to the present invention, it is characterized by including the step of covering the semiconductor wafer with a sealing material, and the step of forming a rewiring layer including an interlayer insulating film having an area larger than that of the semiconductor wafer in plan view , and the 5% weight loss temperature of the above-mentioned interlayer insulating film is 300°C or lower.

In one aspect of the method for manufacturing a semiconductor device of the present invention, it is preferable to include a photosensitive resin composition using at least one compound that can form polyimide, polybenzoxazole, or a polymer having a phenolic hydroxyl group An interlayer insulating film forming step of forming the above-mentioned interlayer insulating film.

In one aspect of the method of manufacturing a semiconductor device according to the present invention, it is preferable that the step of forming the interlayer insulating film includes utilizing the above-mentioned photosensitivity adjusted by additives so that the 5% weight reduction temperature of the interlayer insulating film becomes 300°C or lower. Resin composition The step of forming the above-mentioned interlayer insulating film.

An aspect of the semiconductor device of the present invention is characterized by comprising: a semiconductor wafer, a sealing material covering the semiconductor wafer, and a redistribution layer having a larger area in plan view than the semiconductor wafer, and the wavelength of the interlayer insulating film of the redistribution layer is 1310 nm The absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index is less than 0.0150.

In one aspect of the semiconductor device of the present invention, it is preferable that the sealing material is in direct contact with the interlayer insulating film.

In one aspect of the semiconductor device of the present invention, it is preferable that the sealing material includes an epoxy resin.

In one aspect of the semiconductor device of the present invention, it is preferable that the interlayer insulating film includes at least one selected from polyimide, polybenzoxazole, and a polymer having a phenolic hydroxyl group.

In one aspect of the semiconductor device of the present invention, it is preferable that the interlayer insulating film includes polyimide having a structure of the following general formula (1).

[chem 29] (In the general formula (1), ^X1 is a tetravalent organic group, ^Y1 is a divalent organic group, and m is an integer of 1 or more)

In one aspect of the semiconductor device of the present invention, it is preferable that X in the above general formula ( ¹ ) is a tetravalent organic group containing an aromatic ring, and Y in the above general formula ( ¹ ) is a tetravalent organic group containing an aromatic ring. The divalent organic group of the ring.

In one aspect of the semiconductor device of the present invention, it is preferable that X ¹ in the above general formula (1) includes at least one structure represented by the following general formulas (2) to (4).

[chem 30] [chem 31] [chem 32] (In the general formula (4), R ₉ is an oxygen atom, a sulfur atom, or a divalent organic group)

In one aspect of the semiconductor device of the present invention, it is preferable that X ¹ in the above general formula (1) includes a structure represented by the following general formula (5).

[chem 33]

In one aspect of the semiconductor device of the present invention, Y ¹ in the above general formula (1) preferably includes at least one structure represented by the following general formulas (6) to (8).

[chem 34] (R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are a hydrogen atom, a monovalent aliphatic group with 1 to 5 carbons or a hydroxyl group, which may be the same or different) [Chemical 35] (R ₁₄ to R ₂₁ are a hydrogen atom, a halogen atom, a monovalent organic group with 1 to 5 carbons, or a hydroxyl group, which may be different or the same) [Chemical 36] (R ₂₂ is a divalent group, R ₂₃ to R ₃₀ are a hydrogen atom, a halogen atom, a monovalent aliphatic group with 1 to 5 carbons or a hydroxyl group, which may be the same or different)

In one aspect of the semiconductor device of the present invention, Y ¹ in the above-mentioned general formula (1) preferably includes a structure represented by the following general formula (9).

[chem 37]

In one aspect of the semiconductor device of the present invention, it is preferable that the polybenzoxazole includes a polybenzoxazole having a structure of the following general formula (10).

[chem 38] (In general formula (10), U and V are divalent organic groups)

In one aspect of the semiconductor device of the present invention, U in the general formula (10) is preferably a divalent organic group having 1 to 30 carbon atoms.

In one aspect of the semiconductor device of the present invention, U in the above general formula (10) is preferably a chain alkylene group having 1 to 8 carbon atoms and a part or all of the hydrogen atoms are substituted with fluorine atoms.

In one aspect of the semiconductor device of the present invention, it is preferable that V in the above general formula (10) is a divalent organic group containing an aromatic group.

In one aspect of the semiconductor device of the present invention, it is preferable that V in the above general formula (10) includes at least one structure represented by the following general formulas (6) to (8).

[chem 39] (R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are a hydrogen atom and a monovalent aliphatic group with 1 to 5 carbon atoms, which may be the same or different) [Chemical 40] (R ₁₄ to R ₂₁ are a hydrogen atom, a halogen atom, or a monovalent organic group with 1 to 5 carbon atoms, which may be different or the same) [Chem. 41] (R ₂₂ is a divalent group, and R ₂₃ to R ₃₀ are hydrogen atoms, halogen atoms, and monovalent aliphatic groups with 1 to 5 carbon atoms, which may be the same or different)

In one aspect of the semiconductor device of the present invention, it is preferable that V in the above general formula (10) includes a structure represented by the following general formula (9).

[chem 42]

In one aspect of the semiconductor device of the present invention, V in the general formula (10) is preferably a divalent organic group having 1 to 40 carbon atoms.

In one aspect of the semiconductor device of the present invention, V in the general formula (10) is preferably a divalent chain aliphatic group having 1 to 20 carbon atoms.

In one aspect of the semiconductor device of the present invention, it is preferable that the polymer having a phenolic hydroxyl group includes a novolak-type phenolic resin.

In one aspect of the semiconductor device of the present invention, it is preferable that the polymer having a phenolic hydroxyl group includes a phenol resin not having an unsaturated hydrocarbon group and a modified phenol resin having an unsaturated hydrocarbon group.

In one aspect of the semiconductor device of the present invention, it is preferable that the redistribution layer includes a first interlayer insulating film layer; a second interlayer insulating film layer; and an intermediate layer when the redistribution layer is observed in section. It is a layer different from the first interlayer insulating film layer and the second interlayer insulating film layer, and is provided between the first interlayer insulating film layer and the second interlayer insulating film layer.

In one aspect of the semiconductor device of the present invention, it is preferable that the first interlayer insulating film is in contact with the sealing material, and the absolute difference between the in-plane refractive index and the out-of-plane refractive index of the first interlayer insulating film is The value did not reach 0.0150.

In one aspect of the semiconductor device of the present invention, preferably, the composition of the second interlayer insulating film layer is different from that of the first interlayer insulating film layer.

In one aspect of the semiconductor device of the present invention, it is preferable that the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the above-mentioned second interlayer insulating film layer and the in-plane refractive index of the above-mentioned first interlayer insulating film layer It is different from the absolute value of the difference in out-of-plane refractive index.

In one aspect of the semiconductor device of the present invention, it is preferable that the semiconductor device is a fan-out wafer-level chip size package semiconductor device.

In one aspect of the semiconductor device of the present invention, the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the rewiring layer is preferably 0.0145 or less.

In one aspect of the semiconductor device of the present invention, the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the rewiring layer is preferably 0.0140 or less.

In one aspect of the semiconductor device of the present invention, the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the rewiring layer is preferably 0.0135 or less.

In one aspect of the semiconductor device of the present invention, the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the rewiring layer is preferably 0.0130 or less.

In one aspect of the semiconductor device of the present invention, it is preferable that the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the redistribution layer is 0.0120 or less.

In one aspect of the semiconductor device of the present invention, it is preferable that the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the rewiring layer is 0.0005 or more.

In one aspect of the semiconductor device of the present invention, it is preferable that the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the rewiring layer is 0.0010 or more.

In one aspect of the semiconductor device of the present invention, it is preferable that the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the rewiring layer is 0.0015 or more.

An aspect of the method of manufacturing a semiconductor device of the present invention is characterized by including: a step of covering the semiconductor wafer with a sealing material; and a step of forming a rewiring layer having an area larger than the semiconductor wafer in plan view and including an interlayer insulating film, and The absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film is less than 0.0150.

In one aspect of the method for manufacturing a semiconductor device of the present invention, it is preferable to include a photosensitive resin composition using at least one compound that can form polyimide, polybenzoxazole, or a polymer having a phenolic hydroxyl group An interlayer insulating film forming step of forming the above-mentioned interlayer insulating film.

In one aspect of the method of manufacturing a semiconductor device according to the present invention, it is preferable that the step of forming the interlayer insulating film includes utilizing the method such that the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the above-mentioned interlayer insulating film becomes less than 0.0150 The step of forming the above-mentioned interlayer insulating film with the above-mentioned photosensitive resin composition adjusted by additives. [Effect of Invention]

According to the present invention, it is possible to provide a semiconductor device having excellent adhesion between an interlayer insulating film in a rewiring layer and a sealing material, and a method for manufacturing the same.

Hereinafter, one embodiment of the semiconductor device of the present invention (hereinafter simply referred to as "embodiment") will be described in detail with reference to the drawings. In addition, this invention is not limited to the following embodiment, Various changes can be implemented within the range of the summary.

(semiconductor device) As shown in FIG. 1 , a semiconductor device (semiconductor IC) 1 includes: a semiconductor chip 2 , a sealing material (molding resin) 3 covering the semiconductor chip 2 , and a rewiring layer 4 in close contact with the semiconductor chip 2 and the sealing material 3 .

As shown in FIG. 1 , the sealing material 3 covers the surface of the semiconductor wafer 2 and is formed in an area larger than that of the semiconductor wafer 2 in plan view (observed along arrow A).

The rewiring layer 4 has a plurality of wirings 5 electrically connected to a plurality of terminals 2 a provided on the semiconductor chip 2 , and an interlayer insulating film 6 between the buried wirings 5 . The plurality of terminals 2 a provided on the semiconductor chip 2 are electrically connected to the wiring 5 in the rewiring layer 4 . One end of the wiring 5 is connected to the terminal 2 a, and the other end is connected to the external connection terminal 7 . The entire surface of the wiring 5 between the terminal 2 a and the external connection terminal 7 is covered with an interlayer insulating film 6 .

As shown in FIG. 1 , the rewiring layer 4 is formed larger than the semiconductor wafer 2 in plan view (observed along the arrow A). The semiconductor device 1 shown in FIG. 1 is a fan-out (Fan-Out) wafer-level chip-scale package (WLCSP) semiconductor device. In a fan-out semiconductor device, the interlayer insulating film 6 in the rewiring layer 4 is in close contact not only with the semiconductor chip 2 but also with the sealing material 3 . The semiconductor wafer 2 includes semiconductors such as silicon, and has circuits formed therein.

(redistribution layer) The redistribution layer 4 mainly includes wiring 5 and an interlayer insulating film 6 covering the periphery of the wiring 5 . From the viewpoint of preventing unintended conduction with the wiring 5, the interlayer insulating film 6 is preferably a member with high insulating properties.

Here, the "rewiring layer 4" in this embodiment is a thin film layer having the wiring 5 and the interlayer insulating film 6 as described above, and does not contain an interposer or a printed wiring board. Figure 4 is a comparison diagram of flip-chip BGA and fan-out (Fan-Out) WLCSP. The semiconductor device (semiconductor IC) 1 (refer to FIG. 1 ) uses the rewiring layer 4 , and therefore, as shown in FIG. 4 , is thinner than a semiconductor device using an interposer such as a flip-chip BGA.

In this embodiment, the film thickness of the rewiring layer 4 can be set to about 3 to 30 μm. The film thickness of the rewiring layer 4 may be 1 μm or more, may be 5 μm or more, or may be 10 μm or more. In addition, the film thickness of the rewiring layer 4 may be 40 μm or less, may be 30 μm or less, or may be 20 μm or less.

When the semiconductor device 1 is viewed from above (observed along the arrow A), it becomes as shown in FIG. 2 below. FIG. 2 is a schematic plan view of the semiconductor device of the present embodiment. Furthermore, the sealing material 3 is omitted.

The semiconductor device 1 shown in FIG. 2 is configured such that the area S1 of the rewiring layer 4 is larger than the area S2 of the semiconductor chip 2 . The area S1 of the rewiring layer 4 is not particularly limited. From the viewpoint of increasing the number of external connection terminals, the area S1 of the rewiring layer 4 is preferably more than 1.05 times, preferably 1.1 times, the area S2 of the semiconductor chip 2. Above, more preferably at least 1.2 times, especially preferably at least 1.3 times. The upper limit is not particularly limited, and the area S1 of the rewiring layer 4 may be less than 50 times, less than 25 times, less than 10 times, or less than 5 times the area S2 of the semiconductor chip 2 . Furthermore, in FIG. 2 , the area of the portion of the redistribution layer 4 covering the semiconductor chip 2 is also included in the area S1 of the redistribution layer 4 .

Also, the semiconductor chip 2 and the rewiring layer 4 may have the same or different shapes. In FIG. 2 , the semiconductor chip 2 and the rewiring layer 4 have shapes similar to rectangles, but shapes other than rectangles may also be used.

The rewiring layer 4 may be one layer, or may be a multilayer of two or more layers. The rewiring layer 4 includes the interlayer insulating film 6 between the wiring 5 and the buried wiring 5 , but the rewiring layer 4 may include a layer composed of only the interlayer insulating film 6 or a layer composed of only the wiring 5 .

The wiring 5 is not particularly limited as long as it is a highly conductive member, but copper is generally used.

(Sealing material) The material of the sealing material 3 is not particularly limited, but epoxy resin is preferable from the viewpoint of heat resistance and adhesion with the interlayer insulating film.

As shown in FIG. 1 , the sealing material 3 is preferably in direct contact with the semiconductor chip 2 and the redistribution layer 4 . Thereby, the sealing performance from the surface of the semiconductor wafer 2 to the surface of the rewiring layer 4 can be effectively improved.

The sealing material 3 may be a single layer or a plurality of laminated layers. When the sealing material 3 has a laminated structure, it may be a laminated structure of the same material, or may be a laminated structure of different materials.

(Interlayer insulating film) In the first aspect of this embodiment, the transmittance of i-rays (wavelength: 365 nm) of the interlayer insulating film 6 is 80% or less. In addition, the transmittance is a value when the film thickness of the interlayer insulating film 6 is converted into 10 micrometers. Also, when the film thickness is not 10 microns (set as y microns), the transmittance converted to 10 microns is calculated by using {(transmittance/100) ^10/y }×100 for the measured transmittance . The reason why the adhesion between the interlayer insulating film 6 and the sealing material 3 in the rewiring layer 4 is excellent when the transmittance of i-rays (wavelength: 365 nm) of the interlayer insulating film 6 is 80% or less is not clear, but the present inventors et al speculated as follows.

In the manufacturing process of the fan-out semiconductor device, in order to form the rewiring layer 4, the photosensitive resin composition is coated on the wafer sealing body including the semiconductor wafer 2 and the sealing material 3. Next, the photosensitive resin composition is exposed with light containing i-rays. Thereafter, the photosensitive resin composition is developed and cured to selectively form a part having a cured product of the photosensitive resin composition and a part not having a cured product of the photosensitive resin composition. The cured product of the photosensitive resin composition becomes the interlayer insulating film 6 . Moreover, the wiring 5 is formed in the part which does not have the hardened|cured material of the photosensitive resin composition. Usually, the rewiring layer 4 is multilayered in many cases. That is, the photosensitive resin composition is further coated on the interlayer insulating film 6 and the wiring 5, and the rewiring layer is further formed on the rewiring layer through exposure, development, and curing steps.

