TWI762676B - Semiconductor device and method of manufacturing the same - Google Patents

Abstract

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. The semiconductor device (1) of the present invention is characterized by comprising: a semiconductor wafer (2), a sealing material (3) covering the semiconductor wafer, and a rewiring layer (4) having an area larger than that of the semiconductor wafer in plan view, and the rewiring The i-ray transmittance of the interlayer insulating film (6) between the layers is 80% or less. According to the present invention, a semiconductor device having excellent adhesion between the interlayer insulating film and the sealing material in the rewiring layer and a method for manufacturing the same can be provided.

Description

Semiconductor device and method of manufacturing the same

The present invention relates to a semiconductor device and a method for manufacturing the same.

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 a semiconductor wafer is covered with a sealing material (molding resin) to form an element sealing material, and further a rewiring layer electrically connected to the semiconductor wafer is formed. Among the semiconductor packaging methods, a fan-out semiconductor packaging method has become the mainstream in recent years.

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

For example, as a fan-out type semiconductor device, the following Patent Document 1 is known.

[Prior Art Literature] [Patent Literature]

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

In a fan-out type semiconductor device, high adhesion between the interlayer insulating film in the rewiring layer and the sealing material is required. However, the adhesiveness between the interlayer insulating film and the sealing material in the rewiring layer of the conventional fan-out type semiconductor device is insufficient.

The present invention is made in view of this point, and an object thereof is to provide a semiconductor device having excellent adhesion between the interlayer insulating film and the sealing material in the rewiring layer, and a method for producing the same.

The semiconductor device of the present invention is characterized by comprising: a semiconductor chip, a sealing material covering the semiconductor chip, and a rewiring layer having an area larger than the semiconductor chip in plan view, and the i-ray transmittance of the interlayer insulating film between the rewiring layers is 10 μm in thickness The conversion calculation is less than 80%.

In the present invention, the sealing material and the interlayer insulating film are preferably in direct contact with each other.

In this invention, it is preferable that the said sealing material contains epoxy resin.

唑、及具有酚性羥基之聚合物之至少一種。 In the present invention, it is preferable that the above-mentioned interlayer insulating film comprises a material selected from the group consisting of polyimide, polybenzoyl

At least one of an azole and a polymer having a phenolic hydroxyl group.

In the present invention, it is preferable that the above-mentioned interlayer insulating film contains a compound having the structure of the following general formula (1) Polyimide.

(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)

In the present invention, X ¹ in the general formula (1) is preferably a tetravalent organic group containing an aromatic ring, and Y ¹ in the general formula (1) is a divalent organic group containing an aromatic ring.

In the present invention, X ¹ in the general formula (1) preferably includes at least one structure represented by the following general formula (2) to (4).

[hua 4]

(In the general formula (4), R ₉ is an oxygen atom, a sulfur atom, or a divalent organic group)

In the present invention, X ¹ in the above-mentioned general formula (1) preferably includes a structure represented by the following general formula (5).

In the present invention, it is preferable that Y ¹ in the above general formula (1) includes at least one structure represented by the following general formula (6) to (8).

(R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are hydrogen atoms, monovalent aliphatic groups or hydroxyl groups having 1 to 5 carbon atoms, which may be the same or different)

[hua 7]

(R ₁₄ to R ₂₁ are hydrogen atoms, halogen atoms, monovalent organic groups with 1 to 5 carbon atoms, or hydroxyl groups, which may be different from each other or the same)

(R ₂₂ is a divalent organic group, 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)

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

唑包含含有以下通式(10)之結構之聚苯并

唑。 In the present invention, preferably the above-mentioned polybenzo

The azoles include polybenzos having the structure of the following general formula (10)

azoles.

(In the 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 general formula (10) is preferably a chain alkylene group having 1 to 8 carbon atoms and a part or all of hydrogen atoms substituted by fluorine atoms.

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

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

(R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are hydrogen atoms and monovalent aliphatic groups having 1 to 5 carbon atoms, which may be the same or different)

(R ₁₄ to R ₂₁ are hydrogen atoms, halogen atoms, and monovalent organic groups with 1 to 5 carbon atoms, which may be different from each other or the same)

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

In this invention, it is preferable that V of the said general formula (10) contains the structure represented by following general formula (9).

In the present invention, it is preferable that V in the general formula (10) is 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 this invention, it is preferable that the said polymer which has a phenolic hydroxyl group contains a novolac-type phenol resin.

In this invention, it is preferable that the said polymer which has a phenolic hydroxyl group contains the phenol resin which does not have an unsaturated hydrocarbon group, and the modified phenol resin which has an unsaturated hydrocarbon group.

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

In the present invention, the first interlayer insulating film layer is preferably in contact with the sealing material, and the i-ray transmittance of the first interlayer insulating film layer is preferably 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, the i-ray transmittance of the second interlayer insulating film layer is preferably 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 type wafer-level chip-scale package type 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 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 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 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 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 thickness of 10 μm.

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

In the present invention, the i-ray transmittance of the interlayer insulating film of the above-mentioned rewiring layer can also be set as thick as The degree of 10μm is calculated as 10% or more.

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

The method for manufacturing a semiconductor device of the present invention is characterized by comprising: a step of covering a 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 80% or less in terms of thickness of 10 μm.

唑、具有酚性羥基之聚合物之至少一種化合物之感光性樹脂組合物形成上述層間絕緣膜的層間絕緣膜形成步驟。 In the present invention, it is preferable to include the use of polyimide, polybenzoyl

The photosensitive resin composition of azole and at least one compound of a polymer having a phenolic hydroxyl group forms the interlayer insulating film forming step of the above-mentioned interlayer insulating film.

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

An aspect of the semiconductor device of the present embodiment is characterized by comprising: a semiconductor chip, a sealing material covering the semiconductor chip, a rewiring layer having an area larger than that of the semiconductor chip in plan view, 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, the above-mentioned sealing material and the above-mentioned layer are preferably The insulating film is directly connected to each other.

In one aspect of the semiconductor device of the present invention, the sealing material preferably includes epoxy resin.

唑、及具有酚性羥基之聚合物之至少一種。 In one aspect of the semiconductor device of the present invention, it is preferable that the interlayer insulating film comprises a material selected from the group consisting of polyimide, polybenzoyl

At least one of an azole and a polymer having a phenolic hydroxyl group.

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

(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)

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

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

(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, X ¹ in the above general formula (1) preferably includes a structure represented by the following general formula (5).

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).

(R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are hydrogen atoms, monovalent aliphatic groups or hydroxyl groups having 1 to 5 carbon atoms, which may be the same or different)

(R ₁₄ to R ₂₁ are hydrogen atoms, halogen atoms, monovalent organic groups with 1 to 5 carbon atoms, or hydroxyl groups, which may be different from each other or the same)

(R ₂₂ is a divalent group, 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)

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

唑。 In one aspect of the semiconductor device of the present invention, it is preferable that the above-mentioned interlayer insulating film includes polybenzoyl having a structure of the following general formula (10)

azoles.

(In the 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, preferably U in the above general formula (10) is the number of carbons 1 to 8 chain alkylene groups in which part or all of hydrogen atoms are substituted by fluorine atoms.

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

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

(R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are hydrogen atoms and monovalent aliphatic groups having 1 to 5 carbon atoms, which may be the same or different)

(R ₁₄ to R ₂₁ are hydrogen atoms, halogen atoms, and monovalent organic groups with 1 to 5 carbon atoms, which may be different from each other or the same)

[Chemical 27]

(R ₂₂ is a divalent group, and R ₂₃ to R ₃₀ are a hydrogen atom, a halogen atom, and a monovalent aliphatic group 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 of the above general formula (10) includes a structure represented by the following general formula (9).

In one aspect of the semiconductor device of the present invention, it is preferable that V of the general formula (10) is 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, the polymer having a phenolic hydroxyl group preferably includes a novolac-type phenol 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 having no 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 cross-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, the first interlayer insulating film layer is preferably in contact with the sealing material, and the 5% weight reduction temperature of the first interlayer insulating film layer is preferably 300° C. or lower.

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

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

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

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

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

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

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

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

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

In one aspect of the semiconductor device of the present invention, the 5% weight reduction temperature of the interlayer insulating film of the rewiring layer is preferably 150° C. or higher.

In one aspect of the method for manufacturing a semiconductor device of the present invention, it is characterized by comprising: The step of covering the semiconductor wafer with a sealing material and the 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 5% weight reduction temperature of the interlayer insulating film is below 300°C.

唑、具有酚性羥基之聚合物之至少一種化合物之感光性樹脂組合物形成上述層間絕緣膜的層間絕緣膜形成步驟。 In one aspect of the method for manufacturing a semiconductor device of the present invention, it preferably includes the use of polyimide, polybenzoyl

The photosensitive resin composition of azole and at least one compound of a polymer having a phenolic hydroxyl group forms the interlayer insulating film forming step of the above-mentioned interlayer insulating film.

In one aspect of the method for manufacturing a semiconductor device of the present invention, it is preferable that the interlayer insulating film forming step includes the use of the photosensitivity adjusted by an additive so that the 5% weight reduction temperature of the interlayer insulating film becomes 300° C. or lower. The resin composition is a 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 chip, a sealing material covering the semiconductor chip, and a rewiring layer having an area larger than that of the semiconductor chip in plan view, and the interlayer insulating film of the rewiring layer has a wavelength of 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, the sealing material and the interlayer insulating film are preferably in direct contact with each other.

In one aspect of the semiconductor device of the present invention, the sealing material preferably includes epoxy resin.

唑、及具有酚性羥基之聚合物之至少一種。 In one aspect of the semiconductor device of the present invention, it is preferable that the interlayer insulating film comprises a material selected from the group consisting of polyimide, polybenzoyl

At least one of an azole and a polymer having a phenolic hydroxyl group.

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

(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)

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

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

[Chemical 30]

(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, X ¹ in the above general formula (1) preferably includes a structure represented by the following general formula (5).

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).

(R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are hydrogen atoms, monovalent aliphatic groups or hydroxyl groups having 1 to 5 carbon atoms, which may be the same or different)

(R ₁₄ to R ₂₁ are hydrogen atoms, halogen atoms, monovalent organic groups with 1 to 5 carbon atoms, or hydroxyl groups, which may be different from each other or the same)

(R ₂₂ is a divalent group, 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)

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

唑包含含有以下通式(10)之結構之聚苯并

唑。 In one aspect of the semiconductor device of the present invention, the above-mentioned polybenzo

The azoles include polybenzos having the structure of the following general formula (10)

azoles.