When exposing to form the first redistribution layer or exposing to form the second redistribution layer, if the transmittance of the i-ray (wavelength: 365 nm) of the interlayer insulating film is high, it is due to i-rays cause the sealing material 3 to decompose and deteriorate. Therefore, the adhesion between the interlayer insulating film and the sealing material 3 is lowered. In particular, epoxy resins are easily decomposed and deteriorated by i-rays. Therefore, when an epoxy resin is used for the sealing material 3 , the epoxy resin is decomposed and deteriorated by i-rays, and the adhesion between the interlayer insulating film and the sealing material 3 is reduced.

The interlayer insulating film 6 of the present embodiment has an i-ray transmittance as low as 80% or less for i-rays (wavelength: 365 nm). Therefore, it is presumed that in this embodiment, the decomposition and deterioration of the sealing material 3 by i-rays are less likely to occur, and the adhesion between the interlayer insulating film 6 and the sealing material 3 can be improved. Furthermore, when using an interlayer insulating film having a high transmittance of i-rays (wavelength: 365 nm), the transmittance of i-rays (wavelength: 365 nm) can also be reduced by making the interlayer insulating film thick. However, there arises a disadvantage that the semiconductor device becomes thicker as a whole. The semiconductor device of this embodiment can reduce the transmittance of i-rays (wavelength: 365 nm) without making the entire semiconductor device thicker, and has excellent adhesion between the interlayer insulating film in the rewiring layer and the sealing material.

The transmittance of i-rays (wavelength: 365 nm) of the interlayer insulating film 6 is preferably 80% or less, more preferably 78% or less, from the viewpoint of the adhesion between the interlayer insulating film and the sealing material in the redistribution layer. , preferably less than 76%, preferably less than 74%, preferably less than 72%, preferably less than 70%, preferably less than 68%, preferably less than 66%, preferably less than 64%, Preferably less than 62%, preferably less than 60%, preferably less than 58%, preferably less than 56%, preferably less than 54%, preferably less than 52%, preferably less than 50%, more preferably Preferably less than 48%, preferably less than 46%, preferably less than 44%, preferably less than 42%, preferably less than 40%, preferably less than 38%, preferably less than 36%, more preferably It is less than 34%, preferably less than 32%, preferably less than 30%, preferably less than 28%, preferably less than 26%, preferably less than 24%, preferably less than 22%, preferably less than 22% 20% or less, preferably 18% or less, preferably 16% or less, preferably 14% or less, preferably 12% or less.

Furthermore, the transmittance of i-rays (wavelength: 365 nm) of the interlayer insulating film 6 is preferably 10% or less, preferably 9% or less, preferably 8% or less, preferably 7% or less, preferably 6% or less. % or less, preferably less than 5%, preferably less than 4%, preferably less than 3%, preferably less than 2%.

Also, the lower limit of the transmittance of i-rays (wavelength: 365 nm) of the interlayer insulating film 6 is not particularly limited, but from the viewpoint of making the pattern shape of the interlayer insulating film 6 good, it is preferably 0.1% or more, preferably More than 0.5%, preferably more than 1%, preferably more than 3%, preferably more than 5%, preferably more than 10%, preferably more than 15%, preferably more than 20%, preferably more than 25% or more, preferably 30% or more, preferably 35% or more, preferably 40% or more.

Also, the interlayer insulating film 6 in the rewiring layer 4 may be multilayered. That is, when the rewiring layer 4 is observed in section, the rewiring layer 4 may include a first interlayer insulating film layer; a second interlayer insulating film layer; The two interlayer insulating film layers are different layers, and are arranged between the first interlayer insulating film layer and the second interlayer insulating film layer. The so-called intermediate layer is, for example, wiring 5 .

The first interlayer insulating film layer and the second interlayer insulating film layer may have the same composition or different compositions. The first interlayer insulating film layer and the second interlayer insulating film layer may have the same i-ray transmittance, or may have different i-ray transmittances. The first interlayer insulating film layer and the second interlayer insulating film layer may have the same film thickness or different film thicknesses. It is preferable that the first interlayer insulating film layer and the second interlayer insulating film layer have different compositions, different i-ray transmittances, or different film thicknesses, since each interlayer insulating film layer can have different properties.

When the interlayer insulating film 6 is multi-layered, among the plurality of layers, at least one layer should have an i-ray transmittance of 80% or less, preferably the interlayer insulating film layer (first layer) in contact with the sealing material 3. The i-ray transmittance of the interlayer insulating film layer) is 80% or less. If the i-ray transmittance of the interlayer insulating film layer in contact with the sealing material 3 is 80% or less, the i-ray can be efficiently absorbed when forming the interlayer insulating film layer not in contact with the sealing material 3, and can be Prevent deterioration of sealing materials. The preferable i-ray transmittance range of each interlayer insulating film layer is the same as the preferable i-ray transmittance range of the interlayer insulating film 6 .

The second aspect of this embodiment is characterized in that the 5% weight loss temperature of the interlayer insulating film 6 is 300° C. or lower. Hereinafter, "5% weight reduction temperature" is abbreviated as "weight reduction temperature". When the weight reduction temperature is 300° C. or lower, the interlayer insulating film 6 and the sealing material 3 have excellent adhesion during high-temperature treatment. The reason for this is not certain, but the inventors of the present invention speculate as follows.

In the manufacturing process of the fan-out type semiconductor device 1 (see FIG. 1 ), in order to form the rewiring layer 4 , the photosensitive resin composition is coated on the wafer sealing body including the semiconductor wafer 2 and the sealing material 3 . Next, the photosensitive resin composition is exposed with light containing i-rays. Thereafter, the photosensitive resin composition is developed and cured to selectively form a part having a cured product of the photosensitive resin composition and a part not having a cured product of the photosensitive resin composition. The cured product of the photosensitive resin composition becomes the interlayer insulating film 6 . Moreover, the wiring 5 is formed in the part which does not have the hardened|cured material of the photosensitive resin composition. Usually, the rewiring layer 4 is multilayered in many cases. That is, a photosensitive resin composition is further applied on the interlayer insulating film 6 and the wiring 5, and then exposed, developed, and cured.

However, the step of forming the interlayer insulating film 6 and the wiring 5 may include a reflow step depending on the manufacturing method, and if the sealing material 3 is heated for a long time, gas may be generated from the sealing material 3 . When the density of the interlayer insulating film 6 is high, that is, the weight loss temperature of the interlayer insulating film 6 is high, it is difficult for the gas generated from the sealing material 3 to escape to the outside. Therefore, gas accumulates at the interface between the sealing material 3 and the interlayer insulating film 6 , and the sealing material 3 and the interlayer insulating film 6 are easily peeled off. Epoxy resins in particular are prone to gas generation. Therefore, when an epoxy resin is used for the sealing material 3 , the reduction in the adhesion between the interlayer insulating film 6 and the sealing material 3 is promoted.

The weight loss temperature of the interlayer insulating film 6 of this embodiment is as low as 300°C or lower. Therefore, it is speculated that in this embodiment, the gas easily escapes from the interlayer insulating film, and even under the condition that the gas is easily generated from the sealing material 3, the peeling between the interlayer insulating film 6 and the sealing material 3 is less, and the adhesion during high temperature treatment is relatively small. Sex is higher.

The weight loss temperature of the interlayer insulating film 6 is preferably 300° C. or lower, more preferably 295° C. or lower, and more preferably 290° C. or lower, from the viewpoint of the adhesion between the interlayer insulating film 6 and the sealing material 3 after high-temperature treatment. , preferably below 285°C, preferably below 280°C, preferably below 275°C, preferably below 270°C, preferably below 260°C, preferably below 250°C, preferably below 240°C, Preferably it is below 230°C.

Also, the lower limit of the weight loss temperature of the interlayer insulating film 6 is not particularly limited, and may be 80°C or higher, may be 100°C or higher, may be 120°C or higher, or may be 150°C or higher.

Also, the interlayer insulating film 6 in the rewiring layer 4 may be multilayered. That is, when the rewiring layer 4 is observed in section, the rewiring layer 4 may include: a first interlayer insulating film layer; a second interlayer insulating film layer; The second interlayer insulating film layer is a different layer, and is arranged between the first interlayer insulating film layer and the second interlayer insulating film layer. The so-called intermediate layer is, for example, wiring 5 .

The first interlayer insulating film layer and the second interlayer insulating film layer may have the same composition or different compositions. The first interlayer insulating film layer and the second interlayer insulating film layer may have the same weight reduction temperature or different weight reduction temperatures. The first interlayer insulating film layer and the second interlayer insulating film layer may have the same film thickness or different film thicknesses. It is preferable that the first interlayer insulating film layer and the second interlayer insulating film layer have different compositions, different weight reduction temperatures, or different film thicknesses, since each interlayer insulating film layer can have different properties.

In the case where the interlayer insulating film 6 is multilayered, the weight loss temperature of at least one layer of the interlayer insulating film 6 among the plurality of layers may be 300° C. or lower. However, since the sealing material 3 and the interlayer insulating film layer are easily separated by gas, it is preferable that the weight reduction temperature of the interlayer insulating film 6 of the interlayer insulating film layer in contact with the sealing material 3 be 300° C. or lower. If the weight reduction temperature of the interlayer insulating film 6 of the interlayer insulating film layer in contact with the sealing material 3 is 300° C. or lower, the gas generated in the sealing material 3 can escape efficiently. The preferable weight reduction temperature of each interlayer insulating film layer is the same as the preferable weight reduction temperature of the interlayer insulating film 6 .

The third aspect of this embodiment is characterized in that the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film 6 does not reach 0.0150. Here, the in-plane refractive index refers to the average value of the refractive index of the interlayer insulating film 6 in the x-direction and y-direction with a wavelength of 1310 nm of thickness z, width x, and length y. The so-called out-of-plane refractive index refers to the refractive index at a wavelength of 1310 nm in the z direction. Hereinafter, the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index at a wavelength of 1310 nm is defined as the refractive index difference.

Furthermore, the so-called width x direction of the interlayer insulating film 6 refers to the plane direction of the interlayer insulating film 6 in FIG. 2, and the so-called length y direction refers to the plane direction of the interlayer insulating film 6 in FIG. The so-called thickness z direction is a direction perpendicular to the width x direction and the length y direction.

If the difference in refractive index is less than 0.0150, the adhesion between the interlayer insulating film 6 and the sealing material 3 during high-temperature treatment will be excellent. The reason for this is not certain, but the inventors of the present invention speculate as follows.

In the manufacturing process of the fan-out semiconductor device 1 (see FIG. 1 ), in order to form the rewiring layer 4 , a photosensitive resin composition is coated on the wafer sealing body including the semiconductor wafer 2 and the sealing material 3 . Next, the photosensitive resin composition is exposed with light containing i-rays. Thereafter, the photosensitive resin composition is developed and cured to selectively form a part having a cured product of the photosensitive resin composition and a part not having a cured product of the photosensitive resin composition. The cured product of the photosensitive resin composition becomes the interlayer insulating film 6 . Moreover, the wiring 5 is formed in the part which does not have the hardened|cured material of the photosensitive resin composition. Usually, the rewiring layer 4 is multilayered in many cases. That is, the photosensitive resin composition is further coated on the interlayer insulating film 6 and the wiring 5 to be exposed, developed, and cured.

However, in the step of forming the interlayer insulating film 6 and the wiring 5, a reflow step may be included depending on the manufacturing method. In the reflow process, if heat is applied to the sealing material for a long time, gas may be generated from the sealing material. When the molecular chains of the interlayer insulating film 6 are neatly arranged and stacked in the in-plane direction, that is, when the refractive index difference is large, the gas generated from the sealing material cannot pass through the interlayer insulating film 6 and is difficult to escape to the outside. Therefore, gas accumulates at the interface between the sealing material 3 and the interlayer insulating film 6 , and the sealing material 3 and the interlayer insulating film 6 are easily peeled off. Epoxy resins in particular are prone to gas generation due to high temperature thermal history. Therefore, when an epoxy resin is used for the sealing material 3 , the reduction in the adhesion between the interlayer insulating film 6 and the sealing material 3 is promoted.

The refractive index difference of the interlayer insulating film 6 of this embodiment is as small as less than 0.0150, and the molecular chains of the interlayer insulating film 6 have high randomness. Therefore, it is presumed that in this embodiment, even under the condition that the gas easily escapes from the interlayer insulating film and gas is easily generated from the sealing material 3, the peeling between the interlayer insulating film 6 and the sealing material 3 is less, and the adhesion is also high.

The difference in refractive index of the interlayer insulating film 6 is preferably less than 0.0150, preferably less than 0.0145, more preferably less than 0.0140, from the viewpoint of the adhesion between the interlayer insulating film 6 and the sealing material 3 after high-temperature treatment. Preferably less than 0.0135, preferably less than 0.0130, preferably less than 0.0125, preferably less than 0.0120, preferably less than 0.0115, preferably less than 0.0110, preferably less than 0.0095, preferably less than 0.0090, preferably less than 0.0090 0.0085 or less, preferably 0.0080 or less, preferably 0.0075 or less, preferably 0.0070 or less, preferably 0.0065 or less, preferably 0.0060 or less, preferably 0.0055 or less, preferably 0.0050 or less, preferably 0.0045 or less , preferably less than 0.0040, preferably less than 0.0035, preferably less than 0.0030, preferably less than 0.0025, preferably less than 0.0020, preferably less than 0.0010.

Also, the lower limit of the difference in refractive index of the interlayer insulating film 6 is not particularly limited, and may be not less than 0.0000, not less than 0.0005, not less than 0.0010, or not less than 0.0015.

Also, the interlayer insulating film 6 in the rewiring layer 4 may be multilayered. That is, when the rewiring layer 4 is observed in section, the rewiring layer 4 may include: a first interlayer insulating film layer; a second interlayer insulating film layer; The second interlayer insulating film layer is a different layer, and is arranged between the first interlayer insulating film layer and the second interlayer insulating film layer. The so-called intermediate layer is, for example, wiring 5 .

The first interlayer insulating film layer and the second interlayer insulating film layer may have the same composition or different compositions. The first interlayer insulating film layer and the second interlayer insulating film layer may have the same refractive index difference, or may have different refractive index differences. The first interlayer insulating film layer and the second interlayer insulating film layer may have the same film thickness or different film thicknesses. It is preferable that the first interlayer insulating film layer and the second interlayer insulating film layer have different compositions, different refractive index differences, or different film thicknesses, since each interlayer insulating film layer can have different properties.