(In the 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 of the general formula (10) is preferably a chain alkylene group having 1 to 8 carbon atoms and a part or all of hydrogen atoms substituted by fluorine atoms.

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

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

(R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are hydrogen atoms and monovalent aliphatic groups having 1 to 5 carbon atoms, which may be the same or different)

(R ₁₄ to R ₂₁ are hydrogen atoms, halogen atoms, and monovalent organic groups with 1 to 5 carbon atoms, which may be different from each other or the same)

[Chemical 41]

(R ₂₂ is a divalent group, and R ₂₃ to R ₃₀ are a hydrogen atom, a halogen atom, and a monovalent aliphatic group 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 of the above general formula (10) includes a structure represented by the following general formula (9).

In one aspect of the semiconductor device of the present invention, it is preferable that V of the general formula (10) is 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, the polymer having a phenolic hydroxyl group preferably includes a novolac-type phenol 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 having no unsaturated hydrocarbon group and a modified phenol resin having an unsaturated hydrocarbon group.

In one aspect of the semiconductor device of the present invention, when the rewiring layer is observed in cross-section, preferably, the rewiring layer includes a first interlayer insulating film layer; a second interlayer insulating film 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, it is preferable that the first interlayer insulating film layer 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 layer is The value does not reach 0.0150.

In one aspect of the semiconductor device of 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 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 second interlayer insulating film layer and the in-plane refractive index of the first interlayer insulating film layer are preferably Different from the absolute value of the difference in the out-of-plane refractive index.

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

In one aspect of the semiconductor device of the present invention, the interlayer insulation between the rewiring layers is preferably The absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the edge film is 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, 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 0.0120 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 0.0005 or more.

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 0.0010 or more.

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 0.0015 or more.

One aspect of the method of manufacturing a semiconductor device of the present invention is characterized by comprising: a step of covering a semiconductor chip with a sealing material; and a step of forming a rewiring layer having an area larger than the semiconductor chip 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.

唑、具有酚性羥基之聚合物之至少一種化合物之感光性樹脂組合物形成上述層間絕緣膜的層間絕緣膜形成步驟。 In one aspect of the method for manufacturing a semiconductor device of the present invention, it preferably includes the use of polyimide, polybenzoyl

The photosensitive resin composition of azole and at least one compound of a polymer having a phenolic hydroxyl group forms the interlayer insulating film forming step of the above-mentioned interlayer insulating film.

In one aspect of the method of manufacturing a semiconductor device of the present invention, it is preferable that the interlayer insulating film forming step includes utilizing 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 be less than 0.0150. A step of forming the above-mentioned interlayer insulating film from the above-mentioned photosensitive resin composition adjusted by additives.

According to the present invention, a semiconductor device having excellent adhesion between an interlayer insulating film in a rewiring layer and a sealing material, and a method for producing the same can be provided.

1: Semiconductor device

2: Semiconductor wafer

2a: Terminal

3: sealing material

4: Rewiring layer

5: Wiring

6: Interlayer insulating film

7: External connection terminal

10: Wafer

11: Support body

12: Molding resin

13: Photosensitive resin composition

A: Arrow

S1: Area

S2: Area

FIG. 1 is a schematic cross-sectional view of the semiconductor device of the present 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 the present embodiment.

FIG. 4 is a comparison diagram of a flip-chip BGA and a fan-out (Fan-Out) WLCSP.

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 added and implemented within the range of the summary.

(semiconductor device)

As shown in FIG. 1 , a semiconductor device (semiconductor IC) 1 includes a semiconductor wafer 2 , a sealing material (molding resin) 3 covering the semiconductor wafer 2 , and a rewiring layer 4 in close contact with the semiconductor wafer 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 a larger area than the area of the semiconductor wafer 2 in plan view (viewed along the arrow A).

The rewiring layer 4 has a plurality of wirings 5 electrically connected to the plurality of terminals 2 a provided on the semiconductor chip 2 , and an interlayer insulating film 6 that fills the wirings 5 . The plurality of terminals 2 a provided on the semiconductor chip 2 are electrically connected to the wirings 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 wiring 5 between the terminal 2a and the external connection terminal 7 is covered by the interlayer insulating film 6 over the entire surface.

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

(rewiring layer)

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

Here, the so-called "rewiring layer 4" in the present embodiment is a thin film layer having the wiring 5 and the interlayer insulating film 6 as described above, and does not include an interposer or a printed wiring board. FIG. 4 is a comparison diagram of a flip-chip BGA and a fan-out (Fan-Out) WLCSP. Since the semiconductor device (semiconductor IC) 1 (see FIG. 1 ) uses the rewiring layer 4 , as shown in FIG. 4 , it 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 about 3 to 30 μm. The film thickness of the rewiring layer 4 may be 1 μm or more, 5 μm or more, or 10 μm or more. Moreover, the film thickness of the rewiring layer 4 may be 40 μm or less, 30 μm or less, or 20 μm or less.

When the semiconductor device 1 is viewed in plan (viewed along the arrow A), it is 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.

In the semiconductor device 1 shown in FIG. 2 , the area S1 of the redistribution layer 4 is larger than that of the semiconductor wafer 2 . The area S2 is formed. The area S1 of the rewiring layer 4 is not particularly limited, but from the viewpoint of increasing the number of external connection terminals, the area S1 of the rewiring layer 4 is preferably 1.05 times or more, more preferably 1.1 times the area S2 of the semiconductor chip 2 . More preferably, it is 1.2 times or more, and particularly preferably 1.3 times or more. The upper limit is not particularly limited, and the area S1 of the rewiring layer 4 may be 50 times or less the area S2 of the semiconductor wafer 2, 25 times or less, 10 times or less, or 5 times or less. Furthermore, in FIG. 2 , the area of the part of the redistribution layer 4 covering the semiconductor wafer 2 is also included in the area S1 of the redistribution layer 4 .

In addition, the external shapes of the semiconductor wafer 2 and the rewiring layer 4 may be the same or different. In FIG. 2 , the outer shapes of the semiconductor chip 2 and the redistribution layer 4 are similar in shape to a rectangle, but the shape may also be other than a rectangle.

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 member with high conductivity, and copper is generally used.

(Sealing material)

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

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

The sealing material 3 may be a single layer, or may be composed of 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 a laminated structure of different materials.

(Interlayer insulating film)

The first aspect of the present embodiment is characterized in that the transmittance of the i-ray (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 μm. In addition, when the film thickness is not 10 μm (set as y μm), the transmittance converted to 10 μm is calculated by using {(transmittance/100) ^10/y }×100 for the measured transmittance . If the transmittance of the i-ray (wavelength: 365 nm) of the interlayer insulating film 6 is 80% or less, the reason why the adhesion between the interlayer insulating film 6 and the sealing material 3 in the rewiring layer 4 is excellent is not known, but the inventors of the present invention etc. People speculate as follows.

In the manufacturing process of the fan-out type semiconductor device, in order to form the rewiring layer 4 , the photosensitive resin composition is coated on the chip sealing body including the semiconductor wafer 2 and the sealing material 3 . Next, the photosensitive resin composition is exposed to light containing i-rays. Then, the photosensitive resin composition is developed and cured, whereby a portion having a cured product of the photosensitive resin composition and a portion without a cured product of the photosensitive resin composition are selectively formed. The cured product of the photosensitive resin composition becomes the interlayer insulating film 6 . Moreover, the wiring 5 is formed in the part without the hardened|cured material of the photosensitive resin composition. Usually, the rewiring layer 4 is a multilayer in many cases. That is, between the interlayer insulating film 6 and the The photosensitive resin composition is further coated on the wiring 5, and the rewiring layer is further formed on the rewiring layer through the steps of exposure, development, and curing.

When exposing to form the rewiring layer of the first layer or exposing to form the rewiring layer of the second layer, if the transmittance of the i-ray (wavelength: 365 nm) of the interlayer insulating film is high, due to i The sealing material 3 is decomposed and deteriorated due to radiation. Therefore, the adhesion between the interlayer insulating film and the sealing material 3 decreases. In particular, epoxy resins are easily decomposed and deteriorated by i-rays. Therefore, when the 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 promoted to decrease.

The interlayer insulating film 6 of the present embodiment has an i-ray transmittance such that the transmittance of i-rays (wavelength is 365 nm) is as low as 80% or less. Therefore, in the present embodiment, it is estimated that decomposition and deterioration of the sealing material 3 due to 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, in the case of using an interlayer insulating film with high i-ray (wavelength: 365 nm) transmittance, the i-ray (wavelength: 365 nm) transmittance can be reduced by increasing the thickness of the interlayer insulating film. However, there is a disadvantage that the entire semiconductor device becomes thick. The semiconductor device of this embodiment can reduce the transmittance of i-rays (wavelength: 365 nm) without increasing the thickness of the entire semiconductor device, and has excellent adhesion between the interlayer insulating film and the sealing material in the rewiring layer.

The transmittance of the i-ray (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 rewiring layer. Preferably below 76%, preferably below 74%, preferably below 72%, preferably below 70%, preferably below 68%, preferably below 66%, preferably below 64%, preferably Jiawei 62% or less, preferably 60% or less, preferably 58% or less, preferably 56% or less, preferably 54% or less, preferably 52% or less, preferably 50% or less, preferably 48% % or less, preferably 46% or less, preferably 44% or less, preferably 42% or less, preferably 40% or less, preferably 38% or less, preferably 36% or less, preferably 34% below, preferably below 32%, preferably below 30%, preferably below 28%, preferably below 26%, preferably below 24%, preferably below 22%, preferably below 20% , preferably below 18%, preferably below 16%, preferably below 14%, preferably below 12%.

Furthermore, the transmittance of the i-ray (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, more preferably 6% Below, it is preferably 5% or less, more preferably 4% or less, more preferably 3% or less, more preferably 2% or less.

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

In addition, the interlayer insulating film 6 in the rewiring layer 4 may be a multilayer. That is, when the rewiring layer 4 is observed in cross-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 provided between the first interlayer insulating film layer and the second interlayer insulating film layer. The so-called intermediate layer is, for example, the wiring 5 .

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

In the case where the interlayer insulating film 6 is multi-layered, the i-ray transmittance of at least one of the multiple layers may be 80% or less, and the interlayer insulating film layer in contact with the sealing material 3 is preferred (the first layer). The i-ray transmittance of the interlayer insulating film) 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, when the interlayer insulating film layer not in contact with the sealing material 3 is formed, the i-ray can be absorbed efficiently, and the Prevent deterioration of sealing materials. The range of the preferable i-ray transmittance of each interlayer insulating film layer is the same as the range of the preferable i-ray transmittance of the interlayer insulating film 6 .

In the second aspect of the present embodiment, the 5% weight reduction temperature of the interlayer insulating film 6 is 300° C. or lower. Hereinafter, the "5% weight loss temperature" is abbreviated as "weight loss temperature". If 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 clear, but the inventors of the present invention speculate as follows.

In the manufacturing process of the fan-out type semiconductor device 1 (refer to FIG. 1 ), in order to form a 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 to light containing i-rays. Then, the photosensitive resin composition is developed and cured, whereby a portion having a cured product of the photosensitive resin composition and a portion without a cured product of the photosensitive resin composition are selectively formed. 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. In general, the rewiring layer 4 is often multi-layered. That is, the photosensitive resin composition is further coated on the interlayer insulating film 6 and the wiring 5, and exposed, developed, and cured.

However, in the step of forming the interlayer insulating film 6 and the wiring 5 , depending on the manufacturing method, a reflow step may be included, 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, when the weight reduction 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 is accumulated 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. In particular, epoxy resins tend to generate gas. Therefore, when the epoxy resin is used for the sealing material 3, the adhesion between the interlayer insulating film 6 and the sealing material 3 is promoted to decrease.

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

As for the weight reduction temperature of the interlayer insulating film 6, from the height of the interlayer insulating film 6 and the sealing material 3 From the viewpoint of the adhesiveness after the warm treatment, it is preferably 300°C or lower, preferably 295°C or lower, preferably 290°C or lower, preferably 285°C or lower, preferably 280°C or lower, preferably 275°C Below, it is preferably 270°C or lower, preferably 260°C or lower, preferably 250°C or lower, preferably 240°C or lower, preferably 230°C or lower.

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

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

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

In the case where the interlayer insulating film 6 is a multilayer, the weight reduction temperature of the interlayer insulating film 6 in at least one layer among a plurality of layers may be 300° C. or lower. However, the sealing material 3 is insulated from the interlayer Since the border film layers are easily peeled off by gas, the weight reduction temperature of the interlayer insulating film 6 between the interlayer insulating film layers in contact with the sealing material 3 is preferably 300° C. or lower. If the weight reduction temperature of the interlayer insulating film 6 between the interlayer insulating film layers in contact with the sealing material 3 is 300° C. or lower, the efficiency generated in the sealing material 3 can be efficiently escaped. 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 the present 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 is less than 0.0150. Here, the in-plane refractive index is the average value of the refractive index at a wavelength of 1310 nm in the x-direction and the y-direction of the interlayer insulating film 6 with thickness z, width x, and length y. The so-called out-of-plane refractive index is 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 referred to as the refractive index difference.

Furthermore, the so-called width x direction of the interlayer insulating film 6 is the plane direction of the interlayer insulating film 6 in FIG. 2, and the so-called length y direction is the plane direction of the interlayer insulating film 6 in FIG. 2 and the direction perpendicular to the width x direction, The 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 is excellent. The reason for this is not clear, 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 chip sealing body including the semiconductor wafer 2 and the sealing material 3 . Next, the photosensitive resin composition is exposed to light containing i-rays. Then, the photosensitive resin composition is developed and cured to selectively form a group having a photosensitive resin The part of the cured product of the composition and the part of the cured product without 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. In general, the rewiring layer 4 is often multi-layered. That is, the photosensitive resin composition is further coated on the interlayer insulating film 6 and the wiring 5, and exposed, developed, and cured.

However, in the step of forming the interlayer insulating film 6 and the wiring 5, there is a case where a reflow step is included depending on the manufacturing method. In the reflow step, if heat is applied to the sealing material for a long time, there is a possibility that gas is 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 is accumulated 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. In particular, epoxy resins tend to generate gas due to a high-temperature thermal history. Therefore, when the epoxy resin is used for the sealing material 3, the adhesion between the interlayer insulating film 6 and the sealing material 3 is promoted to decrease.

The refractive index difference of the interlayer insulating film 6 in this embodiment is as small as less than 0.0150, and the randomness of the molecular chains of the interlayer insulating film 6 is high. Therefore, in the present embodiment, even under the condition that gas is easily escaped 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 high.

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

In addition, the lower limit of the refractive index difference of the interlayer insulating film 6 is not particularly limited, and may be 0.0000 or more, 0.0005 or more, 0.0010 or more, or 0.0015 or more.

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

The first interlayer insulating film layer and the second interlayer insulating film layer may have the same composition or may have 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 may have different film thicknesses. If the first interlayer insulating film layer and the second interlayer insulating film layer have different compositions, different refractive index differences, or different film thicknesses, each interlayer insulating film layer can have different properties, which is preferable.

In the case where the interlayer insulating film 6 is multi-layered, if the difference in refractive index of the interlayer insulating film 6 between at least one layer is less than 0.0150 in a plurality of 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 refractive index difference of the interlayer insulating film 6 between the interlayer insulating film layers in contact with the sealing material 3 is less than 0.0150. If the refractive index difference of the interlayer insulating film 6 between the interlayer insulating film layers in contact with the sealing material 3 is less than 0.0150, it becomes possible to efficiently escape the gas generated in the sealing material 3 .

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

(Composition of interlayer insulating film)

唑、或具有酚性羥基之聚合物之至少一種化合物之膜。 The composition of the interlayer insulating film 6 is not particularly limited.

azole, or a film of at least one compound of a polymer having a phenolic hydroxyl group.

(Resin composition for forming interlayer insulating film)

唑前驅物、或具有酚性羥基之聚合物之至少一種化合物之感光性樹脂組合物。層間絕緣膜6之形成中所使用之樹脂組合物可為液體狀，亦可為膜狀。又，層間絕緣膜6之形成中所使用之樹脂組合物可為負型感光性樹脂組合物，亦可為正型感光性樹脂組合物。 The resin composition used in the formation of the interlayer insulating film 6 is not particularly limited as long as it is a photosensitive resin composition.

An azole precursor or a photosensitive resin composition of at least one compound of a polymer having a phenolic hydroxyl group. The resin composition used for the formation of the interlayer insulating film 6 may be liquid or film. Moreover, the resin composition used for formation of the interlayer insulating film 6 may be a negative photosensitive resin composition, and a positive photosensitive resin composition may be sufficient as it.

In this embodiment, the pattern after exposing and developing the photosensitive resin composition is called a relief pattern, and what heat-hardens 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

As a photosensitive resin used for a polyimide precursor composition, a polyamide, a polyamic acid ester, etc. are mentioned. For example, as the polyamic acid ester, a polyamic acid ester containing a repeating unit represented by the following general formula (11) can be used.

R ¹ and R ² are each independently a hydrogen atom, a saturated aliphatic group with a carbon number of 1 to 30, an aromatic group, a monovalent organic group with a carbon-carbon unsaturated double bond, or a carbon-carbon unsaturated double bond a valence ion. 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-mentioned general formula (11) exist as monovalent cations, O is negatively charged (exists as ^-O- ). In addition, X ¹ and Y ¹ may contain a hydroxyl group.

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

(In the general formula (12), R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or an organic group having 1 to 5 carbon atoms, and m ₁ is an integer of 1 to 20)

(In the general formula (13), R ₆ , R ₇ and R ₈ are each independently a hydrogen atom or an organic group having 1 to 5 carbon atoms, and m ₂ is an integer of 1 to 20).

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

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

[Chemical 46]

(In the general formula (4), R ₉ 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 hydroxyl groups.

From the viewpoint of the adhesion 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).

[Chemical 49]

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

(R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are hydrogen atoms and monovalent aliphatic groups having 1 to 5 carbon atoms, which may be the same or different)

(R ₁₄ to R ₂₁ are hydrogen atoms, halogen atoms, and monovalent organic groups with 1 to 5 carbon atoms, which may be different from each other or the same)

(R ₂₂ is a divalent organic group, and R ₂₃ to R ₃₀ are a hydrogen atom, a halogen atom, and a monovalent aliphatic group 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 containing a structure represented by the following general formula (9).

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

As the tetracarboxylic dianhydride used as a raw material, for example, pyromellitic dianhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3', 4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetra Carboxylic 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-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, etc., but not Not limited to these. In addition, these may be used individually or in mixture of 2 or more types.

The diamine used as a raw material includes, for example, p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diphenyl ether Amino diphenyl ether, 4,4'-diamino diphenyl sulfide, 3,4'-diamino diphenyl sulfide, 3,3'-diamino diphenyl sulfide, 4,4'- Diaminodiphenyl bismuth, 3,4'-diaminodiphenyl bismuth, 3,3'-diaminodiphenyl bismuth, 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] bis[4-(3-aminophenoxy)phenyl] bis[4-(3-aminophenoxy)phenyl] 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-tolidine, 9, 9-bis (4-aminophenyl) fluoride and so on. In addition, a part of the hydrogen atoms on these benzene rings may also be substituted. In addition, these may be used individually or in mixture of 2 or more types.

In the synthesis of the polyamic acid ester (A), the tetracarboxylic acid which will be described later is usually preferably used. The tetracarboxylic-acid diester obtained by the esterification reaction of a dianhydride is given directly to the method of the condensation reaction with a diamine.

The alcohol used for the esterification reaction of the said tetracarboxylic dianhydride is the alcohol which has an olefinic double bond. Specifically, 2-hydroxyethyl methacrylate, 2-methacryloyloxyethanol, glycerol diacrylate, glycerol dimethacrylate, etc. are mentioned, but it is not limited to these. These alcohols can be used individually or in mixture of 2 or more types.

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

Examples of the organic dehydrating agent 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 polyamic acid ester (A) used in the present embodiment is preferably 6,000 to 150,000, more preferably 7,000 to 50,000, and more preferably 7,000 to 20,000.