When the interlayer insulating film 6 is multilayered, if the refractive index difference of at least one layer of the interlayer insulating film 6 is less than 0.0150 among a plurality of existing layers, the gap between the sealing material 3 and the interlayer insulating film layer is easily caused by gas. Therefore, it is preferable that the difference in refractive index between the interlayer insulating film 6 and the interlayer insulating film layer in contact with the sealing material 3 is less than 0.0150. If the difference in refractive index between the interlayer insulating film 6 and the interlayer insulating film layer in contact with the sealing material 3 is less than 0.0150, the gas generated in the sealing material 3 can escape efficiently.

The preferred refractive index difference of each interlayer insulating film layer is the same as the preferred refractive index difference of the interlayer insulating film 6 .

(composition of interlayer insulating film) The composition of the interlayer insulating film 6 is not particularly limited. For example, it is preferably a film containing at least one compound selected from polyimide, polybenzoxazole, or a polymer having a phenolic hydroxyl group.

(Resin composition for forming an interlayer insulating film) The resin composition used in the formation of the interlayer insulating film 6 is not particularly limited if it is a photosensitive resin composition, but preferably contains a polyimide precursor, a polybenzoxazole precursor, or a A photosensitive resin composition of at least one compound of a phenolic hydroxyl polymer. The resin composition used for forming the interlayer insulating film 6 may be in the form of a liquid or a film. In addition, the resin composition used for forming the interlayer insulating film 6 may be a negative photosensitive resin composition or a positive photosensitive resin composition.

In this embodiment, the pattern after exposing and developing the photosensitive resin composition is called a relief pattern, and what heat-cured the relief pattern is called a cured relief pattern. This hardened relief pattern becomes the interlayer insulating film 6 .

＜Polyimide Precursor Composition＞ (A) Photosensitive resin Examples of the photosensitive resin used in the polyimide precursor composition include polyamide, polyamide ester, and the like. For example, polyamic acid ester containing a repeating unit represented by the following general formula (11) can be used as polyamic acid ester.

[chem 43] ^R1 and ^R2 are independently a hydrogen atom, a saturated aliphatic group with a carbon number of 1 to 30, an aromatic group, a valent organic group with a carbon-carbon unsaturated double bond, or a carbon-carbon unsaturated double bond One of the valent ions. X ¹ is a tetravalent organic group, Y ¹ is a divalent organic group, and m is an integer of 1 or more. m is preferably 2 or more, more preferably 5 or more.

When R ¹ and R ² of the above general formula (11) exist as monovalent cations, O is negatively charged (exists as ^-O- ). In addition, ^X1 and ^Y1 may also contain a hydroxyl group.

R ¹ and R ² in the general formula (11) preferably have ammonium at the end of the monovalent organic group represented by the following general formula (12) or the monovalent organic group represented by the following general formula (13). The structure of ions.

[chem 44] (In general formula (12), R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or an organic group with 1 to 5 carbons, and m ₁ is an integer of 1 to 20)

[chem 45] (In the general formula (13), R ₆ , R ₇ and R ₈ are each independently a hydrogen atom or an organic group with 1 to 5 carbons, and m ₂ is an integer of 1 to 20).

A plurality of polyamide esters represented by the general formula (11) may also be mixed. Moreover, the polyamic acid ester which copolymerized the polyamic acid ester represented by General formula (11) can also be used.

^X1 is not particularly limited, but ^X1 is preferably a tetravalent organic group including an aromatic group from the viewpoint of the adhesion between the interlayer insulating film 6 and the sealing material 3 . Specifically, X ¹ is preferably a tetravalent organic group including at least one structure represented by the following general formulas (2) to (4).

[chem 46]

[chem 47]

[chem 48] (In the general formula (4), _R9 is any one of an oxygen atom, a sulfur atom, and a divalent organic group)

R ₉ in the general formula (4) is, for example, a divalent organic group having 1 to 40 carbon atoms or a halogen atom. R ₉ may also contain a hydroxyl group.

From the viewpoint of the adhesiveness between the interlayer insulating film 6 and the sealing material 3, X ¹ is particularly preferably a tetravalent organic group including a structure represented by the following general formula (5).

[chem 49]

Y ¹ is not particularly limited, but Y ¹ is preferably a divalent organic group containing an aromatic group from the viewpoint of the adhesion between the interlayer insulating film 6 and the sealing material 3 . Specifically, Y ¹ is preferably a divalent organic group including at least one structure represented by the following general formulas (6) to (8).

[chemical 50] (R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are a hydrogen atom and a monovalent aliphatic group with 1 to 5 carbon atoms, which may be the same or different)

[Chemical 51] (R ₁₄ to R ₂₁ are a hydrogen atom, a halogen atom, or a monovalent organic group with 1 to 5 carbon atoms, which may be different from each other or the same)

[Chemical 52] (R ₂₂ is a divalent organic group, and R ₂₃ to R ₃₀ are hydrogen atoms, halogen atoms, and monovalent aliphatic groups with 1 to 5 carbon atoms, which may be the same or different)

R ₂₂ in the general formula (8) is, for example, a divalent organic group having 1 to 40 carbon atoms or a halogen atom.

From the viewpoint of the adhesiveness between the interlayer insulating film 6 and the sealing material 3, Y ¹ is particularly preferably a divalent organic group including a structure represented by the following general formula (9).

[Chemical 53]

In the above-mentioned polyamic acid ester, X ¹ in the repeating unit is derived from tetracarboxylic dianhydride used as a raw material, and Y ¹ is derived from diamine used as a raw material.

Tetracarboxylic dianhydrides used as raw materials include, for example, pyromellitic dianhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3', 4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenyl-3,3',4,4'-tetracarboxylic dianhydride, Diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis(3,4-o phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, etc., but are not limited to these. Moreover, these may be used individually, and may mix and use 2 or more types.

Examples of diamines used as raw materials include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, Aminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'- Diaminodiphenylene, 3,4'-diaminodiphenylene, 3,3'-diaminodiphenylene, 4,4'-diaminobiphenyl, 3,4'- Diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diamine benzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis (4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4- Aminophenoxy)phenyl]pyridine, bis[4-(3-aminophenoxy)phenyl]pyridine, 4,4-bis(4-aminophenoxy)biphenyl, 4,4- Bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1 ,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis( 4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl)propane, 2, 2-bis[4-(4-aminophenoxy)phenyl)hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, o-toluidine, 9, 9-bis(4-aminophenyl) terpene, etc. In addition, some of the hydrogen atoms on these benzene rings may be substituted. Moreover, these may be used individually, and may mix and use 2 or more types.

In the synthesis of polyamic acid ester (A), it is generally preferable to use the tetracarboxylic acid diester obtained by carrying out the esterification reaction of tetracarboxylic dianhydride described below directly to the condensation reaction with diamine. method.

The alcohols used in the esterification reaction of the said tetracarboxylic dianhydride are alcohols which have an olefinic double bond. Specifically, 2-hydroxyethyl methacrylate, 2-methacryloxyethanol, glycerin diacrylate, glycerin dimethacrylate, etc. are mentioned, but it is not limited to these. These alcohols may be used alone or in combination of two or more.

Regarding the specific synthesis method of the polyamide ester (A) used in this embodiment, a conventionally known method can be used. Regarding the synthesis method, for example, the method described in the specification of International Publication No. 00/43439 can be mentioned. That is, the tetracarboxylic acid diester is once converted into the tetracarboxylic acid diester diacyl chloride, and the tetracarboxylic acid diester diacyl chloride and the diamine are subjected to a condensation reaction in the presence of a basic compound. A method for producing polyamide ester (A). Moreover, the method of producing polyamic acid ester (A) by the method of giving tetracarboxylic-acid diester and diamine to condensation reaction in presence of an organic dehydrating agent is mentioned.

Examples of organic dehydrating agents include dicyclohexylcarbodiimide (DCC), diethylcarbodiimide, diisopropylcarbodiimide, ethylcyclohexylcarbodiimide, Diphenylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1-cyclohexyl-3-(3-dimethylaminopropyl) ) carbodiimide hydrochloride, etc.

The weight average molecular weight of the polyamide ester (A) used in this embodiment is preferably 6,000-150,000, more preferably 7,000-50,000, more preferably 7,000-20,000.

(B1) Photoinitiator When the resin composition used for the formation of the interlayer insulating film 6 is a negative photosensitive resin, a photoinitiator is added. As the photoinitiator, for example, dibenzophenone, methyl o-benzoyl benzoate, 4-benzoyl-4'-methyl diphenyl ketone, dibenzyl ketone, and dibenzoyl ketone, etc. Benzophenone derivatives, 2,2'-diethoxyacetophenone, and 2-hydroxy-2-methylpropiophenone and other acetophenone derivatives, 1-hydroxycyclohexyl phenyl ketone, 9-oxosulfur 𠮿 , 2-Methyl-9-oxosulfur 𠮿 , 2-isopropyl-9-oxothio𠮿 , and diethyl-9-oxosulfur 9-oxosulfur Derivatives, benzoyl derivatives such as benzoyl, benzoyl dimethyl ketal and benzoyl-β-methoxyethyl acetal, benzoin derivatives such as benzoin methyl ether, 2,6-di Azides such as (4'-diazidobenzylidene)-4-methylcyclohexanone and 2,6'-bis(4'-diazidobenzylidene)cyclohexanone, 1- Phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenylpropanedione-2-(O-methoxycarbonyl)oxime, 1-phenylpropanedione -2-(O-ethoxycarbonyl)oxime, 1-phenylpropanedione-2-(O-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(O-ethyl Oxygenyl)oxime, 1-phenyl-3-ethoxyglycerone-2-(O-benzoyl)oxime and other oximes, N-arylglycine such as N-phenylglycine , peroxides such as benzoyl peroxide, aromatic biimidazoles, and titanocenes. Among these, the above-mentioned oximes are preferable in terms of photosensitivity.

The addition amount of these photoinitiators is preferably 1-40 mass parts, more preferably 2-20 mass parts with respect to 100 mass parts of polyamide ester (A). The photosensitivity is made excellent by adding 1 mass part or more of photoinitiators with respect to 100 mass parts of polyamide ester (A). Also, by adding 40 parts by mass or less, thick film curability is excellent.

(B2) Photoacid generator When the resin composition used for forming the interlayer insulating film 6 is a positive photosensitive resin, a photoacid generator is added. By containing a photoacid generator, an acid is generated in an ultraviolet-ray exposed part, and the solubility of an exposed part with respect to alkaline aqueous solution increases. Thereby, it can be used as a positive photosensitive resin composition.

Examples of the photoacid generator include quinonediazide compounds, perium salts, phosphonium salts, diazonium salts, and iodonium salts. Among them, a quinonediazide compound can be preferably used in terms of exhibiting an excellent dissolution inhibiting effect and obtaining a high-sensitivity positive-type photosensitive resin composition. In addition, two or more photoacid generators may be contained.

(C) Additives The i-ray transmittance of the interlayer insulating film in the first aspect of this embodiment can be adjusted by the amount of additives. As an additive to reduce i-ray transmittance, for example, 2-(5-chloro-2H-benzotriazol-2-yl)-6-tert-butyl-4-methylphenol, 2,4,6 - Tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-trisylphenyl) and the like.

In the second aspect of this embodiment, the weight reduction temperature of the interlayer insulating film 6 can be adjusted by the type or amount of additives. By using easily volatile additives, the density of the interlayer insulating film can be lowered, and the weight reduction temperature can be lowered. As an additive for lowering the weight loss temperature, polyethylene glycol, polypropylene glycol, or the like can be used, for example. The amount of additives can be appropriately adjusted according to the target weight reduction temperature. In addition, the weight reduction temperature of the interlayer insulating film 6 can be lowered by lowering the temperature of thermosetting of the relief pattern.

In the third aspect of this embodiment, the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film 6 can be adjusted by the type or amount of additives. If an additive with a fluffy structure is used, the additive will enter between the polymer molecular chains, and the arrangement of the polymer molecular chains will be disordered. Due to the chaotic arrangement of the polymer molecular chains, the intermolecular force between the polymer molecular chains decreases, and the molecular chains become easy to arrange randomly in the in-plane direction and the out-of-plane direction, which can make the in-plane refractive index and the out-of-plane refractive index The difference becomes smaller. As an additive which has a fluffy structure, the additive etc. which have a bicyclic structure are mentioned, for example. As an additive for reducing the refractive index difference, bicyclooctane, adamantane, etc. can be used, for example. In addition, the amount of the additive may be appropriately adjusted according to the difference between the target in-plane refractive index and the out-of-plane refractive index. In addition, the difference between the in-plane refractive index and the out-of-plane refractive index can also be made small by changing the temperature at the time of thermal curing of the relief pattern.

(D) solvent There are no particular limitations as long as it is a solvent capable of dissolving or dispersing each component. For example, N-methyl-2-pyrrolidone, γ-butyrolactone, acetone, methyl ethyl ketone, dimethyl sulfoxide, etc. are mentioned. These solvents can be used in the range of 30-1500 mass parts with respect to 100 mass parts of (A) photosensitive resins according to coating film thickness and viscosity.

(E) Other A crosslinking agent may also be included in the polyimide precursor composition. As a cross-linking agent, it can be used to cross-link the (A) photosensitive resin after exposure and development of the polyimide precursor composition, or to form a cross-linked network by itself. the cross-linking agent. By using a crosslinking agent, the heat resistance and chemical resistance of the cured film (interlayer insulating film) can be further enhanced.

In addition, a sensitizer for improving photosensitivity, an adhesive auxiliary agent for improving adhesion with a substrate, and the like may also be included.

(development) After exposing the polyimide precursor composition, the useless part is rinsed with a developing solution. The developer used is not particularly limited, and in the case of a polyimide precursor composition for developing with a solvent, N,N-dimethylformamide, dimethylsulfide, Good solvents such as N,N-dimethylacetamide, N-methyl-2-pyrrolidone, cyclopentanone, γ-butyrolactone, acetates, etc. Mixed solvents of poor solvents such as hydrocarbons, etc. Rinsing and cleaning with a poor solvent etc. are performed as needed after image development.

In the case of a polyimide precursor composition developed by an alkaline aqueous solution, an aqueous solution of tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, and potassium hydroxide are preferred , sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclo Aqueous solutions of basic compounds such as hexylamine, ethylenediamine, hexamethylenediamine, etc.

(thermohardening) By heating the developed and exposed polyimide precursor composition, the polyimide precursor is ring-closed to form polyimide. This polyimide becomes the hardened relief pattern, that is, the interlayer insulating film 6 .

In the first aspect and the second aspect of this embodiment, the heating temperature is not particularly limited, but it is preferable that the heating temperature be a relatively low temperature from the viewpoint of the influence on other components. It is preferably below 250°C, more preferably below 230°C, even more preferably below 200°C, especially preferably below 180°C.

In the third aspect of this implementation, the heating temperature for thermally hardening the polyimide precursor composition is not particularly limited, and generally there is a tendency that the lower the heating hardening temperature is, the more the refractive index difference becomes Small. The heating temperature is preferably 200°C or lower, more preferably 180°C or lower, and more preferably 160°C or lower from the viewpoint of expressing the refractive index difference of the present embodiment, that is, less than 0.0150.

＜Polyimide＞ The structure of the cured relief pattern formed from the polyimide precursor composition is the following general formula (1).