(B1) Photoinitiator

、2-甲基-9-氧硫

、2-異丙基-9-氧硫

、及二乙基-9-氧硫

等9-氧硫

衍生物，苯偶醯、苯偶醯二甲基縮酮及、苯偶醯-β-甲氧基乙基縮醛等苯偶醯衍生物，安息香甲醚等安息香衍生物，2,6-二(4'-二疊氮苯亞甲基)-4-甲基環己酮、及2,6'-二(4'-二疊氮苯亞甲基)環己酮等疊氮類，1-苯基-1,2-丁二酮-2-(O-甲氧基羰基)肟、1-苯基丙二酮-2-(O-甲氧基羰基)肟、1-苯基丙二酮-2-(O-乙氧基羰基)肟、1-苯基丙二酮-2-(O-苯甲醯基)肟、1,3-二苯基丙三酮-2-(O-乙氧基羰基)肟、1-苯基-3-乙氧基丙三酮-2-(O-苯甲醯基)肟等肟類，N-苯基甘胺酸等N-芳基甘胺酸類，過氧化苯甲醯等過氧化物類，芳香族聯咪唑類、以及二茂鈦類等。該等中，於光感度之方面而言較佳為上述肟類。 When the resin composition used for formation of the interlayer insulating film 6 is a negative photosensitive resin, a photoinitiator is added. As the photoinitiator, for example, dibenzophenone, methyl o-benzoylbenzoate, 4-benzyl-4'-methylbenzophenone, dibenzyl ketone, and fenone are used. Benzophenone derivatives, 2,2'-diethoxyacetophenone, and acetophenone derivatives such as 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, 9-oxothioate

, 2-methyl-9-oxothio

, 2-isopropyl-9-oxothio

, and diethyl-9-oxothio

Iso-9-oxosulfur

Derivatives, benzil derivatives such as benzil, benzil dimethyl ketal, and benzil-β-methoxyethyl acetal, benzoin derivatives such as benzoin methyl ether, 2,6-dibenzoin derivatives (4'-Diazidobenzylidene)-4-methylcyclohexanone, and azides such as 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-benzyl) oxime, 1,3-diphenylglycerol-2-(O-ethyl) Oximes such as oxycarbonyl) oxime, 1-phenyl-3-ethoxyglycerol-2-(O-benzyl) oxime, N-arylglycines such as N-phenylglycine , peroxides such as benzyl peroxide, aromatic biimidazoles, and titanocenes. Among these, the above-mentioned oximes are preferable in terms of photosensitivity.

The amount of these photoinitiators added is preferably 1 to 40 parts by mass, more preferably 2 to 20 parts by mass, with respect to 100 parts by mass of the polyamic acid ester (A). It is excellent in photosensitivity by adding 1 mass part or more of photoinitiators with respect to 100 mass parts of polyamic acid esters (A). Moreover, by adding 40 mass parts or less, it is excellent in thick-film curability.

(B2) Photoacid generator

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

As a photoacid generator, a quinonediazide compound, a pernium salt, a phosphonium salt, a diazonium salt, an iodonium salt, etc. are mentioned. Among them, a quinonediazide compound can be preferably used in view of exhibiting an excellent dissolution inhibitory effect and obtaining a high-sensitivity positive photosensitive resin composition. Moreover, two or more types of photoacid generators may be contained.

(C) Additives

等。 The i-ray transmittance of the interlayer insulating film in the first aspect of the present embodiment can be adjusted by the amount of additives. As an additive for reducing 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-tris

Wait.

In the second aspect of the present embodiment, the weight reduction temperature of the interlayer insulating film 6 can be adjusted by the type or amount of the additive. By using a volatile additive, the density of the interlayer insulating film can be lowered, and the weight reduction temperature can be lowered. As an additive which lowers the weight reduction temperature, polyethylene glycol, polypropylene glycol, etc. 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 thermal curing of the relief pattern.

In the third aspect of the present 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 the additive. If an additive with a fluffy structure is used, the additive enters between the polymer molecular chains, and the arrangement of the polymer molecular chains is disordered. Due to the disordered arrangement of the polymer molecular chains, the intermolecular force between the polymer molecular chains is reduced, and the molecular chains are easily arranged in a random shape in the in-plane and out-of-plane directions, which can make the in-plane refractive index and the out-of-plane refractive index possible. difference becomes smaller. As an additive which has a bulky structure, the additive which has a bicyclic structure etc. are mentioned, for example. As an additive which reduces 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 target difference between the 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 reduced by changing the temperature during thermal curing of the relief pattern.

(D) Solvent

If it is a solvent which can dissolve or disperse each component, it will not specifically limit. 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 to 1500 parts by mass with respect to 100 parts by mass of the (A) photosensitive resin according to the thickness of the coating film and the 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, or the cross-linking agent itself can form a cross-linked network when the polyimide precursor composition is exposed to light, developed, and then cured by heating. the crosslinking agent. By using a crosslinking agent, the heat resistance and chemical resistance of the cured film (interlayer insulating film) can be further strengthened.

In addition, a sensitizer for improving the photosensitivity, an adhesive adjuvant for improving the adhesion to a base material, and the like may also be included.

(development)

After exposing the polyimide precursor composition, useless parts are rinsed with a developer. The developer to be used is not particularly limited, and in the case of a polyimide precursor composition for development with a solvent, N,N-dimethylformamide, dimethylsulfoxide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, cyclopentanone, γ-butyrolactone, acetates and other good solvents, these good solvents are compatible with lower alcohols, water, aromatic Mixed solvents of poor solvents such as family hydrocarbons, etc. Rinse and wash with a poor solvent etc. as needed after development.

In the case of a polyimide precursor composition developed by an alkaline aqueous solution, it is preferably an aqueous solution of tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide , sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclic Aqueous solutions of compounds showing basicity such as hexylamine, ethylenediamine, and hexamethylenediamine.

(heat hardening)

By heating the polyimide precursor composition after development and exposure, 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 the present embodiment, the heating temperature is not particularly limited, but from the viewpoint of influence on other members, the heating temperature is preferably a lower temperature. Preferably it is 250 degrees C or less, More preferably, it is 230 degrees C or less, More preferably, it is 200 degrees C or less, More preferably, it is 180 degrees C or less.

In the third aspect of the present embodiment, the heating temperature for thermosetting the polyimide precursor composition is not particularly limited. Generally, there is a tendency as follows: the lower the thermosetting temperature, the greater the difference in refractive index. Small. The heating temperature is preferably 200°C or lower, preferably 180°C or lower, and more preferably 160°C or lower, from the viewpoint of showing the refractive index difference of the present embodiment, that is, less than 0.0150.

<Polyimide>

The structure of the hardened relief pattern formed from the above-mentioned polyimide precursor composition becomes the following general formula (1).

X 1 , Y ¹ , and m in the general formula (1) are the same as X ¹ , Y ¹ , and m in the general formula (11), X ¹ is ^a tetravalent organic group, Y ¹ is a divalent organic group, and m is 1 the above integers. 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 alkali-soluble polyimide, the terminal of the polyimide can also be a hydroxyl group.

< polybenzo

azole precursor composition> (A) Photosensitive resin

唑前驅物組合物中所使用之感光性樹脂，可使用包含下述通式(14)所表示之重複單元的聚(鄰羥基醯胺)。 as polybenzo

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

(In the 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 carbon atoms, more preferably a chain alkylene group having 1 to 15 carbon atoms (wherein, a chain The hydrogen atom of the alkylene group may also be substituted with a halogen atom), especially a chain alkylene group having 1 to 8 carbon atoms and a hydrogen atom substituted with a fluorine atom.

In addition, 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, and more preferably includes 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 hydrogen atoms and monovalent aliphatic groups having 1 to 5 carbon atoms, which may be the same or different)

(R ₁₄ to R ₂₁ are hydrogen atoms, halogen atoms, and monovalent organic groups with 1 to 5 carbon atoms, which may be different from each other or the same)

(R ₂₂ is a divalent organic group, and R ₂₃ to R ₃₀ are a hydrogen atom, a halogen atom, and a monovalent aliphatic group 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 adhesion between the interlayer insulating film 6 and the sealing material 3, V is particularly preferably a divalent organic group including a structure represented by the following general formula (9).

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 bivalent chain aliphatic group having 1 to 40 carbon atoms, particularly preferably It is a bivalent chain aliphatic group with 1 to 20 carbon atoms.

唑前驅物一般可由二羧酸衍生物與含有羥基之二胺類而合成。具體而言可藉由如下方式而合成：將二羧酸衍生物轉換為二鹵化物衍生物之後，進行其與二胺類之反應。作為二鹵化物衍生物，較佳為二氯化物衍生物。 polybenzo

The azole precursors are generally synthesized from dicarboxylic acid derivatives and hydroxyl-containing diamines. 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 preferred.

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

As a method of synthesizing a dichloride derivative, it can be synthesized by the following method: A method of reacting an acid derivative with the above-mentioned halogenating agent in a solvent, a method of distilling off excess components after the reaction is performed in an excess halogenating agent, and the like.

As the dicarboxylic acid used for the dicarboxylic acid derivative, for example, 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) bismuth, 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 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, dodecafluorooctanedioic acid, azelaic acid, sebacic acid 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, eicosanedioic acid, docosanedioic acid, tetracosanedioic acid, tetracosanedioic acid, Pentacosanedioic acid, Hexadecanedioic acid, Heptacosanedioic acid, Hecosanedioic acid, Hecosanedioic acid, Triacosanedioic acid, Triacosanedioic acid, Thirty Dioxanedioic acid, diglycolic acid, etc. These can also be used in combination.

Examples of hydroxyl-containing diamines include 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) bismuth, 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 in the light-irradiated portion. As a photoacid generator, a naphthoquinone diazonium compound, an aryldiazonium salt, a diaryl iodonium salt, a triaryl perionium salt, etc. are mentioned. Among them, the sensitivity of the naphthoquinone diazonium compound is high and is preferable.

(C) Additives

The preferred types or amounts of additives are the same as those described in the item of polyimide precursor composition.

(D) Solvent

If it is a solvent which can dissolve or disperse each component, it will not specifically limit.

(E) Other

唑前驅物組合物可包含交聯劑、增感劑、接著助劑、熱酸產生劑等。 polybenzo

The azole precursor composition may contain a crosslinking agent, a sensitizer, an adjuvant, a thermal acid generator, and the like.

(development)

唑前驅物組合物進行曝光後，藉由顯影液沖洗無用部分。所使用之顯影液並無特別限制，例如可列舉氫氧化鈉、氫氧化鉀、矽酸鈉、氨、乙胺、二乙胺、三乙胺、三乙醇胺、氫氧化四甲基銨等之鹼性 水溶液作為較佳者。 for p-polybenzone

After exposure to the azole precursor composition, useless parts are rinsed with a developer. The developer to be used is not particularly limited, and examples thereof include alkalis such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide. Aqueous aqueous solution is preferred.

唑前驅物組合物為中心而加以說明，但亦可為負型之聚苯并

唑前驅物組合物。 In the above, the positive polybenzo

The azole precursor composition is centered on the description, but it can also be a negative-type polybenzo

azole precursor composition.