[Chemical 54]

X ¹ , Y 1 ^, m in general formula (1) are the same as X ¹ , Y ¹ , m in general formula (11), X ¹ is a tetravalent organic group, Y ¹ is a divalent organic group, m is 1 An integer of the above. Preferred X ¹ , Y ¹ , and m in the general formula (11) are also preferred in the polyimide of the general formula (1) for the same reason.

In the case of the alkali-soluble polyimide, the terminal of the polyimide may be a hydroxyl group.

＜Polybenzoxazole precursor composition＞ (A) Photosensitive resin As the photosensitive resin used in the polybenzoxazole precursor composition, poly(o-hydroxyamide) containing a repeating unit represented by the following general formula (14) can be used.

[Chemical 55] (In general formula (14), U and V are divalent organic groups)

From the viewpoint of the adhesion between the interlayer insulating film 6 and the sealing material 3, U is preferably a divalent organic group having 1 to 30 carbons, more preferably a chain alkylene group having 1 to 15 carbons (wherein the chain The hydrogen atom of the alkylene group may also be replaced by a halogen atom), especially a chain alkylene group having 1 to 8 carbon atoms and the hydrogen atom being replaced by a fluorine atom.

Also, from the viewpoint of the adhesion between the interlayer insulating film 6 and the sealing material 3, V is preferably a divalent organic group including an aromatic group, more preferably a group represented by the following general formulas (6) to (8). A divalent organic radical of at least one structure.

[Chemical 56] (R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are a hydrogen atom and a monovalent aliphatic group with 1 to 5 carbon atoms, which may be the same or different)

[Chemical 57] (R ₁₄ to R ₂₁ are a hydrogen atom, a halogen atom, or a monovalent organic group with 1 to 5 carbon atoms, which may be different from each other or the same)

[Chemical 58] (R ₂₂ is a divalent organic group, and R ₂₃ to R ₃₀ are hydrogen atoms, halogen atoms, and monovalent aliphatic groups with 1 to 5 carbon atoms, which may be the same or different)

R ₂₂ in the general formula (8) is, for example, a divalent organic group having 1 to 40 carbon atoms or a halogen atom.

From the viewpoint of the adhesiveness between the interlayer insulating film 6 and the sealing material 3, V is more preferably a divalent organic group including a structure represented by the following general formula (9).

[Chemical 59]

From the viewpoint of the adhesion between the interlayer insulating film 6 and the sealing material 3, V is preferably a divalent organic group having 1 to 40 carbon atoms, more preferably a divalent chain aliphatic group having 1 to 40 carbon atoms, and is especially preferred. It is a divalent chain aliphatic group having 1 to 20 carbon atoms.

Polybenzoxazole precursors can generally be synthesized from dicarboxylic acid derivatives and diamines containing hydroxyl groups. Specifically, it can be synthesized by converting a dicarboxylic acid derivative into a dihalide derivative and then reacting it with diamines. As the dihalide derivative, a dichloride derivative is preferable.

Dichloride derivatives can be synthesized by reacting a halogenating agent with a dicarboxylic acid derivative. As the halogenating agent, thionyl chloride, phosphonyl chloride, phosphonyl chloride, phosphorus pentachloride, etc., which are generally used in the acyl chloride reaction of carboxylic acids can be used.

As a method of synthesizing dichloride derivatives, it can be synthesized by the method of reacting dicarboxylic acid derivatives with the above-mentioned halogenating agent in a solvent. After reacting in excess halogenating agent, the excess components are distilled off. method etc.

Examples of dicarboxylic acids used in dicarboxylic acid derivatives include isophthalic acid, terephthalic acid, 2,2-bis(4-carboxyphenyl)-1,1,1,3,3, 3-hexafluoropropane, 4,4'-dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxytetraphenylsilane, bis(4-carboxyphenyl)sulfone, 2 ,2-bis(p-carboxyphenyl)propane, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6 - Naphthalene dicarboxylic acid, malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid , 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3-methyl Glutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, octafluoroadipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, decane Acid, hexadecanedioic acid, 1,9-nonanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid Alkanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, hexadecanedioic acid, docosanedioic acid, tricosanedioic acid, tetradecanedioic acid, Hexacanedioic acid, hexacanedioic acid, heptacanedioic acid, octadecanedioic acid, hexacanedioic acid, triacanedioic acid, triacanedioic acid, thirty Dioxanedioic acid, diglycolic acid, etc. These can also be used in combination.

As diamines containing a hydroxyl group, for example, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis( 3-amino-4-hydroxyphenyl)propane, bis(4-amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)propane, bis(4-amino- 3-hydroxyphenyl) phenyl, 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4- Amino-3-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, etc. These can also be used in combination.

(B2) Photoacid generator The photoacid generator has a function of increasing the solubility of the alkaline aqueous solution of the light-irradiated part. Examples of photoacid generators include diazonaphthoquinone compounds, aryldiazonium salts, diaryliodonium salts, triaryliumium salts, and the like. Among them, the diazonaphthoquinone compound is preferable due to its high sensitivity.

(C) Additives The type or amount of the preferred additive is the same as that described in the item of the polyimide precursor composition.

(D) solvent There are no particular limitations as long as it is a solvent capable of dissolving or dispersing each component.

(E) Other The polybenzoxazole precursor composition may contain a crosslinking agent, a sensitizer, an adhesive agent, a thermal acid generator, and the like.

(development) After exposing the polybenzoxazole precursor composition, the useless part is rinsed with a developing solution. The developer used is not particularly limited, for example, alkalis such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide, etc. An aqueous solution is preferred.

In the above, the positive type polybenzoxazole precursor composition is mainly described, but the negative type polybenzoxazole precursor composition may also be used.

(thermohardening) After developing, the polybenzoxazole precursor composition is heated to close the ring of the polybenzoxazole precursor to form polybenzoxazole. This polybenzoxazole becomes the hardened relief pattern, that is, the interlayer insulating film 6 .

The heating temperature for thermosetting the polybenzoxazole precursor composition is not particularly limited, but from the viewpoint of the influence on other components, the heating temperature is preferably a relatively low temperature. The heating temperature is preferably lower than 250°C, more preferably lower than 230°C, more preferably lower than 200°C, especially preferably lower than 180°C.

＜Polybenzoxazole＞ The structure of the cured relief pattern formed from the polybenzoxazole precursor composition is the following general formula (10).

[Chemical 60]

U and V in the general formula (10) are the same as U and V in the general formula (14). The preferable U and V in the general formula (14) are also preferable in the polybenzoxazole of the general formula (10) for the same reason.

＜Polymers with phenolic hydroxyl groups＞ (A) Photosensitive resin A resin having a phenolic hydroxyl group in the molecule is soluble in alkali. Specific examples thereof include vinyl polymers containing monomer units having phenolic hydroxyl groups such as poly(hydroxystyrene), phenol resins, poly(hydroxyamides), poly(hydroxyphenylene) ethers, and polynaphthols.

Among these, phenolic resins are preferable, and novolak-type phenolic resins are particularly preferable in terms of low cost and small volume shrinkage during curing.

Phenolic resin is a polycondensation product of phenol or its derivatives and aldehydes. Polycondensation is carried out in the presence of catalysts such as acid or alkali. The phenol resin obtained when using an acid catalyst is especially called a novolac type phenol resin.

Examples of phenol derivatives include phenol, cresol, ethylphenol, propylphenol, butylphenol, amylphenol, benzylphenol, adamantanephenol, benzyloxyphenol, xylenol, catechol, m-benzene Diphenol, ethyl resorcinol, hexyl resorcinol, hydroquinone, pyrogallol, phloroglucinol, 1,2,4-trihydroxybenzene, rosebic acid, biquinone, Bisphenol A, bisphenol AF, bisphenol B, bisphenol F, bisphenol S, dihydroxydiphenylmethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,4-bis(3 -hydroxyphenoxybenzene), 2,2-bis(4-hydroxy-3-methylphenyl)propane, α,α'-bis(4-hydroxyphenyl)-1,4-diisopropylbenzene , 9,9-bis(4-hydroxy-3-methylphenyl) terpene, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2,2-bis(2-hydroxy-5 -biphenyl)propane, dihydroxybenzoic acid, etc.

Examples of aldehyde compounds include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, pivalaldehyde, butyraldehyde, valeraldehyde, hexanal, trioxane, glyoxal, cyclohexylaldehyde, diphenylacetaldehyde, ethylbutyl Aldehyde, benzaldehyde, glyoxylic acid, 5-northene-2-carboxyaldehyde, malondialdehyde, succinaldehyde, glutaraldehyde, salicaldehyde, naphthalene formaldehyde, terephthalaldehyde, etc.

It is preferable that (A) component contains (a) the phenol resin which does not have an unsaturated hydrocarbon group, and (b) the modified phenol resin which has an unsaturated hydrocarbon group. The above-mentioned (b) component is more preferably formed by further modification through the reaction of phenolic hydroxyl group and polybasic acid anhydride.

Also, as component (b), from the viewpoint of further improving mechanical properties (elongation at break, modulus of elasticity, and residual stress), it is preferable to use a compound modified by having an unsaturated hydrocarbon group having 4 to 100 carbon atoms. permanent phenolic resin.

(b) Modified phenolic resins with unsaturated hydrocarbon groups are generally phenol or its derivatives and compounds with unsaturated hydrocarbon groups (preferably those with 4 to 100 carbons) (hereinafter referred to as "compounds containing unsaturated hydrocarbon groups" according to the situation) ") (hereinafter referred to as "unsaturated hydrocarbon group-modified phenol derivatives") and polycondensation products of aldehydes, or reaction products of phenolic resins and compounds containing unsaturated hydrocarbon groups.

The phenol derivative used here is the same as the phenol derivative mentioned above as a raw material of the phenol resin of (A) component.

It is preferable that the unsaturated hydrocarbon group of the unsaturated hydrocarbon group-containing compound contains two or more unsaturated groups from the viewpoint of the adhesiveness of the resist pattern and thermal shock resistance. Also, from the standpoint of compatibility when forming a resin composition and flexibility of a cured film, the compound containing an unsaturated hydrocarbon group is preferably one having 8 to 80 carbon atoms, and more preferably one having 10 to 60 carbon atoms.

Examples of compounds containing unsaturated hydrocarbon groups include unsaturated hydrocarbons having 4 to 100 carbon atoms, polybutadiene having carboxyl groups, epoxidized polybutadiene, linolenic alcohol, oleyl alcohol, unsaturated fatty acids, and unsaturated fatty acids ester. Examples of suitable unsaturated fatty acids include crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vacantoleic acid, codoleic acid, erucic acid, tetradecenoic acid, linolenic acid, α-linolenic acid, lynic acid, stearidonic acid, arachidonic acid, eicosapentaenoic acid, herring acid and docosahexaenoic acid. Among these, esters of unsaturated fatty acids with 8 to 30 carbons and monohydric to trihydric alcohols with 1 to 10 carbons are more preferred, especially unsaturated fatty acids with 8 to 30 carbons and trihydric alcohols esters of glycerol.

Esters of unsaturated fatty acids with 8 to 30 carbon atoms and glycerol can be commercially obtained in the form of vegetable oils. Vegetable oils include non-drying oils with an iodine value of 100 or less, semi-drying oils with an iodine value of more than 100 and less than 130, or drying oils with an iodine value of 130 or more. Examples of non-drying oils include olive oil, morning glory seed oil, Polygonum multiflorum seed oil, camellia oleifera oil, camellia oil, castor oil, and peanut oil. Examples of semi-dry oils include corn oil, cottonseed oil, and sesame oil. Examples of drying oils include tung oil, linseed oil, soybean oil, walnut oil, safflower oil, sunflower oil, perilla seed oil, and mustard oil. Moreover, the processed vegetable oil obtained by processing these vegetable oils can also be used.

Among the above-mentioned vegetable oils, it is preferable to use a non-drying oil from the viewpoint of preventing gelation accompanying excessive reaction progress and improving yield in the reaction of phenol or its derivatives or phenol resin with vegetable oil. On the other hand, from the viewpoint of improving the adhesiveness of the resist pattern, mechanical properties, and thermal shock resistance, it is preferable to use a drying oil. Among drying oils, tung oil, linseed oil, soybean oil, walnut oil, and safflower oil are preferred, and tung oil and linseed oil are more preferred, since the effects of the present invention can be more effectively and reliably exerted.

These unsaturated hydrocarbon group-containing compounds can be used alone or in combination of two or more.

When preparing the component (b), first, the above-mentioned phenol derivative is reacted with the above-mentioned unsaturated hydrocarbon group-containing compound to produce an unsaturated hydrocarbon group-modified phenol derivative. Preferably, the above reaction is carried out at 50-130°C. As for the reaction ratio of the phenol derivative and the compound containing an unsaturated hydrocarbon group, from the viewpoint of improving the flexibility of the cured film (resist pattern), it is preferable to contain an unsaturated hydrocarbon group relative to 100 parts by mass of the phenol derivative. The hydrocarbon group compound is 1-100 mass parts, More preferably, it is 5-50 mass parts. When the unsaturated hydrocarbon group-containing compound is less than 1 part by mass, the flexibility of the cured film tends to decrease, and when it exceeds 100 parts by mass, the heat resistance of the cured film tends to decrease. In the above reaction, p-toluenesulfonic acid, trifluoromethanesulfonic acid, etc. may also be used as a catalyst if necessary.

The phenol resin modified by the unsaturated hydrocarbon group-containing compound is produced by polycondensing the unsaturated hydrocarbon group-modified phenol derivative and aldehydes produced by the above reaction. As the aldehydes, the same aldehydes as those used to obtain the phenol resin can be used.

The reaction between the above-mentioned aldehydes and the above-mentioned unsaturated hydrocarbon group-modified phenol derivative is a polycondensation reaction, and the previously known synthesis conditions of the phenolic resin can be used. The reaction is preferably carried out in the presence of a catalyst such as an acid or a base, more preferably using an acid catalyst. Examples of the acid catalyst include hydrochloric acid, sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid, and oxalic acid. These acid catalysts may be used alone or in combination of two or more.

Usually, it is preferable to carry out the above reaction at a reaction temperature of 100-120°C. In addition, although the reaction time varies depending on the type or amount of the catalyst used, it is usually 1 to 50 hours. After the reaction is completed, the reaction product is dehydrated under reduced pressure at a temperature below 200° C., thereby obtaining a phenol resin modified by a compound containing an unsaturated hydrocarbon group. In addition, solvents such as toluene, xylene, and methanol can be used in the reaction.

A phenol resin modified by a compound containing an unsaturated hydrocarbon group can also be obtained by polycondensing the above-mentioned unsaturated hydrocarbon group-modified phenol derivative with a compound other than phenol such as m-xylene and aldehydes . In this case, the molar ratio of the compound other than phenol to the compound obtained by reacting the phenol derivative and the unsaturated hydrocarbon group-containing compound is preferably less than 0.5.

The component (b) can also be obtained by reacting the phenol resin of the component (a) with an unsaturated hydrocarbon group-containing compound.