(heat hardening)

唑前驅物組合物進行加熱，藉此使聚苯并

唑前驅物閉環，形成聚苯并

唑。該聚苯并

唑成為硬化凸紋圖案、亦即層間絕緣膜6。 After development, the polybenzo

The azole precursor composition is heated, thereby making the polybenzo

Ring closure of azole precursors to form polybenzos

azoles. The polybenzo

The azole becomes the hardened relief pattern, that is, the interlayer insulating film 6 .

唑前驅物組合物熱硬化之加熱溫度並無特別限定，自對其他構件之影響之觀點考慮，較佳為加熱溫度係較低之溫度。該加熱溫度較佳為250℃以下，更佳為230℃以下，更佳為200℃以下，尤佳為180℃以下。 to make polybenzoate

The heating temperature for thermal hardening of the azole precursor composition is not particularly limited, but from the viewpoint of influence on other components, the heating temperature is preferably a lower temperature. The heating temperature is preferably 250°C or lower, more preferably 230°C or lower, more preferably 200°C or lower, and particularly preferably 180°C or lower.

< polybenzo

azole>

唑前驅物組合物形成之硬化凸紋圖案之結構成為下述通式(10)。 by the above-mentioned polybenzo

The structure of the hardened relief pattern formed by the azole precursor composition has the following general formula (10).

唑中亦較佳。 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 the same as those of the polybenzoyl group of the general formula (10) for the same reason.

azoles are also preferred.

<Polymer with phenolic hydroxyl group> (A) Photosensitive resin

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

Among these, a phenol resin is preferable, and a novolac-type phenol resin is particularly preferable in view of low cost and small volume shrinkage during curing.

Phenolic resins are polycondensation products of phenol or its derivatives and aldehydes. The polycondensation is carried out in the presence of a catalyst such as an acid or a base. The phenol resin obtained when an acid catalyst is used is particularly referred to as a novolac-type phenol resin.

Examples of the phenol derivatives include phenol, cresol, ethylphenol, propylphenol, butylphenol, amylphenol, benzylphenol, adamantanephenol, benzyloxyphenol, xylenol, catechol, m-phenylene Diphenol, ethyl resorcinol, hexyl resorcinol, hydroquinone, pyrogallol, phloroglucinol, 1,2,4-trihydroxybenzene, rose red acid, biquinol, 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-hydroxybenzene) yl)-1,4-diisopropylbenzene, 9,9-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane , 2,2-bis(2-hydroxy-5-biphenyl) propane, dihydroxybenzoic acid, etc.

烷、乙二醛、環己基醛、二苯基乙醛、乙基丁醛、苯甲醛、乙醛酸、5-降

烯-2-羧基醛、丙二醛、丁二醛、戊二醛、柳醛、萘甲醛、對苯二甲醛等。 Examples of the aldehyde compound include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, pivalaldehyde, butyraldehyde, valeraldehyde, hexanal, tris

Alkane, glyoxal, cyclohexylaldehyde, diphenylacetaldehyde, ethylbutyraldehyde, benzaldehyde, glyoxylic acid, 5-nor

Alkene-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. It is more preferable that the said (b) component is modified|denatured by the reaction of a phenolic hydrocarbon group and a polybasic acid anhydride.

In addition, as the component (b), it is preferable to use a compound modified by a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms, from the viewpoint that the mechanical properties (elongation at break, elastic modulus, and residual stress) can be further improved. phenolic resin.

(b) Modified phenol resins having unsaturated hydrocarbon groups are generally phenol or its derivatives and compounds having unsaturated hydrocarbon groups (preferably those having 4 to 100 carbon atoms) (hereinafter referred to as "compounds containing unsaturated hydrocarbon groups" depending on the situation ") of the reaction product (hereinafter referred to as "unsaturated hydrocarbon group-modified phenol derivative") and the polycondensation product of aldehydes, or the reaction product of a phenol resin and a compound containing an unsaturated hydrocarbon group.

The phenol derivative used herein can be the same as the above-mentioned phenol derivative as a raw material of the phenol resin of the component (A).

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

Examples of compounds containing an unsaturated hydrocarbon group include unsaturated hydrocarbons having 4 to 100 carbon atoms, polybutadiene having a carboxyl group, epoxidized polybutadiene, linolenic alcohol, oleyl alcohol, unsaturated fatty acids, and unsaturated fatty acids. ester. Examples of suitable unsaturated fatty acids include crotonic acid, myristic acid, palmitoleic acid, oleic acid, elaidic acid, linoleic acid, codoleic acid, erucic acid, arachidonic acid, linoleic acid, Alpha-linolenic acid, eleric acid, stearidonic acid, arachidonic acid, eicosapentaenoic acid, herring acid and docosahexaenoic acid. Among these, esters of unsaturated fatty acids with 8-30 carbon atoms and mono- to tri-hydric alcohols with 1-10 carbon atoms are more preferable, especially unsaturated fatty acids with 8-30 carbon atoms and trivalent alcohols of glycerol esters.

Esters of unsaturated fatty acids having 8 to 30 carbon atoms and glycerol are commercially available in the form of vegetable oils. Vegetable oils include non-drying oils with an iodine value of less than 100, semi-drying oils with an iodine value of more than 100 and less than 130, or drying oils with an iodine value of more than 130. Examples of non-drying oils include olive oil, morning glory seed oil, Polygonum multiflorum seed oil, camellia oil, camellia oil, castor oil, and peanut oil. Examples of semi-drying 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 vegetable oils, non-drying oils are preferably used from the viewpoints of preventing gelation accompanying excessive reaction progress in the reaction between phenol or its derivatives or phenol resin and vegetable oil and improving yield. On the other hand, it is preferable to use a drying oil from a viewpoint of improving the adhesiveness of a resist pattern, a mechanical property, and thermal shock resistance. Among the drying oils, tung oil, linseed oil, soybean oil, walnut oil, and safflower oil are preferable, and tung oil and linseed oil are more preferable, since the effects of the present invention can be more effectively and surely exhibited.

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

In preparing the component (b), first, the above-mentioned phenol derivative is reacted with the above-mentioned unsaturated hydrocarbon group-containing compound to prepare an unsaturated hydrocarbon group-modified phenol derivative. The above reaction is preferably carried out at 50 to 130°C. As for the reaction ratio of the phenol derivative and the unsaturated hydrocarbon group-containing compound, from the viewpoint of improving the flexibility of the cured film (resist pattern), it is preferable to contain the unsaturated hydrocarbon group with respect to 100 parts by mass of the phenol derivative. The compound of the hydrocarbon group is 1 to 100 parts by mass, more preferably 5 to 50 parts by mass. There exists a tendency for the flexibility of a cured film to fall that the compound containing an unsaturated hydrocarbon group is less than 1 mass part, and there exists a tendency for the heat resistance of a cured film to fall when it exceeds 100 mass parts. In the above reaction, p-toluenesulfonic acid, trifluoromethanesulfonic acid, etc. can also be used as a catalyst as needed.

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

The reaction of the above-mentioned aldehydes and the above-mentioned unsaturated hydrocarbon group-modified phenol derivative is a polycondensation reaction, and the synthesis conditions of previously known phenol resins can be used. The reaction is preferably carried out in the presence of a catalyst such as an acid or a base, and more preferably an acid catalyst is used. 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.

It is usually preferable to carry out the above reaction at a reaction temperature of 100 to 120°C. In addition, the reaction time varies depending on the type and amount of the catalyst used, but is usually 1 to 50 hours. After the reaction is completed, the reaction product is dehydrated under reduced pressure at a temperature of 200° C. or lower, 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 for the reaction.

A phenol resin modified with 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 a phenol such as m-xylene and aldehydes . In this case, the molar ratio of the compound other than the phenol to the compound obtained by reacting the phenol derivative with 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) above with an unsaturated hydrocarbon group-containing compound.

The unsaturated hydrocarbon group-containing compound to be reacted with the phenol resin can be the same as the above-mentioned unsaturated hydrocarbon group-containing compound.

Preferably, the reaction of the phenol resin and the unsaturated hydrocarbon group-containing compound is usually carried out at 50 to 130°C. Moreover, from the viewpoint of improving the flexibility of the cured film (resist pattern), the reaction ratio of the phenol resin and the unsaturated hydrocarbon group-containing compound is preferably 100 parts by mass of the unsaturated hydrocarbon group-containing compound. The compound is 1 to 100 parts by mass, more preferably 2 to 70 parts by mass, still more preferably 5 to 50 parts by mass. When the amount of 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 possibility of gelation during the reaction tends to increase, and curing The tendency for the heat resistance of the film 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 for the reaction.

The polybasic acid anhydride is further reacted with the phenolic hydroxyl group remaining in the phenolic 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 carrying out acid modification with a polybasic acid anhydride and introducing a carboxyl group, the solubility of the component (b) with respect to an alkaline aqueous solution (developing solution) is further improved.

The polybasic acid anhydride is not particularly limited as long as it has an acid anhydride group formed by dehydration condensation of the carboxyl groups of a polybasic acid having a plurality of carboxyl groups. Examples of polybasic acid anhydrides 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, terrestrial 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, Alkane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic dianhydride and dianisole tetracarboxylic dianhydride Aromatic tetrabasic acid dianhydrides such as anhydrides. These can be used alone or in combination of two or more. Among these, the polybasic acid anhydride is preferably a dibasic acid anhydride, and 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 has a good shape.

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

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

(B2) Photoacid generator

As a photoacid generator, a diazonaphthoquinone compound, an aryldiazonium salt, a diaryl iodonium salt, a triaryl perionium salt, etc. are mentioned. Among them, the sensitivity of the naphthoquinone diazonium compound is high and is preferable.

(C) Additives

The preferred types or amounts of additives are the same as those described in the item of polyimide precursor composition.

(D) Solvent

If it is a solvent which can dissolve or disperse each component, it will not specifically limit.

(E) Other

Thermal crosslinking agents, sensitizers, adjuvants, dyes, surfactants, dissolution accelerators, crosslinking accelerators, and the like may be included. 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 to form a bridge structure. Thereby, it becomes possible to harden at a low temperature, and the brittleness of the film or the melting of the film can be prevented. 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 can be preferably used.

(development)

After exposing the polymer having a phenolic hydroxyl group, useless parts are washed with a developer. The developer to be used is not particularly limited. For example, sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide can be suitably used. (TMAH) and other alkaline aqueous solutions.

(heat hardening)

After development, the polymers having phenolic hydroxyl groups are thermally cross-linked to each other by heating the polymers having phenolic hydroxyl groups. The cross-linked polymer becomes the hardened relief pattern, that is, the 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 influence on other members, the heating temperature is preferably a lower temperature. The heating temperature is preferably 250° C. or lower, more preferably 230° C. or lower, more preferably 200° C. or lower, and particularly preferably 180° C. or lower.

(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 after the previous step is prepared is prepared. Then, in FIG. 3B , the wafer 10 after the previous step is diced to form a plurality of semiconductor chips 2 . The semiconductor wafer 2 may also be a purchased item. The semiconductor wafer 2 prepared as described above is attached to the support 11 at predetermined 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 mold resin 12 is reversed (see FIG. 3E ). As shown in FIG. 3E, the semiconductor wafer 2 and the molding resin 12 are present on substantially the same plane. Then, the photosensitive resin composition 13 is coated on the semiconductor wafer 2 and the molding resin 12 by the steps shown in FIG. 3F . Next, the applied photosensitive resin composition 13 is exposed and developed to form a relief pattern (relief pattern forming step). In addition, the photosensitive resin composition 13 may be either positive type or negative type. Further, the relief pattern is heated to form a hardened relief pattern (layer inter-insulating film forming step). Furthermore, wiring is formed in the site|part where the hardened relief pattern is not formed (wiring formation process).

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 multi-layered. Therefore, the rewiring layer forming step may include a plurality of relief pattern forming steps, a plurality of interlayer insulating film forming steps, and a plurality of wiring forming steps.

Then, in FIG. 3G , a plurality of external connection terminals 7 corresponding to the semiconductor wafers 2 are formed (bumps are formed), and dicing is performed between the semiconductor wafers 2 . Thereby, the 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-mentioned 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.

唑、具有酚性羥基之聚合物之至少一種化合物的感光性樹脂組合物而形成層間絕緣膜。 In this embodiment, in the above-mentioned interlayer insulating film forming step, it is preferable to form polyimide, polybenzyl

An interlayer insulating film is formed from a photosensitive resin composition of at least one compound of azole and a polymer having a phenolic hydroxyl group.

In the first aspect of the present 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 the second aspect of the present embodiment, the weight reduction temperature of the hardened relief pattern (interlayer insulating film) formed through the above steps can be set to 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 the present embodiment, the difference in refractive index of the hardened relief pattern (interlayer insulating film) formed through the above steps can be set to be less than 0.0150. Here, the difference in refractive index of the interlayer insulating film can be adjusted by the amount of the additive.

唑、具有酚性羥基之聚合物之至少一種化合物的感光性樹脂組合物而形成層間絕緣膜。 In this embodiment, in the above-mentioned interlayer insulating film forming step, it is preferable to form polyimide, polybenzyl

An interlayer insulating film is formed from a photosensitive resin composition of at least one compound of azole and a polymer having a phenolic hydroxyl group.

[Example]

Hereinafter, the Example performed in order to clarify the effect of this invention is demonstrated. In the examples, the following materials and measurement methods were used.

[Example]

Hereinafter, the Example performed in order to clarify the effect of this invention is demonstrated.

(Polymer A-1: Synthesis of Polyimide Precursor)

4,4'-Oxydiphthalic dianhydride (ODPA), which is a tetracarboxylic dianhydride, was put into a separable flask having a capacity of 2 liters. Furthermore, 2-hydroxyethyl methacrylate (HEMA) and γ-butyrolactone were put and stirred at room temperature, and pyridine was added while stirring to obtain a reaction mixture. After the exotherm due to the reaction was over, it was left to cool to room temperature for 16 hours.

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

The obtained reaction solution was added to ethanol to generate a precipitate containing a crude polymer. The resulting 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, the obtained precipitate was separated by filtration, and then vacuum-dried to obtain a powdery polymer (polyimide precursor (polymer A- 1)). The mass of the compound used in Component A-1 is shown in Table 1 below.

(Synthesis of polymers A-2~A-4)

A polyimide precursor (polymer A-2) was obtained by reacting in the same manner as the method described in the above-mentioned polymer A-1, except that the tetracarboxylic dianhydride and the diamine were changed as shown in Table 1 below. ~A- 4).

(Polymer B-1: Polybenzo

Synthesis of azole precursors)

唑前驅物(聚合物B-1))。關於聚合物B-1中所使用之化合物之質量，如下述表1所示。 In a 0.5-liter flask equipped with a stirrer and a thermometer, 15.48 g of 4,4'-diphenyl ether dicarboxylic acid as dicarboxylic acid and N-methylpyrrolidone were charged. After cooling the flask to 5°C, thionium chloride was added dropwise and allowed to react for 30 minutes to obtain a solution of dicarboxylate chloride. Next, a 0.5-liter flask with a stirrer and a thermometer was charged with N-methylpyrrolidone. After stirring and dissolving 18.30 g of bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 2.18 g of m-aminophenol which are bisaminophenols, pyridine was added. Then, the solution of dicarboxylate chloride was added dropwise over 30 minutes while maintaining the temperature at 0 to 5°C, and stirring was continued for 30 minutes. The solution was poured into 3 liters of water, the precipitate was recovered, washed with pure water 3 times, and then dried under reduced pressure to obtain a polymer (polybenzoic acid).

azole precursor (polymer B-1)). The mass of the compound used in the polymer B-1 is shown in Table 1 below.

(Synthesis of polymers B-2~B-3)

唑前驅物(聚合物B-2~B-3)。 The reaction was carried out in the same manner as the method described in the above-mentioned polymer B-1, except that the dicarboxylic acid and bisaminophenol were changed as shown in Table 1 below to obtain polybenzoyl

azole precursors (polymers B-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 the polymer C-1.

C1: cresol novolak resin (cresol/formaldehyde novolac resin, m-cresol/p-cresol (molar ratio) = 60/40, polystyrene conversion weight average molecular weight = 12,000, Asahi Organic Materials Co., Ltd. Company manufacture, trade name "EP4020G")

C2: C2 was synthesized as shown below.

<C2: Synthesis of a phenolic resin modified by a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms>

100 parts by mass of phenol, 43 parts by mass of linseed oil, and 0.1 part by mass of trifluoromethanesulfonic acid were mixed, and the mixture was stirred at 120° C. for 2 hours to obtain a vegetable oil-modified phenol derivative (a). 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 the mixture was stirred at 90° C. for 3 hours. Next, the temperature was raised to 120° C. and stirred under reduced pressure for 3 hours, then 29 g of succinic anhydride and 0.3 g of triethylamine were added to the reaction liquid, and the mixture was stirred at 100° C. for 1 hour under atmospheric pressure. The reaction solution was cooled to room temperature to obtain a phenolic resin (hereinafter referred to as "C2 resin") modified by a compound having an unsaturated hydrocarbon group having a carbon number of 4 to 100 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.

[Examples 1 to 11, Comparative Examples 1 to 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 mass part.

Using the compounds described in Table 2, the photosensitive resin compositions of Examples 1 to 11 and Comparative Examples 1 to 2 were prepared at the compounding amounts described in Tables 3 and 4.

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

(1) i-ray transmittance measurement test

Using the photosensitive resin composition produced in each Example and each Comparative Example, a fan-out wafer-level chip-scale package type semiconductor device was produced. The interlayer insulating film with a thickness of 10 μm was taken out as completely as possible from the fabricated semiconductor device. The i-ray transmittance was measured by measuring the interlayer insulating film taken out using a UV-1800 apparatus manufactured by Shimadzu Corporation under the conditions of a scanning speed of a medium speed and a sampling pitch of 0.5 nm.

(2) Deterioration test of sealing material

As an epoxy-based sealing material, R4000 series manufactured by Nagase Chemical Co., Ltd. is prepared. Next, the sealing material was spin-coated on the silicon wafer by aluminum sputtering so that the thickness would be about 150 μm, and the epoxy-based sealing material was hardened by thermal curing at 130°C. The photosensitive resin composition produced in each Example and each comparative example was apply|coated on the said epoxy-type cured film so that a final film thickness might become 10 micrometers. For the coated photosensitive resin composition, the exposure conditions were 200 mJ/cm ² in Examples 1 to 4, 10 and Comparative Example 1, and 500 mJ/cm in Examples 5 to 7, 11 and Comparative Example 2. The exposure conditions of ² were exposed to the entire surface under the exposure conditions of 700 mJ/cm ² in Examples 8 and 9. Thereafter, thermal curing was performed at 200° C. for 2 hours to prepare a first-layer cured film with a thickness of 10 μm.

The photosensitive resin composition used for the formation of the first-layer cured film was applied on the first-layer cured film, and the entire surface was exposed to light under the same conditions as in the production of the first-layer cured film, followed by thermosetting. Then, a second-layer cured film with a thickness of 10 microns was produced.

The test piece after the formation of the second-layer cured film was cut out by a FIB apparatus (manufactured by Nippon Electronics Co., Ltd., JIB-4000), and the presence or absence of pores in the epoxy portion was confirmed to evaluate the progress of deterioration. Spend. The case where no voids were found was made into ○, and the case in which even one void was found was made into ×.

(3) Adhesion test with sealing material

A stylus was placed on the sample produced in the sealing material deterioration test, and an adhesion test was performed using a traction tester (manufactured by Quad Group, Sebastian 5 type). That is, the adhesiveness of the epoxy-type sealing material and the hardening relief pattern produced from the photosensitive resin composition produced in each Example and each comparative example was tested.

Evaluation: Adhesion strength is 70 MPa or more‧‧‧Adhesion ◎

More than 50MPa and less than -70MPa‧‧‧adhesion ○

More than 30MPa and less than -50MPa‧‧‧adhesive force△

Less than 30MPa‧‧‧contact force×

Using the photosensitive resin compositions described in Examples 1 to 11, a fan-out type wafer-level chip-scale package semiconductor device containing an epoxy resin in a mold resin was produced, and as a result, it was possible to operate without problems.

(Polymer H-1: Synthesis of Polyimide Precursor)

4,4'-Oxydiphthalic dianhydride (ODPA), which is a tetracarboxylic dianhydride, was put into a separable flask having a capacity of 2 liters. Furthermore, 2-hydroxyethyl methacrylate (HEMA) and γ-butyrolactone were put and stirred at room temperature, and pyridine was added while stirring to obtain a reaction mixture. After the exotherm due to the reaction was over, it was left to cool to room temperature for 16 hours.

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

The obtained reaction solution was added to ethanol to generate a precipitate containing a crude polymer. The resulting 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, the obtained precipitate was separated by filtration, and then vacuum-dried to obtain a powdery polymer (polyimide precursor (polymer H- 1)). About the mass of the compound used in the ingredient H-1, as shown in Table 5 below shown.