As the unsaturated hydrocarbon group-containing compound to be reacted with the phenol resin, the same ones as those described above for the unsaturated hydrocarbon group-containing compound can be used.

It is preferable to carry out the reaction of the phenol resin and the compound containing an unsaturated hydrocarbon group usually at 50-130 degreeC. Also, from the viewpoint of improving the flexibility of the cured film (resist pattern), the reaction ratio between the phenol resin and the unsaturated hydrocarbon group-containing compound is preferably 100 parts by mass of the phenol resin. The compound is 1-100 mass parts, More preferably, it is 2-70 mass parts, More preferably, it is 5-50 mass parts. If the unsaturated hydrocarbon group-containing compound is less than 1 part by mass, the flexibility of the cured film tends to decrease, and if it exceeds 100 parts by mass, the possibility of gelation during the reaction tends to increase, and hardening The heat resistance of the film tends to decrease. At this time, p-toluenesulfonic acid, trifluoromethanesulfonic acid, etc. may also be used as a catalyst as needed. In addition, solvents such as toluene, xylene, methanol, and tetrahydrofuran can be used in the reaction.

Further, the polybasic acid anhydride is reacted with the remaining phenolic hydroxyl groups in the phenol resin modified by the unsaturated hydrocarbon group-containing compound produced by the method described above. Thereby, the acid-modified phenol resin can also be used as (b) component. By acid-modifying with polybasic acid anhydride and introducing a carboxyl group, the solubility of (b) component with respect to alkaline aqueous solution (developing solution) improves further.

The polybasic acid anhydride is not particularly limited as long as it has an acid anhydride group formed by dehydration condensation of carboxyl groups of a polybasic acid having a plurality of carboxyl groups. Examples of the polybasic acid anhydride include phthalic anhydride, succinic anhydride, octenyl succinic anhydride, penta(dodecenyl)succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, Diformic anhydride, Methyltetrahydrophthalic anhydride, Methylhexahydrophthalic anhydride, Resilicate anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, Methylendomethylene Dibasic acid anhydrides such as tetrahydrophthalic anhydride, tetrabromophthalic anhydride and trimellitic anhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butane Aromatic tetracarboxylic dianhydrides such as alkane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic dianhydride, and benzophenone tetracarboxylic dianhydride. These can be used alone or in combination of two or more. Among these, the polybasic acid anhydride is preferably a dibasic acid anhydride, more preferably at least one selected from the group consisting of tetrahydrophthalic anhydride, succinic anhydride, and hexahydrophthalic anhydride. In this case, there is an advantage that a resist pattern can be formed and thus have a good shape.

Moreover, the alkali-soluble resin which has (A) phenolic hydroxyl group can further contain the phenol resin which made polybasic acid anhydride react and performed acid modification. The solubility of (A) component with respect to alkaline aqueous solution (developing solution) can be further improved by making (A) component contain the phenol resin acid-denatured with the polybasic acid anhydride.

Examples of the polybasic acid anhydride include phthalic anhydride, succinic anhydride, octenyl succinic anhydride, penta(dodecenyl) succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, Hydrogen phthalic anhydride, Methyl tetrahydro phthalic anhydride, Methyl hexahydro phthalic anhydride, Resilicate anhydride, 3,6-endomethylene tetrahydro phthalic anhydride, Methyl endophthalic anhydride Dibasic acid anhydrides such as methylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride, trimellitic anhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dicarboxylic acid Anhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride and other aliphatic and aromatic tetracarboxylic dianhydrides. These can be used alone or in combination of two or more. Among these, the polybasic acid anhydride is preferably a dibasic acid anhydride, more preferably, for example, one or more selected from the group consisting of tetrahydrophthalic anhydride, succinic anhydride, and hexahydrophthalic anhydride.

(B2) Photoacid generator Examples of the photoacid generator include diazonaphthoquinone compounds, aryldiazonium salts, diaryliodonium salts, triaryliumium salts, and the like. Among them, the diazonaphthoquinone compound is preferable due to its high sensitivity.

(C) Additives The type or amount of the preferred additive is the same as that described in the item of the polyimide precursor composition.

(D) solvent There are no particular limitations as long as it is a solvent capable of dissolving or dispersing each component.

(E) Other It may contain thermal crosslinking agent, sensitizer, adhesive agent, dye, surfactant, dissolution accelerator, crosslinking accelerator, etc. However, when the photosensitive resin film after pattern formation is heated and hardened by containing a thermal crosslinking agent, a thermal crosslinking agent component and (A) component react and form a bridge structure. This makes it possible to harden at low temperature, and prevents brittleness of the film and melting of the film. As the thermal crosslinking agent component, specifically, a compound having a phenolic hydroxyl group, a compound having a hydroxymethylamine group, and a compound having an epoxy group are preferably used.

(development) After exposing the polymer having a phenolic hydroxyl group, useless parts are rinsed with a developing solution. The developer used is not particularly limited, for example, sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide can be suitably used Alkaline aqueous solution such as (TMAH).

(thermohardening) After the development, the polymers having phenolic hydroxyl groups are thermally crosslinked with each other by heating the polymers having phenolic hydroxyl groups. The crosslinked polymer becomes a cured relief pattern, that is, an interlayer insulating film 6 .

The heating temperature for thermosetting the polymer having a phenolic hydroxyl group is not particularly limited, but from the viewpoint of the influence on other members, the heating temperature is preferably a relatively low temperature. The heating temperature is preferably below 250°C, more preferably below 230°C, even more preferably below 200°C, especially preferably below 180°C.

(Manufacturing method of semiconductor device) The manufacturing method of the semiconductor device of this embodiment is demonstrated using FIG. 3. FIG. In FIG. 3A, the wafer 10 completed in the previous step is prepared. Then, in FIG. 3B , the wafer 10 completed in the previous step is diced to form a plurality of semiconductor wafers 2 . The semiconductor wafer 2 can also be purchased. The semiconductor wafers 2 prepared as described above are attached to the support 11 at specific intervals as shown in FIG. 3C.

Next, the mold resin 12 is applied from the semiconductor wafer 2 to the support 11, and mold sealing is performed as shown in FIG. 3D. Next, the support body 11 is peeled off, and the molding resin 12 is reversed (see FIG. 3E ). As shown in FIG. 3E , the semiconductor wafer 2 and the molding resin 12 appear on substantially the same plane. Then, the photosensitive resin composition 13 is coated on the semiconductor wafer 2 and the molding resin 12 through the steps shown in FIG. 3F . Then, the applied photosensitive resin composition 13 is exposed and developed to form a relief pattern (relief pattern forming step). Furthermore, the photosensitive resin composition 13 may be either positive or negative. Furthermore, the relief pattern is heated to form a cured relief pattern (interlayer insulating film forming step). Furthermore, wiring is formed in the portion where the hardened relief pattern is not formed (wiring forming step).

Furthermore, in this embodiment, the above-described relief pattern forming step, interlayer insulating film forming step, and wiring forming step are combined as a rewiring layer forming step for forming a rewiring layer connected to the semiconductor wafer 2 .

The interlayer insulating film in the rewiring layer may also be multilayered. Therefore, the rewiring layer forming step may also include a plurality of emboss pattern forming steps, a plurality of interlayer insulating film forming steps, and a plurality of wiring forming steps.

Furthermore, in FIG. 3G , a plurality of external connection terminals 7 corresponding to each semiconductor wafer 2 are formed (bumps are formed), and crystal dicing is performed between each semiconductor wafer 2 . Thereby, a semiconductor device (semiconductor IC) 1 can be obtained as shown in FIG. 3H. In this embodiment, a plurality of fan-out semiconductor devices 1 can be obtained by the manufacturing method shown in FIG. 3 .

In this embodiment, the i-ray transmittance of the cured relief pattern (interlayer insulating film) formed through the above steps can be set to 80% or less. Here, the i-ray transmittance of the interlayer insulating film can be adjusted by the amount of the additive.

In this embodiment, it is preferable to combine a photosensitive resin with at least one compound that can form polyimide, polybenzoxazole, or a polymer having a phenolic hydroxyl group in the above-mentioned interlayer insulating film forming step. material to form an interlayer insulating film.

In the first aspect of this embodiment, the i-ray transmittance of the hardened relief pattern (interlayer insulating film) formed through the above steps can be set to 80% or less. Here, the i-ray transmittance of the interlayer insulating film can be adjusted by the amount of the additive.

In the second aspect of this embodiment, the weight reduction temperature of the cured relief pattern (interlayer insulating film) formed through the above steps can be set to be 300° C. or lower. Here, the weight reduction temperature of the interlayer insulating film can be adjusted by the amount of the additive.

In the third aspect of this embodiment, the difference in refractive index of the cured relief pattern (interlayer insulating film) formed through the above steps can be set to be less than 0.0150. Here, the refractive index difference of the interlayer insulating film can be adjusted by the amount of the additive.

In this embodiment, it is preferable to combine a photosensitive resin with at least one compound that can form polyimide, polybenzoxazole, or a polymer having a phenolic hydroxyl group in the above-mentioned interlayer insulating film forming step. material to form an interlayer insulating film. [Example]

Hereinafter, examples performed in order to clarify the effects of the present invention will be described. In the examples, the following materials and measurement methods were used. [Example] Hereinafter, examples performed in order to clarify the effects of the present invention will be described.

(Polymer A-1: Synthesis of Polyimide Precursor) 4,4'-oxydiphthalic dianhydride (ODPA) which is tetracarboxylic dianhydride was put into the 2-liter separable flask. Furthermore, 2-hydroxyethyl methacrylate (HEMA) and (gamma)-butyrolactone were put and stirred at room temperature, and pyridine was added, stirring, and the reaction mixture was obtained. After the exothermic heat generated by the reaction ended, it was left to cool to room temperature and left for 16 hours.

Next, under ice-cooling, while stirring a solution in which dicyclohexylcarbodiimide (DCC) was dissolved in γ-butyrolactone, it was added to the reaction mixture over 40 minutes. Then, what suspended 4,4'- diamino diphenyl ether (DADPE) as a diamine in (gamma)-butyrolactone was added over 60 minutes, stirring. Furthermore, after stirring at room temperature for 2 hours, ethanol was added and stirred for 1 hour, and then γ-butyrolactone was added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction liquid.

The obtained reaction solution was added to ethanol to generate a precipitate containing a crude polymer. The generated crude polymer was separated by filtration, and dissolved in tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to water to precipitate the polymer, and the obtained precipitate was separated by filtration and then vacuum-dried to obtain a powdered polymer (polyimide precursor (polymer A- 1)). The mass of the compound used for component A-1 is shown in Table A1 shown below.

(Synthesis of polymers A-2 to A-4) As shown in the following Table 1, the tetracarboxylic dianhydride and diamine were changed, except that the reaction was carried out in the same manner as described in the above-mentioned polymer A-1, and a polyimide precursor (polymer A-2) was obtained. ~A-4).

(Polymer B-1: Synthesis of Polybenzoxazole Precursor) Into a 0.5-liter flask equipped with a stirrer and a thermometer, 15.48 g of 4,4'-diphenyl ether dicarboxylic acid and N-methylpyrrolidone were charged as a dicarboxylic acid. After cooling the flask to 5° C., thionyl chloride was added dropwise and allowed to react for 30 minutes to obtain a solution of dicarboxyl chloride. Next, N-methylpyrrolidone was placed in a 0.5-liter flask equipped with a stirrer and a thermometer. After stirring and dissolving 18.30 g of bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 2.18 g of m-aminophenol as bisaminophenol, pyridine was added. Then, while maintaining the temperature at 0 to 5° C., the solution of dicarboxyl chloride was added dropwise over 30 minutes, and stirring was continued for 30 minutes. The solution was poured into 3 liters of water, the precipitate was collected, washed with pure water three times, and then dried under reduced pressure to obtain a polymer (polybenzoxazole precursor (polymer B-1)). The mass of the compound used for polymer B-1 is shown in Table 1 below.

(Synthesis of polymers B-2 to B-3) Except for changing the dicarboxylic acid and bisaminophenol as shown in Table 1 below, the reaction was carried out in the same manner as described in the above-mentioned polymer B-1, and a polybenzoxazole precursor (polymer B-1) was obtained. 2～B-3).

(Polymer C-1: Synthesis of Phenolic Resin) A phenol resin containing 85 g of the C1 resin shown below and 15 g of the C2 resin shown below was prepared as polymer C-1. C1: cresol novolac resin (cresol/formaldehyde novolak resin, m-cresol/p-cresol (molar ratio) = 60/40, polystyrene-equivalent weight average molecular weight = 12,000, manufactured by Asahi Organic Materials Co., Ltd., Product name "EP4020G")

C2: C2 was synthesized as shown below. <C2: Synthesis of phenolic resin modified by a compound having an unsaturated hydrocarbon group with 4 to 100 carbons> 100 parts by mass of phenol, 43 parts by mass of linseed oil, and 0.1 part by mass of trifluoromethanesulfonic acid were mixed, stirred at 120° C. for 2 hours, and a vegetable oil-modified phenol derivative (a) was obtained. Next, 130 g of the vegetable oil-modified phenol derivative (a), 16.3 g of paraformaldehyde, and 1.0 g of oxalic acid were mixed, and stirred at 90° C. for 3 hours. Next, after heating up to 120 degreeC and stirring for 3 hours under reduced pressure, 29 g of succinic anhydride and 0.3 g of triethylamine were added to the reaction liquid, and it stirred at 100 degreeC for 1 hour under atmospheric pressure. The reaction solution was cooled to room temperature to obtain a phenolic resin modified by a compound having an unsaturated hydrocarbon group having 4 to 100 carbons (hereinafter referred to as "C2 resin") as a reaction product (acid value 120 mgKOH/ g).

(Synthesis of Polymer C-2) 100 g of the following C1 resin was prepared as polymer C-2.

[Table 1] polymer Tetracarboxylic dianhydride (A) A mass (g) Diamine (B) Mass of B (g) Polyimide Precursor Polymer A-1 4,4'-Oxydiphthalic dianhydride (ODPA) 147.11 4,4'-Diaminodiphenyl ether (DADPE) 92.9 Polymer A-2 4,4'-Oxydiphthalic dianhydride (ODPA) 147.11 2,2'-Bisdimethyl-4,4'-diaminobiphenyl (m-TB) 98.5 Polymer A-3 4,4'-Oxydiphthalic dianhydride (ODPA) 147.11 p-phenylenediamine (PPD) 50.18 Polymer A-4 stilbenic dianhydride 229.2 2,2'-Bis(trifluoromethyl)benzidine (TFMB) 148.51 Dicarboxylic acid (C) Mass of C (g) Diaminophenol (D) D mass (g) Polybenzoxazole Precursor Polymer B-1 4,4'-Diphenyl ether dicarboxylic acid 15.48 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane 18.3 Polymer B-2 sebacic acid 12.13 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane 18.3 Polymer B-3 Dicyclopentadiene dicarboxylic acid 11.3 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane 18.3 Cresol Novolak Resin (E) Mass of E (g) Modified phenolic resin (F) Mass of F (g) Phenolic resin Polymer C-1 C1 resin 85 C2 resin 15 Polymer C-2 C1 resin 100 C2 resin 0

[Examples 1-11, Comparative Examples 1-2] It prepared like Table 2 shown below, and obtained the solution of the photosensitive resin composition. In addition, the unit of Table 2 is a mass part.