(Synthesis of polymers H-2~H-4)

The reaction was carried out in the same manner as the method described in the above-mentioned polymer H-1, except that the tetracarboxylic dianhydride and the diamine were changed as shown in Table 5 below to obtain a polyimide precursor (polymer H-2 ~H-4).

(Polymer I-1: polybenzo

Synthesis of azole precursors)

唑前驅物(聚合物I-1))。關於聚合物I-1中所使用之化合物之質量，如下述表5所示。 In a 0.5-liter flask equipped with a stirrer and a thermometer, 15.48 g of 4,4'-diphenyl ether dicarboxylic acid as dicarboxylic acid and N-methylpyrrolidone were charged. After cooling the flask to 5°C, thionyl chloride was added dropwise to react for 30 minutes to obtain a solution of dicarboxylate chloride. Next, a 0.5-liter flask with a stirrer and a thermometer was charged with N-methylpyrrolidone. After stirring and dissolving 18.30 g of bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 2.18 g of m-aminophenol which are bisaminophenols, pyridine was added. Then, the solution of dicarboxylate chloride was added dropwise over 30 minutes while maintaining the temperature at 0 to 5°C, and stirring was continued for 30 minutes. The solution was poured into 3 liters of water, the precipitate was recovered, washed with pure water 3 times, and then dried under reduced pressure to obtain a polymer (polybenzoic acid).

azole precursor (polymer I-1)). The mass of the compound used in the polymer I-1 is shown in Table 5 below.

(Synthesis of polymers I-2~I-3)

唑前驅物(聚合物I-2~I-3)。 The reaction was carried out in the same manner as the method described in the above-mentioned polymer I-1, except that the dicarboxylic acid and bisaminophenol were changed as shown in Table 5 below to obtain polybenzoyl

azole precursors (polymers I-2~I-3).

(Polymer J-1: Synthesis of Phenolic Resin)

A phenol resin containing 85 g of the J1 resin shown below and 15 g of the J2 resin shown below was prepared as the polymer J-1.

J1: cresol novolak resin (cresol/formaldehyde novolac resin, m-cresol/p-cresol (molar ratio) = 60/40, polystyrene conversion weight average molecular weight = 12,000, manufactured by Asahi Organic Materials Co., Ltd., Trade name "EP4020G")

J2: J2 was synthesized as follows.

<J2: Synthesis of Phenolic Resin Modified with Compounds Having Unsaturated Hydrocarbon Groups of 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, and the mixture was stirred at 120° C. for 2 hours to obtain a vegetable oil-modified phenol derivative (a). 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 the mixture was stirred at 90° C. for 3 hours. Next, the temperature was raised to 120° C. and stirred under reduced pressure for 3 hours, then 29 g of succinic anhydride and 0.3 g of triethylamine were added to the reaction liquid, and the mixture was stirred at 100° C. for 1 hour under atmospheric pressure. The reaction solution was cooled to room temperature to obtain a phenolic resin (hereinafter referred to as "J2 resin") modified by a compound having an unsaturated hydrocarbon group having a carbon number of 4 to 100 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.

[Examples 12 to 22, Comparative Examples 3 to 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 mass part.

Using the compounds described in Table 6, the photosensitive resin compositions of Examples 12 to 22 and Comparative Examples 3 to 4 were prepared at the compounding amounts described in Tables 7 and 8.

The produced photosensitive resin composition was subjected to (4) a 5% weight reduction temperature measurement test, (5) a reflow resistance test of the sealing material, and (6) an adhesion test with the sealing material. The results of each test are shown in Table 7 below.

(4) 5% weight loss temperature measurement test

Using the photosensitive resin compositions prepared in Examples and Comparative Examples, a fan-out wafer-level chip-scale package semiconductor device was fabricated. The interlayer insulating film with a thickness of 10 μm was taken out as completely as possible from the fabricated semiconductor device. Using a DTG-60A apparatus manufactured by Shimadzu Corporation, the interlayer insulating film taken out was measured at a temperature increase rate of 10° C./min under a nitrogen atmosphere, and the 5% weight loss temperature was measured.

(5) Reflow resistance test of sealing material

R4000 series manufactured by Nagase Chemical Co., Ltd. is prepared as epoxy-based sealing material. Next, the sealing material was spin-coated on the aluminum sputtered silicon wafer so as to have a thickness of about 150 μm, and the epoxy-based sealing material was cured by thermal 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 a final film thickness might become 10 micrometers. For the coated photosensitive resin composition, in Examples 12 to 15, 21, and Comparative Example 3, the exposure conditions were 200 mJ/cm ² , and in Examples 16 to 18, 22, and Comparative Example 4, the exposure conditions were 500 mJ/cm The exposure conditions of ² were in Examples 19 and 20 under the exposure conditions of 700 mJ/cm ² . After exposing the entire surface, thermal curing was performed at 180° C. for 2 hours to form a first-layer cured film with a thickness of 10 μm.

The photosensitive resin composition used for the formation of the first-layer cured film was applied on the first-layer cured film, and the entire surface was exposed to light under the same conditions as when the first-layer cured film was formed, and then it was heated. It was hardened to form a second-layer cured film with a thickness of 10 μm.

After the second layer of cured film was formed, the test piece was placed in a continuous calciner using a mesh belt type (Koyo Under simulated reflow conditions manufactured by Thermo Systems, model name 6841-20AMC-36), it was heated to a peak temperature of 260° C. under a nitrogen atmosphere. The so-called simulated reflow conditions are based on the reflow conditions described in Item 7.6 of IPC/JEDEC J-STD-020A, the standard specification of the American semiconductor industry group related to the evaluation method of semiconductor devices, and the melting point of the solder is assumed. Standardized for high temperature of 220°C.

The cured film processed under the above-mentioned simulated reflow conditions was cut out with a FIB apparatus (manufactured by Nippon Electronics Co., Ltd., JIB-4000), and the degree of deterioration was evaluated by confirming the presence or absence of voids in the epoxy portion. The case where no voids were found was made into ○, and the case in which even one void was found was made into ×.

(6) Adhesion test with sealing material

The sample photosensitive resin cured film prepared in the test of (5) was placed with a stylus, and the adhesion test was performed using a traction tester (manufactured by Quad Group, Sebastian 5 type).

Evaluation: Adhesion strength is 70 MPa or more‧‧‧‧‧‧‧‧‧‧adhesive force◎

More than 50MPa and less than -70MPa‧‧‧adhesion ○

More than 30MPa and less than -50MPa‧‧‧adhesive force△

Less than 30MPa‧‧‧‧‧‧ close contact ×

From Tables 7 and 8, it can be seen that when the 5% weight reduction temperature is 300°C or lower, it can be confirmed from the results of the tests (4) to (6) of 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 portion, and in the adhesion test with the sealing material, the evaluation of the adhesion force was any of ⊚, ∘, and Δ.

On the other hand, as can be seen from Tables 7 and 8, from the results of the tests (4) to (6) of the photosensitive resin compositions of Comparative Examples 3 and 4, it was confirmed that the 5% weight reduction temperature exceeded 300°C. In this case, 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 x.

Using the photosensitive resin compositions of Examples 12 to 22, it was produced in the mold resin containing the ring Oxygen resin fan-out type wafer-level chip-scale packaged semiconductor devices can operate without problems as a result.

(Polymer O-1: Synthesis of Polyimide Precursor)

4,4'-Oxydiphthalic dianhydride (ODPA), which is a tetracarboxylic dianhydride, was put into a separable flask having a capacity of 2 liters. Furthermore, 2-hydroxyethyl methacrylate (HEMA) and γ-butyrolactone were put and stirred at room temperature, and pyridine was added while stirring to obtain a reaction mixture. After the exotherm due to the reaction was over, it was left to cool to room temperature for 16 hours.

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

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

(Synthesis of polymers O-2~O-4)

A polyimide precursor (polymer O-2) was obtained by reacting in the same manner as the method described in the above-mentioned polymer O-1, except that the tetracarboxylic dianhydride and the diamine were changed as shown in the following Table 9. ~O-4).

(Polymer P-1: polybenzo

Synthesis of azole precursors)

唑前驅物(聚合物P-1))。關於聚合物P-1中所使用之化合物之質量，如下述表9所示。 In a 0.5-liter flask equipped with a stirrer and a thermometer, 15.48 g of 4,4'-diphenyl ether dicarboxylic acid as dicarboxylic acid and N-methylpyrrolidone were charged. After cooling the flask to 5°C, thionium chloride was added dropwise and allowed to react for 30 minutes to obtain a solution of dicarboxylate chloride. Next, a 0.5-liter flask with a stirrer and a thermometer was charged with N-methylpyrrolidone. After stirring and dissolving 18.30 g of bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 2.18 g of m-aminophenol which are bisaminophenols, pyridine was added. Then, the solution of dicarboxylate chloride was added dropwise over 30 minutes while maintaining the temperature at 0 to 5°C, and stirring was continued for 30 minutes. The solution was poured into 3 liters of water, the precipitate was recovered, washed with pure water 3 times, and then dried under reduced pressure to obtain a polymer (polybenzoic acid).

azole precursor (polymer P-1)). The mass of the compound used in the polymer P-1 is shown in Table 9 below.

(Synthesis of polymers P-2~P-3)

唑前驅物(聚合物P-2~P-3)。 The reaction was carried out in the same manner as the method described in the above-mentioned polymer P-1, except that the dicarboxylic acid and bisaminophenol were changed as shown in Table 9 below to obtain polybenzoyl

azole precursors (polymers P-2~P-3).

(Polymer Q-1: Synthesis of Phenolic Resin)

Prepare a phenol resin containing 85 g of the Q1 resin shown below and 15 g of the Q2 resin shown below as polymer Q-1.

Q1: Cresol novolak resin (cresol/formaldehyde novolak resin, m-cresol/p-cresol (molar ratio) = 60/40, polystyrene conversion weight average molecular weight = 12,000, manufactured by Asahi Organic Materials Co., Ltd., Trade name "EP4020G")

Q2: Q2 was synthesized as follows.

<Q2: Synthesis of a phenolic resin modified by a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms>

100 parts by mass of phenol, 43 parts by mass of linseed oil, and 0.1 part by mass of trifluoromethanesulfonic acid were mixed, and the mixture was stirred at 120° C. for 2 hours to obtain a vegetable oil-modified phenol derivative (a). 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 the mixture was stirred at 90° C. for 3 hours. Next, the temperature was raised to 120° C. and stirred under reduced pressure for 3 hours, then 29 g of succinic anhydride and 0.3 g of triethylamine were added to the reaction liquid, and the mixture was stirred at 100° C. 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") modified by a compound having an unsaturated hydrocarbon group having a carbon number of 4 to 100 as a reaction product (acid value: 120 mgKOH/g) ).