Using the compound described in Table 2, each photosensitive resin composition of Examples 1-11 and Comparative Examples 1-2 was produced by the compounding quantity described in Table 3 and Table 4.

(1) i-ray transmittance measurement test, (2) sealing material deterioration test, and (3) adhesiveness test with sealing material were performed about the produced photosensitive resin composition. The results of each test are shown in Table 3 below.

(1) Measurement test of i-ray transmittance Using the photosensitive resin composition produced in each Example and each comparative example, a fan-out wafer-level chip size packaging type semiconductor device was produced. An interlayer insulating film with a thickness of 10 μm was taken out as thoroughly as possible from the manufactured semiconductor device. The UV-1800 device manufactured by Shimadzu Corporation was used to measure the taken-out interlayer insulating film under the conditions of a medium scanning speed and a sampling interval of 0.5 nm, thereby measuring the i-ray transmittance.

(2) Sealing Material Deterioration Test As an epoxy-based sealing material, R4000 series manufactured by Nagase Chemical Co., Ltd. was prepared. Next, the sealing material was spin-coated on the aluminum-sputtered silicon wafer to a thickness of about 150 micrometers, and thermally cured at 130° C. to harden the epoxy-based sealing material. The photosensitive resin composition produced in each Example and each comparative example was apply|coated on the said epoxy-type cured film so that the final film thickness might become 10 micrometers. For the coated photosensitive resin composition, the exposure conditions were 200 mJ/cm2 in Examples 1-4, 10 and Comparative Example 1, and 500 mJ/ ^cm2 in Examples 5-7, 11 and Comparative Example 2. The exposure conditions of 700 mJ/cm ² in Examples 8 and 9 were used to expose ^the entire surface. Thereafter, thermosetting was carried out at 200° C. for 2 hours to form a first-layer cured film with a thickness of 10 μm.

Apply the photosensitive resin composition used in the formation of the first cured film on the first cured film, expose the entire surface under the same conditions as when producing the first cured film, and then heat-cure it And make the second layer of cured film with a thickness of 10 microns.

Cut the cross-section of the test piece after the formation of the second layer of cured film by FIB device (manufactured by JEOL Corporation, JIB-4000), and then confirm the presence or absence of pores in the epoxy part to evaluate the degree of deterioration. The case where no pore was found was made ◯, and the case where even one pore was found was made x.

(3) Adhesion test with sealing material The sample produced in the sealing material deterioration test was set up with a stylus, and the adhesion test was carried out using a traction tester (manufactured by Quad Group, Sebastian 5 type). That is, the adhesiveness of the epoxy-type sealing material and the cured relief pattern produced from the photosensitive resin composition produced in each Example and each comparative example was tested. Evaluation: Adhesion strength of 70 MPa or more・・・Adhesive force◎ More than 50 MPa and less than -70 MPa・・・Adhesive force○ More than 30 MPa and less than -50 MPa・・・Adhesive force△ Less than 30 MPa・・・Adhesive force×

[Table 2] Photoinitiator D-1 photoacid generator D-2 crosslinking agent E-1 i Radiation transmittance adjuster F-1 2-(5-Chloro-2H-benzotriazol-2-yl)-6-tert-butyl-4-methylphenol F-2 2,4,6-Tri(2-Hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-tris(3-methylphenyl) solvent G-1 γ-butyrolactone G-2 DMSO G-3 Propylene Glycol Monomethyl Ether Acetate G-4 ethyl lactate

[table 3] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 polymer A-1 100 A-2 100 A-3 100 A-4 100 B-1 100 B-2 100 B-3 100 C-1 100 C-2 100 Photoinitiator D-1 2 2 2 2 photoacid generator D-2 10 10 10 15 15 crosslinking agent E-1 15 15 i Radiation transmittance adjuster F-1 2 2 2 1 4 4 4 3 3 F-2 solvent G-1 160 160 160 160 225 225 225 G-2 40 40 40 40 G-3 25 25 25 G-4 120 120 i Ray transmittance (%) 10 20 twenty three 65 18 15 30 25 41 Sealing material deterioration test 〇 〇 〇 〇 〇 〇 〇 〇 〇 Adhesion test with sealing material ◎ 〇 〇 △ 〇 〇 △ 〇 △

[Table 4] Example 10 Example 11 Comparative example 1 Comparative example 2 polymer A-1 100 A-2 A-3 A-4 100 B-1 100 B-2 B-3 100 C-1 C-2 Photoinitiator D-1 2 2 photoacid generator D-2 10 10 crosslinking agent E-1 i Radiation transmittance adjuster F-1 F-2 2 4 solvent G-1 160 225 160 225 G-2 40 40 G-3 25 25 G-4 i Ray transmittance (%) 8 twenty two 85 88 Deterioration of sealing material 〇 〇 x x Adhesion with sealing material ◎ 〇 x x

Using the photosensitive resin compositions described in Examples 1 to 11, a fan-out wafer-level chip size package type semiconductor device in which epoxy resin was included in the molding resin was produced, and it was able to operate without problems.

(Polymer H-1: Synthesis of Polyimide Precursor) 4,4'-oxydiphthalic dianhydride (ODPA) which is tetracarboxylic dianhydride was put into the 2-liter separable flask. Furthermore, 2-hydroxyethyl methacrylate (HEMA) and (gamma)-butyrolactone were put and stirred at room temperature, and pyridine was added, stirring, and the reaction mixture was obtained. After the exothermic heat generated by the reaction ended, it was left to cool to room temperature and left for 16 hours.

Next, under ice-cooling, while stirring a solution in which dicyclohexylcarbodiimide (DCC) was dissolved in γ-butyrolactone, it was added to the reaction mixture over 40 minutes. Then, what suspended 4,4'- diamino diphenyl ether (DADPE) as a diamine in (gamma)-butyrolactone was added over 60 minutes, stirring. Furthermore, after stirring at room temperature for 2 hours, ethanol was added and stirred for 1 hour, and then γ-butyrolactone was added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction liquid.

The obtained reaction solution was added to ethanol to generate a precipitate containing a crude polymer. The generated crude polymer was separated by filtration, and dissolved in tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to water to precipitate the polymer, and the obtained precipitate was separated by filtration and vacuum-dried to obtain a powdered polymer (polyimide precursor (polymer H- 1)). The mass of the compound used for component H-1 is shown in Table 5 shown below.

(Synthesis of Polymers H-2～H-4) As shown in the following Table 5, the tetracarboxylic dianhydride and the diamine were changed, except that the reaction was carried out in the same manner as described in the above-mentioned polymer H-1, and a polyimide precursor (polymer H-2) was obtained. ~H-4).

(Polymer I-1: Synthesis of Polybenzoxazole Precursor) Into a 0.5-liter flask equipped with a stirrer and a thermometer, 15.48 g of 4,4'-diphenyl ether dicarboxylic acid and N-methylpyrrolidone were charged as a dicarboxylic acid. After the flask was cooled to 5°C, thionyl chloride was added dropwise to react for 30 minutes to obtain a solution of dicarboxylic acid chloride. Next, N-methylpyrrolidone was placed in a 0.5-liter flask equipped with a stirrer and a thermometer. After stirring and dissolving 18.30 g of bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 2.18 g of m-aminophenol as bisaminophenol, pyridine was added. Then, while maintaining the temperature at 0 to 5° C., the solution of dicarboxyl chloride was added dropwise over 30 minutes, and stirring was continued for 30 minutes. The solution was poured into 3 liters of water, the precipitate was recovered, washed three times with pure water, and then dried under reduced pressure to obtain a polymer (polybenzoxazole precursor (polymer I-1)). The mass of the compound used for polymer I-1 is shown in Table 5 below.

(Synthesis of polymers I-2 to I-3) The dicarboxylic acid and bisaminophenol were changed as shown in Table 5 below, and the reaction was carried out in the same manner as described in the above-mentioned polymer I-1, to obtain a polybenzoxazole precursor (polymer I- 2～1-3).

(Polymer J-1: Synthesis of Phenolic Resin) A phenol resin containing 85 g of J1 resin shown below and 15 g of J2 resin shown below was prepared as polymer J-1. J1: Cresol novolac resin (cresol/formaldehyde novolak resin, m-cresol/p-cresol (molar ratio) = 60/40, polystyrene-equivalent weight average molecular weight = 12,000, manufactured by Asahi Organic Materials Co., Ltd., Product name "EP4020G")

J2: J2 was synthesized as shown below. <J2: Synthesis of phenolic resin modified by a compound having an unsaturated hydrocarbon group with 4 to 100 carbons> 100 parts by mass of phenol, 43 parts by mass of linseed oil, and 0.1 part by mass of trifluoromethanesulfonic acid were mixed, stirred at 120° C. for 2 hours, and a vegetable oil-modified phenol derivative (a) was obtained. Next, 130 g of the vegetable oil-modified phenol derivative (a), 16.3 g of paraformaldehyde, and 1.0 g of oxalic acid were mixed, and stirred at 90° C. for 3 hours. Next, after heating up to 120 degreeC and stirring for 3 hours under reduced pressure, 29 g of succinic anhydride and 0.3 g of triethylamine were added to the reaction liquid, and it stirred at 100 degreeC for 1 hour under atmospheric pressure. The reaction solution was cooled to room temperature to obtain a phenol resin modified by a compound having an unsaturated hydrocarbon group having 4 to 100 carbons (hereinafter referred to as "J2 resin") as a reaction product (acid value 120 mgKOH/ g).

(Synthesis of Polymer J-2) 100 g of the following J1 resin was prepared as polymer J-2.

[table 5] polymer Tetracarboxylic dianhydride (A) A mass (g) Diamine (B) Mass of B (g) Polyimide Precursor Polymer H-1 4,4'-Oxydiphthalic dianhydride (ODPA) 147.11 4,4'-Diaminodiphenyl ether (DADPE) 92.9 Polymer H-2 4,4'-Oxydiphthalic dianhydride (ODPA) 147.11 2,2'-Bisdimethyl-4,4'-diaminobiphenyl (m-TB) 98.5 Polymer H-3 4,4'-Oxydiphthalic dianhydride (ODPA) 147.11 I-Phenylenediamine (PPD) 50.18 Polymer H-4 stilbenic dianhydride 229.2 I-Phenylenediamine (PPD) 50.18 Dicarboxylic acid (C) Mass of C (g) Diaminophenol (D) D mass (g) Polybenzoxazole Precursor Polymer I-1 4,4'-Diphenyl ether dicarboxylic acid 15.48 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane 18.3 Polymer I-2 sebacic acid 12.13 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane 18.3 Polymer I-3 Dicyclopentadiene dicarboxylic acid 11.3 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane 18.3 Cresol Novolak Resin (E) Mass of E (g) Modified phenolic resin (F) Mass of F (g) Phenolic resin Polymer J-1 J1 resin 85 J2 resin 15 Polymer J-2 J1 resin 100 J2 resin 0

[Examples 12-22, Comparative Examples 3-4] It prepared like Table 6 shown below, and obtained the solution of the photosensitive resin composition. In addition, the unit of Table 6 is a mass part.

Using the compound described in Table 6, each photosensitive resin composition of Examples 12-22 and Comparative Examples 3-4 was produced by the compounding quantity described in Table 7 and Table 8.

(4) 5% weight reduction temperature measurement test, (5) reflow resistance test of sealing material, (6) adhesion test with sealing material were performed about the produced photosensitive resin composition. The results of each test are shown in Table 7 below.

(4) 5% weight loss temperature measurement test A fan-out wafer-level chip size package type semiconductor device was manufactured using the photosensitive resin composition prepared in the examples and comparative examples. An interlayer insulating film with a thickness of 10 μm was taken out as thoroughly as possible from the manufactured semiconductor device. Using a DTG-60A device manufactured by Shimadzu Corporation, the taken-out interlayer insulating film was measured in a nitrogen atmosphere at a temperature increase rate of 10°C/min, and the 5% weight loss temperature was measured.

(5) Reflow resistance test of sealing materials R4000 series manufactured by Nagase Chemical Co., Ltd. was prepared as an epoxy-based sealing material. Next, the sealing material was spin-coated on the aluminum-sputtered silicon wafer to a thickness of about 150 μm, and the epoxy-based sealing material was cured by heat curing at 130°C.

The photosensitive resin composition produced in the Example and the comparative example was apply|coated on the said epoxy-type cured film so that the final film thickness might become 10 micrometers. For the coated photosensitive resin composition, the exposure conditions were 200 mJ/cm2 in Examples 12-15, 21, and Comparative Example 3, and 500 mJ/ ^cm2 in Examples 16-18, 22, and Comparative Example 4. /cm ² of the exposure conditions, in Examples 19 and 20, the exposure conditions of 700 mJ/cm ² were used to expose the entire surface, and then thermally cured at 180°C for 2 hours to make the first layer with a thickness of 10 μm. hardened film.

Apply the photosensitive resin composition used in the formation of the first layer cured film on the first layer cured film, expose the entire surface under the same conditions as when forming the first layer cured film, and then heat it. Harden to form a second cured film with a thickness of 10 μm.

The test piece after the formation of the second layer of cured film was heated to the peak temperature in a nitrogen atmosphere under simulated reflow conditions using a mesh belt continuous baking furnace (manufactured by Koyo Thermo Systems, model name 6841-20AMC-36) 260°C. The so-called simulated reflow conditions are based on the form of reflow conditions recorded in item 7.6 of the standard specification IPC/JEDEC J-STD-020A of the American Semiconductor Industry Association related to the evaluation method of semiconductor devices, and the melting point of the solder is assumed Standardized for the high temperature of 220°C.

Cut the cross-section of the cured film processed under the above-mentioned simulated reflow conditions with a FIB device (manufactured by JEOL Ltd., JIB-4000), and then confirm the presence or absence of pores in the epoxy part to evaluate the degree of deterioration. The case where no pore was found was made ◯, and the case where even one pore was found was made x.

(6) Adhesion test with sealing material The photosensitive resin cured film of the sample prepared in the test of (5) was put on a vertical probe, and the adhesion test was carried out using a traction tester (manufactured by Quad Group, Sebastian 5 type). Evaluation: Adhesion strength of 70 MPa or more・・・・・・・・・・・・・・・・・・・・Adhesive force◎ More than 50 MPa and less than -70 MPa・・・Adhesive force○ More than 30 MPa and less than -50 MPa・・・Adhesive force△ Less than 30 MPa・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・～

[Table 6] Photoinitiator K-1 photoacid generator K-2 crosslinking agent L-1 Weight Loss Temperature Regulator M-1 polyethylene glycol 3000 M-2 Polypropylene Glycol 3000 solvent N-1 γ-butyrolactone N-2 DMSO N-3 Propylene Glycol Monomethyl Ether Acetate N-4 ethyl lactate

[Table 7] Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 polymer H-1 100 H-2 100 H-3 100 H-4 100 I-1 100 I-2 100 I-3 100 J-1 100 J-2 100 Photoinitiator K-1 2 2 2 2 photoacid generator K-2 10 10 10 15 15 crosslinking agent L-1 15 15 Weight Loss Temperature Regulator M-1 15 15 15 15 12 12 12 16 16 M-2 solvent N-1 160 160 160 160 225 225 225 N-2 40 40 40 40 N-3 25 25 25 N-4 120 120 weight loss temperature 285 290 292 296 293 293 298 291 296 Reflow resistance test 〇 〇 〇 〇 〇 〇 〇 〇 〇 Adhesion test with sealing material ◎ 〇 〇 △ 〇 〇 △ 〇 △

[Table 8] Example 21 Example 22 Comparative example 3 Comparative example 4 polymer H-1 100 H-2 H-3 H-4 100 I-1 100 I-2 I-3 100 J-1 J-2 Photoinitiator K-1 2 2 photoacid generator K-2 10 10 crosslinking agent L-1 Weight Loss Temperature Regulator M-1 M-2 15 12 solvent N-1 160 225 160 225 N-2 40 40 N-3 25 25 N-4 weight loss temperature 286 290 308 310 Reflow resistance test 〇 〇 x x Adhesion test with sealing material ◎ 〇 x x

From Tables 7 and 8, it can be seen that when the 5% weight loss temperature is 300° C. or less, according to the results of the tests (4) to (6) performed on the photosensitive resin compositions of Examples 12 to 22, In the reflow resistance test of the sealing material, no voids were found in the epoxy part, and in the adhesion test with the sealing material, the evaluation of the adhesion force was either ◎, ○, or △.

On the other hand, according to Tables 7 and 8, it can be seen that according to the results of the tests (4) to (6) carried out with respect to the photosensitive resin compositions of Comparative Examples 3 and 4, it can be confirmed that the 5% weight loss temperature exceeds 300°C. In some cases, in the reflow resistance test of the sealing material, voids were found in the epoxy part, and in the adhesion test with the sealing material, the evaluation of the adhesion force was ×.

Using the photosensitive resin compositions of Examples 12 to 22, a fan-out wafer-level chip size package type semiconductor device in which epoxy resin was included in the mold resin was fabricated, and as a result, it was able to operate without any problem.

(Polymer O-1: Synthesis of Polyimide Precursor) 4,4'-oxydiphthalic dianhydride (ODPA) which is tetracarboxylic dianhydride was put into the 2-liter separable flask. Furthermore, 2-hydroxyethyl methacrylate (HEMA) and (gamma)-butyrolactone were put and stirred at room temperature, and pyridine was added, stirring, and the reaction mixture was obtained. After the exothermic heat generated by the reaction ended, it was left to cool to room temperature and left for 16 hours.

Next, under ice-cooling, while stirring a solution in which dicyclohexylcarbodiimide (DCC) was dissolved in γ-butyrolactone, it was added to the reaction mixture over 40 minutes. Then, what suspended 4,4'- diamino diphenyl ether (DADPE) as a diamine in (gamma)-butyrolactone was added over 60 minutes, stirring. Furthermore, after stirring at room temperature for 2 hours, ethanol was added and stirred for 1 hour, and then γ-butyrolactone was added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction liquid.

The obtained reaction solution was added to ethanol to generate a precipitate containing a crude polymer. The generated crude polymer was separated by filtration, and dissolved in tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to water to precipitate the polymer, and the obtained precipitate was separated by filtration and then vacuum-dried to obtain a powdered polymer (polyimide precursor (polymer O- 1)). The mass of the compound used for component O-1 is shown in Table 9 shown below.

(Synthesis of Polymer O-2～O-4) As shown in the following Table 9, the tetracarboxylic dianhydride and the diamine were changed, except that the reaction was carried out in the same manner as described in the above-mentioned polymer O-1, and a polyimide precursor (polymer O-2) was obtained. ~O-4).

(Polymer P-1: Synthesis of Polybenzoxazole Precursor) Into a 0.5-liter flask equipped with a stirrer and a thermometer, 15.48 g of 4,4'-diphenyl ether dicarboxylic acid and N-methylpyrrolidone were charged as a dicarboxylic acid. After cooling the flask to 5° C., thionyl chloride was added dropwise and allowed to react for 30 minutes to obtain a solution of dicarboxyl chloride. Next, N-methylpyrrolidone was placed in a 0.5-liter flask equipped with a stirrer and a thermometer. After stirring and dissolving 18.30 g of bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 2.18 g of m-aminophenol as bisaminophenol, pyridine was added. Then, while maintaining the temperature at 0 to 5° C., the solution of dicarboxyl chloride was added dropwise over 30 minutes, and stirring was continued for 30 minutes. The solution was poured into 3 liters of water, and the precipitate was recovered, washed three times with pure water, and then dried under reduced pressure to obtain a polymer (polybenzoxazole precursor (polymer P-1)). The mass of the compound used for polymer P-1 is shown in Table 9 below.

(Synthesis of Polymers P-2～P-3) Except that the dicarboxylic acid and the bisaminophenol were changed as shown in Table 9 below, the reaction was carried out in the same manner as described in the above-mentioned polymer P-1 to obtain a polybenzoxazole precursor (polymer P- 2～P-3).

(Polymer Q-1: Synthesis of Phenolic Resin) A phenol resin containing 85 g of Q1 resin shown below and 15 g of Q2 resin shown below was prepared as polymer Q-1. Q1: Cresol novolak resin (cresol/formaldehyde novolac resin, m-cresol/p-cresol (molar ratio) = 60/40, polystyrene-equivalent weight average molecular weight = 12,000, manufactured by Asahi Organic Materials Co., Ltd., Product name "EP4020G")

Q2: Q2 was synthesized as follows. <Q2: Synthesis of phenolic resin modified by a compound having an unsaturated hydrocarbon group with 4 to 100 carbons> 100 parts by mass of phenol, 43 parts by mass of linseed oil, and 0.1 part by mass of trifluoromethanesulfonic acid were mixed, stirred at 120° C. for 2 hours, and a vegetable oil-modified phenol derivative (a) was obtained. Next, 130 g of the vegetable oil-modified phenol derivative (a), 16.3 g of paraformaldehyde, and 1.0 g of oxalic acid were mixed, and stirred at 90° C. for 3 hours. Next, after heating up to 120 degreeC and stirring for 3 hours under reduced pressure, 29 g of succinic anhydride and 0.3 g of triethylamine were added to the reaction liquid, and it stirred at 100 degreeC for 1 hour under atmospheric pressure. The reaction solution was cooled to room temperature to obtain a phenolic resin (hereinafter referred to as "Q2 resin") (acid value 120 mgKOH/ g).

(Synthesis of Polymer Q-2) 100 g of the following Q1 resin was prepared as polymer Q-2.

[Table 9] polymer Tetracarboxylic dianhydride (A) A mass (g) Diamine (B) Mass of B (g) Polyimide Precursor Polymer O-1 4,4'-Oxydiphthalic dianhydride (ODPA) 147.11 4,4'-Diaminodiphenyl ether (DADPE) 92.9 Polymer O-2 4,4'-Oxydiphthalic dianhydride (ODPA) 147.11 2,2'-Bisdimethyl-4,4'-diaminobiphenyl (m-TB) 98.5 Polymer O-3 4,4'-Oxydiphthalic dianhydride (ODPA) 147.11 p-phenylenediamine (PPD) 50.18 Polymer O-4 stilbenic dianhydride 229.2 2,2'-Bis(trifluoromethyl)benzidine (TFMB) 148.51 Dicarboxylic acid (C) Mass of C (g) Diaminophenol (D) D mass (g) Polybenzoxazole Precursor Polymer P-1 4,4'-Diphenyl ether dicarboxylic acid 15.48 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane 18.3 Polymer P-2 sebacic acid 12.13 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane 18.3 Polymer P-3 Dicyclopentadiene dicarboxylic acid 11.3 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane 18.3 Cresol Novolak Resin (E) Mass of E (g) Modified phenolic resin (F) Mass of F (g) Phenolic resin Polymer Q-1 Q1 resin 85 Q2 resin 15 Polymer Q-2 Q1 resin 100 Q2 resin 0

[Examples 23 to 33, Comparative Examples 5 to 6] It prepared like Table 10 shown below, and obtained the solution of the photosensitive resin composition. In addition, the unit of Table 10 is a mass part.

Each photosensitive resin composition of Examples 23-33 and Comparative Examples 5-6 was produced with the compounding quantity described in Table 11 and Table 12 using the compound described in Table 10.

(7) Refractive index difference measurement test, (8) Reflow resistance test of sealing material, (9) Adhesion test with sealing material were performed about the produced photosensitive resin composition. The results of each test are shown in Table 11 below.

(7) Refractive index difference measurement test A fan-out WLCS semiconductor device was manufactured using the photosensitive resin compositions prepared in Examples and Comparative Examples. An interlayer insulating film with a thickness of 10 μm was taken out as thoroughly as possible from the manufactured semiconductor device. The difference between the in-plane refractive index and the out-of-plane refractive index at a wavelength of 1310 nm was measured for the taken-out interlayer insulating film using a Metricon coupler device (PC-2010).

(8) Reflow resistance test of sealing materials R4000 series manufactured by Nagase Chemical Co., Ltd. was prepared as an epoxy-based sealing material. Next, the sealing material was spin-coated on the aluminum-sputtered silicon wafer to a thickness of about 150 μm, and the epoxy-based sealing material was cured by heat curing at 130°C.

The photosensitive resin composition produced in the Example and the comparative example was apply|coated on the said epoxy-type cured film so that the final film thickness might become 10 micrometers. For the coated photosensitive resin composition, the exposure conditions were 200 mJ/cm2 in Examples 23-26, 32, and Comparative Example 5, and 500 mJ/ ^cm2 in Examples 27-29, 33, and Comparative Example 6. /cm ² exposure conditions, after exposing the entire surface, heat hardening at 150°C for 4 hours to form the first layer of cured film with a thickness of 10 μm.

Coat the photosensitive resin composition used in the formation of the first layer cured film on the first layer cured film, expose the entire surface under the same conditions as the first layer cured film, and then use It is thermally cured to form a second cured film with a thickness of 10 μm.

The test piece after the formation of the second layer of cured film was heated to the peak temperature in a nitrogen atmosphere under simulated reflow conditions using a mesh belt continuous baking furnace (manufactured by Koyo Thermo Systems, type name 6841-20AMC-36) 260°C. The so-called simulated reflow conditions are based on the form of reflow conditions recorded in item 7.6 of the standard specification IPC/JEDEC J-STD-020A of the American Semiconductor Industry Association related to the evaluation method of semiconductor devices, and the melting point of the solder is assumed to be Standardized for the high temperature of 220°C.

Cut the cross-section of the cured film processed under the above-mentioned simulated reflow conditions with a FIB device (manufactured by JEOL Ltd., JIB-4000), and then confirm the presence or absence of pores in the epoxy part to evaluate the degree of deterioration. The case where no pore was found was made ◯, and the case where even one pore was found was made x.

(9) Adhesion test with sealing material The samples produced in (8) were tested for adhesion using a traction tester (manufactured by Quad Group, Sebastian 5) on the cured film of the photosensitive resin with a vertical stylus. Evaluation: Adhesion strength of 70 MPa or more・・・・・・・・・・・・・・・・・・・・Adhesive force◎ More than 50 MPa and less than -70 MPa・・・Adhesive force○ More than 30 MPa and less than -50 MPa・・・Adhesive force△ Less than 30 MPa・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・・～

[Table 10] Photoinitiator R-1 photoacid generator R-2 crosslinking agent S-1 Refractive Index Difference Adjuster T-1 Bicyclooctane T-2 Adamantane T-3 N-(4-Bromophenyl)phthalimide solvent U-1 γ-butyrolactone U-2 DMSO U-3 Propylene Glycol Monomethyl Ether Acetate U-4 ethyl lactate

[Table 11] Example 23 Example 24 Example 25 Example 26 Example 27 Example 28 Example 29 Example 30 Example 31 polymer O-1 100 O-2 100 O-3 100 O-4 100 P-1 100 P-2 100 P-3 100 Q-1 100 Q-2 100 Photoinitiator R-1 2 2 2 2 photoacid generator R-2 10 10 10 15 15 crosslinking agent S-1 15 15 Refractive Index Difference Adjuster T-1 10 10 10 10 8 8 8 12 12 T-2 T-3 solvent U-1 160 160 160 160 225 225 225 U-2 40 40 40 40 U-3 25 25 25 U-4 120 120 Refractive index difference 0.0140 0.0142 0.0144 0.0148 0.0142 0.0143 0.0147 0.0143 0.0148 Reflow resistance test 〇 〇 〇 〇 〇 〇 〇 〇 〇 Adhesion test with sealing material ◎ 〇 〇 △ 〇 〇 △ 〇 △

[Table 12] Example 32 Example 33 Comparative Example 5 Comparative Example 6 polymer O-1 100 O-2 O-3 O-4 100 P-1 100 P-2 P-3 100 Q-1 Q-2 Photoinitiator R-1 2 2 photoacid generator R-2 10 10 crosslinking agent S-1 Refractive Index Difference Adjuster T-1 T-2 10 8 T-3 30 30 solvent U-1 160 225 160 225 U-2 40 40 U-3 25 25 U-4 Refractive index difference 0.0141 0.0143 0.0163 0.0166 Reflow resistance test 〇 〇 x x Adhesion test with sealing material ◎ 〇 x x

According to Tables 11 and 12, it can be seen that according to the results of the tests (7) to (9) carried out on the photosensitive resin compositions of Examples 23 to 33, it can be confirmed that when the difference in refractive index is less than 0.0150, the sealing material In the reflow resistance test, no voids were found in the epoxy part, and in the adhesion test with the sealing material, the evaluation of the adhesion force was either ◎, ○, or △.

On the other hand, according to Tables 11 and 12, it can be confirmed that when the difference in refractive index exceeds 0.0150, according to the results of the tests (7) to (9) carried out with respect to the photosensitive resin compositions of Comparative Examples 5 and 6, In the reflow resistance test of the sealing material, voids were found in the epoxy part, and in the adhesion test with the sealing material, the evaluation of the adhesion force was ×.

In addition, fan-out wafer-level chip size package type semiconductor devices in which epoxy resin was included in the molding resin were fabricated using the photosensitive resin compositions of Examples 23 to 33, and as a result, they were able to operate without problems. [Industrial availability]

The present invention can be preferably applied to a semiconductor device including a semiconductor chip and a redistribution layer connected to the semiconductor chip, especially a Fan-Out WLCS semiconductor device.

1: Semiconductor device 2: Semiconductor wafer 2a: terminal 3: Sealing material 4: Redistribution layer 5: Wiring 6: Interlayer insulation film 7: External connection terminal 8: Flip chip BGA 9: Fan-Out WLCSP 10:Wafer 11: Support body 12: Molding resin 13: Photosensitive resin composition 14: Sealing resin 15: Solder bumps 16: Solder ball 17: Intermediary layer A: arrow S1: area of redistribution layer S2: Area of semiconductor chip

FIG. 1 is a schematic cross-sectional view of a semiconductor device according to this embodiment. FIG. 2 is a schematic plan view of the semiconductor device of the present embodiment. 3A to 3H are examples of manufacturing steps of the semiconductor device of this embodiment. Figure 4 is a comparison diagram of flip-chip BGA and fan-out (Fan-Out) WLCSP.