(Synthesis of polymer Q-2)

100 g of the following Q1 resin was prepared as polymer Q-2.

[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 mass part.

Using the compounds described in Table 10, the photosensitive resin compositions of Examples 23 to 33 and Comparative Examples 5 to 6 were prepared at the compounding amounts described in Tables 11 and 12.

(7) The refractive index difference measurement test, (8) the reflow resistance test of the sealing material, and (9) the adhesion test with the 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

Using the photosensitive resin compositions prepared in Examples and Comparative Examples, a fan-out wafer-level chip-scale package semiconductor device was produced. The interlayer insulating film with a thickness of 10 μm was taken out as completely as possible from the fabricated semiconductor device. About the extracted interlayer insulating film, the difference between the in-plane refractive index and the out-of-plane refractive index at a wavelength of 1310 nm was measured using a pyran coupler device (PC-2010) manufactured by METRICON.

(8) Reflow resistance test of sealing material

R4000 series manufactured by Nagase Chemical Co., Ltd. is prepared as epoxy-based sealing material. Next, the sealing material was spin-coated on the aluminum sputtered silicon wafer so as to have a thickness of about 150 μm, and the epoxy-based sealing material was cured by thermal 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 a final film thickness might become 10 micrometers. For the coated photosensitive resin composition, in Examples 23-26, 32, and Comparative Example 5, the exposure conditions were 200 mJ/cm ² , and in Examples 27-29, 33, and Comparative Example 6, the exposure conditions were 500 mJ/cm As for the exposure conditions of ² , after exposing the entire surface, thermal curing was performed at 150° C. for 4 hours to prepare a first-layer cured film with a thickness of 10 μm.

The photosensitive resin composition used for the formation of the first-layer cured film was applied on the first-layer cured film, and the entire surface was exposed to light under the same conditions as when the first-layer cured film was formed. It was thermally cured to form a second-layer cured film with a thickness of 10 μm.

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

The cured film processed under the above-mentioned simulated reflow conditions was cut out with a FIB apparatus (manufactured by Nippon Electronics Co., Ltd., JIB-4000), and the degree of deterioration was evaluated by confirming the presence or absence of voids in the epoxy portion. The case where no voids were found was made into ○, and the case in which even one void was found was made into ×.

(9) Adhesion test with sealing material

The sample photosensitive resin cured film produced in the test of (8) was placed with a stylus, and the adhesion test was performed using a traction tester (manufactured by Quad Group, Sebastian 5 type).

Evaluation: Adhesion strength is 70 MPa or more‧‧‧‧‧‧‧‧‧‧adhesive force◎

More than 50MPa and less than -70MPa‧‧‧adhesion ○

More than 30MPa and less than -50MPa‧‧‧adhesive force△

Less than 30MPa‧‧‧‧‧‧ close contact ×

From Tables 11 and 12, it can be seen from the results of the tests (7) to (9) conducted on the photosensitive resin compositions of Examples 23 to 33 that when the refractive index difference 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 any of ⊚, ∘, and Δ.

On the other hand, as can be seen from Tables 11 and 12, when the difference in refractive index exceeds 0.0150, it can be confirmed from the results of the tests (7) to (9) of the photosensitive resin compositions of Comparative Examples 5 and 6 that 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 x.

Moreover, using the photosensitive resin compositions of Examples 23 to 33, a fan-out type wafer-level chip-scale package semiconductor device containing an epoxy resin in a mold resin was produced, and as a result, it was possible to operate without problems.

[Industrial Availability]

The present invention can be preferably applied to a semiconductor device including a semiconductor chip and a rewiring layer connected to the semiconductor chip, especially a fan-out type wafer-level chip-scale package type semiconductor device.

1‧‧‧Semiconductor device

2‧‧‧Semiconductor chip

2a‧‧‧Terminal

3‧‧‧Sealing material

4‧‧‧Rewiring layer

5‧‧‧Wiring

6‧‧‧Interlayer insulating film

7‧‧‧External connection terminal

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Claims (36)

A semiconductor device, comprising: a semiconductor chip, a sealing material covering the semiconductor chip, and a rewiring layer having an area larger than the semiconductor chip in plan view, and the i-ray transmittance of the interlayer insulating film between the rewiring layers is 10 μm in thickness The conversion calculation is less than 80%. The semiconductor device of claim 1, wherein the sealing material is in direct contact with the interlayer insulating film. The semiconductor device according to claim 1 or 2, wherein said sealing material comprises epoxy resin. The semiconductor device according to claim 1 or 2, wherein the above-mentioned interlayer insulating film comprises a material selected from the group consisting of polyimide, polybenzoyl

At least one of an azole and a polymer having a phenolic hydroxyl group. The semiconductor device of claim 4, wherein the interlayer insulating film comprises a polyimide having a structure of the following general formula (1),

(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). The semiconductor device according to claim 5, wherein X ¹ in the general formula (1) is a tetravalent organic group containing an aromatic ring, and Y ¹ in the general formula (1) is a divalent organic group containing an aromatic ring base. The semiconductor device of claim 5, wherein X ¹ in the general formula (1) includes at least one structure represented by the following general formula (2) to general formula (4),

(In the general formula (4), R ₉ is an oxygen atom, a sulfur atom, or a divalent organic group). The semiconductor device of claim 7, wherein X ¹ in the above general formula (1) includes a structure represented by the following general formula (5),

The semiconductor device according to claim 5, wherein Y ¹ in the above general formula (1) comprises at least one structure represented by the following general formula (6) to general formula (8),

(R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are hydrogen atoms, monovalent aliphatic groups or hydroxyl groups having 1 to 5 carbon atoms, which may be the same or different)

(R ₁₄ to R ₂₁ are hydrogen atoms, halogen atoms, monovalent organic groups with 1 to 5 carbon atoms, or hydroxyl groups, which may be different from each other or the same) [Chem. 8]

(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). The semiconductor device of claim 9, wherein Y ¹ in the above general formula (1) includes a structure represented by the following general formula (9),

The semiconductor device of claim 4, wherein the above-mentioned polybenzo

The azoles include polybenzos having the structure of the following general formula (10)

azole,

(In the general formula (10), U and V are divalent organic groups). The semiconductor device of claim 11, wherein U of the general formula (10) is a divalent carbon number of 1 to 30 organic base. The semiconductor device according to claim 12, wherein U of the general formula (10) is a chain alkylene group having 1 to 8 carbon atoms and a part or all of hydrogen atoms substituted by fluorine atoms. The semiconductor device according to claim 11, wherein V of the general formula (10) is a divalent organic group containing an aromatic group. The semiconductor device of claim 14, wherein V of the general formula (10) includes at least one structure represented by the following general formulas (6) to (8),

(R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are hydrogen atoms and monovalent aliphatic groups having 1 to 5 carbon atoms, which may be the same or different)

(R ₁₄ to R ₂₁ are hydrogen atoms, halogen atoms, and monovalent organic groups with 1 to 5 carbon atoms, which may be different from each other or the same)

(R ₂₂ is a divalent organic group or an oxygen atom, and R ₂₃ to R ₃₀ are a hydrogen atom, a halogen atom, or a monovalent aliphatic group having 1 to 5 carbon atoms, which may be the same or different). The semiconductor device of claim 15, wherein V of the above general formula (10) includes a structure represented by the following general formula (9),

The semiconductor device according to claim 11, wherein V of the general formula (10) is a divalent organic group having 1 to 40 carbon atoms. The semiconductor device according to claim 17, wherein V of the general formula (10) is a divalent chain aliphatic group having 1 to 20 carbon atoms. The semiconductor device of claim 4, wherein the polymer having a phenolic hydroxyl group comprises phenolic Varnish-type phenolic resin. The semiconductor device according to claim 4, wherein the polymer having a phenolic hydroxyl group comprises a phenol resin having no 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 cross-section, the rewiring layer comprises: a first interlayer insulating film layer; a second interlayer insulating film layer; The first interlayer insulating film layer and the second interlayer insulating film layer are different layers, and are provided between the first interlayer insulating film layer and the second interlayer insulating film layer. The semiconductor device of claim 21, wherein 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. The semiconductor device of claim 21, wherein the composition of the second interlayer insulating film layer is different from that of the first interlayer insulating film layer. The semiconductor device of claim 21, wherein 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. The semiconductor device of claim 1 or 2, wherein the semiconductor device is a fan-out type wafer-level chip-scale package type semiconductor device. The semiconductor device according to claim 1 or 2, wherein the i-ray transmittance of the interlayer insulating film between the rewiring layers is 70% or less in terms of a thickness of 10 μm. The semiconductor device of claim 26, wherein the i-ray transmittance of the interlayer insulating film of the rewiring layer is 60% or less in terms of a thickness of 10 μm. The semiconductor device of claim 26, wherein the i-ray transmittance of the interlayer insulating film of the rewiring layer is 50% or less in terms of a thickness of 10 μm. The semiconductor device of claim 26, wherein the i-ray transmittance of the interlayer insulating film of the rewiring layer is 40% or less in terms of a thickness of 10 μm. The semiconductor device according to claim 26, wherein the i-ray transmittance of the interlayer insulating film of the rewiring layer is 30% or less in terms of a thickness of 10 μm. The semiconductor device according to claim 1 or 2, wherein the i-ray transmittance of the interlayer insulating film between the rewiring layers is 5% or more in terms of a thickness of 10 μm. The semiconductor device of claim 31, wherein the i-ray transmittance of the interlayer insulating film of the rewiring layer is 10% or more in terms of thickness of 10 μm. The semiconductor device of claim 31, wherein the i-ray transmittance of the interlayer insulating film of the rewiring layer is 20% or more in terms of a thickness of 10 μm. A method of manufacturing a semiconductor device, comprising: a step of covering a 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 i of the interlayer insulating film The radiation transmittance is 80% or less in terms of thickness of 10 μm. As claimed in claim 34, the method for manufacturing a semiconductor device, which comprises using a formable polyimide, polybenzoyl

The photosensitive resin composition of azole and at least one compound of a polymer having a phenolic hydroxyl group forms the interlayer insulating film forming step of the above-mentioned interlayer insulating film. The method for manufacturing a semiconductor device according to claim 35, wherein said interlayer insulating film forming step comprises using said photosensitive resin composition adjusted with additives such that i-ray transmittance of said interlayer insulating film becomes 80% or less in terms of thickness of 10 μm step of forming the above-mentioned interlayer insulating film.

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