1: Semiconductor device

2: Semiconductor wafer

2a: terminal

3: Sealing material

4: Redistribution layer

5: Wiring

6: Interlayer insulation film

7: External connection terminal

A: arrow

Claims (70)

A semiconductor device, characterized in that it comprises: a semiconductor wafer, sealing material, and A redistribution layer with a larger area in plan view than the above-mentioned semiconductor wafer, and The sealing material has a portion directly in contact with the interlayer insulating film of the redistribution layer, The 5% weight loss temperature of the interlayer insulating film of the rewiring layer is 300°C or lower. The semiconductor device according to claim 1, wherein the sealing material includes epoxy resin. The semiconductor device according to claim 1 or 2, wherein the interlayer insulating film comprises at least one selected from polyimide, polybenzoxazole, and a polymer having a phenolic hydroxyl group. The semiconductor device according to claim 3, wherein the interlayer insulating film comprises polyimide having a structure of the following general formula (1), [Chemical 15] (In the general formula (1), X ¹ is a tetravalent organic group, Y ¹ is a divalent organic group, and m is an integer of 1 or more). Such as the semiconductor device ^of claim 4, wherein X in the above general formula (1) is a tetravalent organic group containing an aromatic ring, and Y in the above general formula ( ¹ ) is a divalent organic group containing an aromatic ring base. The semiconductor device according to claim 4, wherein ^X in the above general formula (1) includes at least one structure represented by the following general formula (2) to general formula (4), [Chemical 16] [chemical 17] [chemical 18] (In the general formula (4), R ₉ is an oxygen atom, a sulfur atom, or a divalent organic group). Such as the semiconductor device of claim 6, wherein ^X in the above-mentioned general formula (1) comprises a structure represented by the following general formula (5), [Chemical 19] . The semiconductor device according to claim 4, wherein ^Y in the above general formula (1) includes at least one structure represented by the following general formula (6) to general formula (8), [Chem. 20] (R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are a hydrogen atom, a monovalent aliphatic group with 1 to 5 carbons or a hydroxyl group, which may be the same or different) [Chem. 21] (R ₁₄ to R ₂₁ are a hydrogen atom, a halogen atom, a monovalent organic group with 1 to 5 carbons, or a hydroxyl group, which may be different from each other or the same) [Chemical 22] (R ₂₂ is a divalent organic group or an oxygen atom, and R ₂₃ to R ₃₀ are a hydrogen atom, a halogen atom, a monovalent aliphatic group with 1 to 5 carbon atoms, or a hydroxyl group, which may be the same or different). Such as the semiconductor device of claim 8, wherein Y in the above-mentioned general formula (1) ¹ comprises the structure represented by the following general formula (9), [Chemical 23] . The semiconductor device according to claim 3, wherein the polybenzoxazole includes a polybenzoxazole having a structure of the following general formula (10), [Chem. 24] (In the general formula (10), U and V are divalent organic groups). The semiconductor device according to claim 10, wherein U in the above general formula (10) is a divalent organic group having 1 to 30 carbon atoms. The semiconductor device according to claim 11, wherein U in the above general formula (10) is a chain alkylene group having 1 to 8 carbon atoms and part or all of the hydrogen atoms are substituted with fluorine atoms. The semiconductor device according to claim 10, wherein V in the above general formula (10) is a divalent organic group containing an aromatic group. The semiconductor device according to claim 13, wherein V of the above general formula (10) includes at least one structure represented by the following general formulas (6) to (8), [Chem. 25] (R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are a hydrogen atom and a monovalent aliphatic group with 1 to 5 carbon atoms, which may be the same or different) [Chemical 26] (R ₁₄ to R ₂₁ are a hydrogen atom, a halogen atom, or a monovalent organic group with 1 to 5 carbon atoms, which may be different or the same) [Chemical 27] (R ₂₂ is a divalent organic group or an oxygen atom, and R ₂₃ to R ₃₀ are hydrogen atoms, halogen atoms, or monovalent aliphatic groups with 1 to 5 carbon atoms, which may be the same or different). Such as the semiconductor device of claim 14, wherein V of the above-mentioned general formula (10) comprises a structure represented by the following general formula (9), [Chemical 28] . The semiconductor device according to claim 10, wherein V in the above general formula (10) is a divalent organic group having 1 to 40 carbon atoms. The semiconductor device according to claim 16, wherein V in the above general formula (10) is a divalent chain aliphatic group having 1 to 20 carbon atoms. The semiconductor device according to claim 3, wherein the polymer having a phenolic hydroxyl group comprises a novolak type phenolic resin. The semiconductor device according to claim 3, wherein the polymer having a phenolic hydroxyl group includes a phenol resin not having an unsaturated hydrocarbon group and a modified phenol resin having an unsaturated hydrocarbon group. The semiconductor device according to claim 1 or 2, wherein when the rewiring layer is observed in section, the rewiring layer includes: a first interlayer insulating film layer; a second interlayer insulating film layer; and an intermediate layer, which is the same as the above-mentioned The first interlayer insulating film layer and the second interlayer insulating film layer are different layers, and are disposed between the first interlayer insulating film layer and the second interlayer insulating film layer. The semiconductor device according to claim 20, wherein the first interlayer insulating film layer is in contact with the sealing material, and the 5% weight reduction temperature of the first interlayer insulating film layer is 300°C or lower. The semiconductor device according to claim 20, wherein the composition of the second interlayer insulating film layer is different from that of the first interlayer insulating film layer. The semiconductor device according to claim 20, wherein the 5% weight loss temperature of the second interlayer insulating film layer is different from the 5% weight loss temperature of the first interlayer insulating film layer. The semiconductor device according to claim 1 or 2, wherein the semiconductor device is a fan-out wafer-level chip size package semiconductor device. The semiconductor device according to claim 1 or 2, wherein the 5% weight loss temperature of the interlayer insulating film of the rewiring layer is 280°C or lower. The semiconductor device according to claim 25, wherein the 5% weight loss temperature of the interlayer insulating film of the rewiring layer is 260°C or lower. The semiconductor device according to claim 25, wherein the 5% weight reduction temperature of the interlayer insulating film of the rewiring layer is 240°C or lower. The semiconductor device according to claim 25, wherein the 5% weight reduction temperature of the interlayer insulating film of the rewiring layer is 220°C or lower. The semiconductor device according to claim 25, wherein the 5% weight loss temperature of the interlayer insulating film of the rewiring layer is 200°C or lower. The semiconductor device according to claim 1 or 2, wherein the 5% weight reduction temperature of the interlayer insulating film of the rewiring layer is 80° C. or higher. The semiconductor device according to claim 30, wherein the 5% weight reduction temperature of the interlayer insulating film of the rewiring layer is 100°C or lower. The semiconductor device according to claim 30, wherein the 5% weight reduction temperature of the interlayer insulating film of the rewiring layer is 150°C or lower. A method of manufacturing a semiconductor device, characterized by comprising: a step of forming a wafer sealing body with a semiconductor wafer and a sealing material, and A step of forming a rewiring layer having an area larger than the semiconductor wafer in plan view and including an interlayer insulating film, and The sealing material has a portion directly in contact with the interlayer insulating film of the redistribution layer, The 5% weight loss temperature of the interlayer insulating film is 300°C or lower. The method for manufacturing a semiconductor device according to Claim 33, which includes forming the above-mentioned interlayer insulating film using a photosensitive resin composition that can form at least one compound of polyimide, polybenzoxazole, and a polymer having a phenolic hydroxyl group Interlayer insulating film forming step. The method for manufacturing a semiconductor device according to claim 34, wherein the step of forming the interlayer insulating film includes forming the interlayer insulating film using the photosensitive resin composition adjusted with additives so that the 5% weight reduction temperature of the interlayer insulating film becomes 300°C or lower. Insulation film step. A semiconductor device, characterized in that it comprises: a semiconductor wafer, sealing material, and A redistribution layer with a larger area in plan view than the above-mentioned semiconductor wafer, and The sealing material has a portion directly in contact with the interlayer insulating film of the redistribution layer, The absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index at the wavelength of 1310 nm of the interlayer insulating film of the rewiring layer is less than 0.0150. The semiconductor device according to claim 36, wherein said sealing material comprises epoxy resin. The semiconductor device according to claim 36 or 37, wherein the interlayer insulating film includes at least one selected from polyimide, polybenzoxazole, and a polymer having a phenolic hydroxyl group. The semiconductor device according to claim 38, wherein the interlayer insulating film comprises polyimide having a structure of the following general formula (1), [Chemical 29] (In the general formula (1), X ¹ is a tetravalent organic group, Y ¹ is a divalent organic group, and m is an integer of 1 or more). Such as the semiconductor device of claim 39, wherein X in the above general formula (1) is a quaternary organic group containing an aromatic ring, and Y in the above general formula ( ¹ ) is a ^divalent organic group containing an aromatic ring . The semiconductor device according to claim 39, wherein ^X in the above-mentioned general formula (1) includes at least one structure represented by the following general formula (2) to general formula (4), [Chemical 30] [chem 31] [chem 32] (In the general formula (4), R ₉ is an oxygen atom, a sulfur atom, or a divalent organic group). Such as the semiconductor device of claim 41, wherein ^X in the above-mentioned general formula (1) comprises a structure represented by the following general formula (5), [Chemical 33] . The semiconductor device according to claim 39, wherein ^Y in the above general formula (1) includes at least one structure represented by the following general formula (6) to general formula (8), [Chemical 34] (R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are a hydrogen atom, a monovalent aliphatic group with 1 to 5 carbons or a hydroxyl group, which may be the same or different) [Chemical 35] (R ₁₄ to R ₂₁ are a hydrogen atom, a halogen atom, a monovalent organic group with 1 to 5 carbons, or a hydroxyl group, which may be different or the same) [Chemical 36] (R ₂₂ is a divalent group or an oxygen atom, and R ₂₃ to R ₃₀ are a hydrogen atom, a halogen atom, a monovalent aliphatic group with 1 to 5 carbon atoms, or a hydroxyl group, which may be the same or different). Such as the semiconductor device of claim 43, wherein ^Y in the above general formula (1) comprises a structure represented by the following general formula (9), [Chemical 37] . The semiconductor device according to claim 38, wherein the polybenzoxazole includes a polybenzoxazole having a structure of the following general formula (10), [Chemical 38] (In the general formula (10), U and V are divalent organic groups). The semiconductor device according to claim 45, wherein U in the above general formula (10) is a divalent organic group having 1 to 30 carbon atoms. The semiconductor device according to claim 46, wherein U in the above general formula (10) is a chain alkylene group having 1 to 8 carbon atoms and part or all of the hydrogen atoms are substituted by fluorine atoms. The semiconductor device according to claim 45, wherein V in the above general formula (10) is a divalent organic group containing an aromatic group. The semiconductor device according to claim 48, wherein V of the above general formula (10) includes at least one structure represented by the following general formulas (6) to (8), [Chemical 39] (R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are a hydrogen atom and a monovalent aliphatic group with 1 to 5 carbon atoms, which may be the same or different) [Chemical 40] (R ₁₄ to R ₂₁ are a hydrogen atom, a halogen atom, or a monovalent organic group with 1 to 5 carbon atoms, which may be different or the same) [Chem. 41] (R ₂₂ is a divalent group or an oxygen atom, and R ₂₃ to R ₃₀ are hydrogen atoms, halogen atoms, or monovalent aliphatic groups with 1 to 5 carbon atoms, which may be the same or different). Such as the semiconductor device of claim 49, wherein V of the above-mentioned general formula (10) comprises a structure represented by the following general formula (9), [化42] . The semiconductor device according to claim 45, wherein V in the above general formula (10) is a divalent organic group having 1 to 40 carbon atoms. The semiconductor device according to claim 51, wherein V in the above general formula (10) is a divalent chain aliphatic group having 1 to 20 carbon atoms. The semiconductor device according to claim 38, wherein the polymer having a phenolic hydroxyl group includes a novolac type phenolic resin. The semiconductor device according to claim 38, wherein the polymer having a phenolic hydroxyl group includes a phenol resin not having an unsaturated hydrocarbon group and a modified phenol resin having an unsaturated hydrocarbon group. The semiconductor device according to claim 36 or 37, wherein when the redistribution layer is observed in section, the redistribution layer includes: a first interlayer insulating film layer; a second interlayer insulating film layer; and an intermediate layer, which is the same as the above-mentioned The first interlayer insulating film layer and the second interlayer insulating film layer are different layers, and are disposed between the first interlayer insulating film layer and the second interlayer insulating film layer. The semiconductor device according to claim 55, wherein the first interlayer insulating film is in contact with the sealing material, and the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the first interlayer insulating film is less than 0.0150. The semiconductor device according to claim 55, wherein the composition of the second interlayer insulating film layer is different from that of the first interlayer insulating film layer. The semiconductor device according to Claim 55, wherein the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the second interlayer insulating film layer is the difference between the in-plane refractive index and the out-of-plane refractive index of the first interlayer insulating film layer The absolute values of the differences are different. The semiconductor device according to claim 36 or 37, wherein the semiconductor device is a fan-out wafer-level chip size package semiconductor device. The semiconductor device according to claim 36 or 37, wherein the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the rewiring layer is 0.0145 or less. The semiconductor device according to Claim 60, wherein the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the redistribution layer is 0.0140 or less. The semiconductor device according to Claim 60, wherein the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the redistribution layer is 0.0135 or less. The semiconductor device according to claim 60, wherein the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the redistribution layer is 0.0130 or less. The semiconductor device according to claim 60, wherein the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the rewiring layer is 0.0120 or less. The semiconductor device according to claim 36 or 37, wherein the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the rewiring layer is 0.0005 or more. The semiconductor device according to Claim 65, wherein the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the rewiring layer is 0.0010 or more. The semiconductor device according to claim 65, wherein the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the rewiring layer is 0.0015 or more. A method of manufacturing a semiconductor device, characterized by comprising: a step of forming a wafer sealing body with a semiconductor wafer and a sealing material, and A step of forming a rewiring layer having an area larger than the semiconductor wafer in plan view and including an interlayer insulating film, and The sealing material has a portion directly in contact with the interlayer insulating film of the redistribution layer, The absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film is less than 0.0150. The method of manufacturing a semiconductor device according to claim 68, which includes forming the above-mentioned interlayer insulating film using a photosensitive resin composition that can form at least one compound of polyimide, polybenzoxazole, and a polymer having a phenolic hydroxyl group Interlayer insulating film forming step. The method of manufacturing a semiconductor device according to claim 69, wherein the step of forming the interlayer insulating film includes using additives to adjust the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film to less than 0.0150. The step of forming the above-mentioned interlayer insulating film from the above-mentioned photosensitive resin composition.