TWI840154B - Semiconductor device and method for manufacturing the same - Google Patents

Abstract

The purpose of the present invention is to provide a semiconductor device having excellent adhesion between an interlayer insulating film and a sealing material in a redistribution layer and a method for manufacturing the same. The semiconductor device (1) of the present invention is characterized in that it comprises: a semiconductor chip (2), a sealing material (3) covering the semiconductor chip, and a redistribution layer (4) having an area larger than the semiconductor chip when viewed from above, and the i-ray transmittance of the interlayer insulating film (6) of the redistribution layer is less than 80%. According to the present invention, a semiconductor device having excellent adhesion between an interlayer insulating film and a sealing material in a redistribution layer and a method for manufacturing the same can be provided.

Description

Semiconductor device and method for manufacturing the same

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

There are various semiconductor packaging techniques for semiconductor devices. For example, there is a semiconductor packaging technique in which a semiconductor chip is covered with a sealing material (molding resin) to form a component sealing material, and then a redistribution layer electrically connected to the semiconductor chip is formed. Among semiconductor packaging techniques, the fan-out semiconductor packaging technique has become mainstream in recent years.

In a fan-out semiconductor package, a semiconductor chip is covered with a sealing material to form a chip seal having a chip size larger than the semiconductor chip. Furthermore, a redistribution layer is formed to the area between the semiconductor chip and the sealing material. The redistribution layer is formed with a thinner film thickness. In addition, the redistribution layer can be formed to the area of the sealing material, so 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 document] [Patent document]

[Patent Document 1] Japanese Patent Publication No. 2011-129767

[The problem the invention is trying to solve]

In a fan-out semiconductor device, a higher degree of adhesion is required between an interlayer insulating film in a redistribution layer and a sealing material. However, the adhesion between the interlayer insulating film in a redistribution layer and a sealing material in a conventional fan-out semiconductor device is not sufficient.

The present invention is made in view of this point, and its purpose is to provide a semiconductor device with excellent adhesion between the interlayer insulating film and the sealing material in the redistribution layer, and a manufacturing method thereof. [Technical means to solve the problem]

The semiconductor device of the present invention is characterized in that it comprises: a semiconductor chip, a sealing material covering the semiconductor chip, and a redistribution layer having an area larger than the semiconductor chip when viewed from above, wherein the i-ray transmittance of the interlayer insulating film of the redistribution layer is less than 80% when converted to a thickness of 10 μm.

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

In the present invention, it is preferred that the sealing material comprises epoxy resin.

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

In the present invention, it is preferred that the interlayer insulating film comprises a polyimide having a structure represented by the following general formula (1). (In the general formula (1), ^X1 is a tetravalent organic group, ^Y1 is a divalent organic group, and m is an integer greater than or equal to 1)

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

In the present invention, it is preferred that ^X1 in the above general formula (1) comprises at least one structure represented by the following general formulas (2) to (4). [Chemistry 3] [Chemistry 4] (In the general formula (4), _R9 is an oxygen atom, a sulfur atom, or a divalent organic group)

In the present invention, it is preferred that ^X1 in the above general formula (1) comprises a structure represented by the following general formula (5).

In the present invention, it is preferred that ^Y1 in the above general formula (1) comprises 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 having 1 to 5 carbon atoms or hydroxyl groups, and may be the same or different) [Chemistry 7] (R ₁₄ to R ₂₁ are hydrogen atoms, halogen atoms, monovalent organic groups having 1 to 5 carbon atoms, or hydroxyl groups, and may be different from each other or the same) [Chemistry 8] (R ₂₂ is a divalent organic group, R ₂₃ to R ₃₀ are hydrogen atoms, halogen atoms, monovalent aliphatic groups with 1 to 5 carbon atoms, or hydroxyl groups, which may be the same or different)

In the present invention, it is preferred that ^Y1 in the above general formula (1) comprises a structure represented by the following general formula (9).

In the present invention, it is preferred that the polybenzoxazole comprises a polybenzoxazole having a structure represented by the following general formula (10). (In the general formula (10), U and V are divalent organic groups)

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

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

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

In the present invention, it is preferred that V in the above general formula (10) comprises 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 having 1 to 5 carbon atoms, and may be the same or different) [Chemical 12] (R ₁₄ to R ₂₁ are hydrogen atoms, halogen atoms, or monovalent organic groups having 1 to 5 carbon atoms, and may be different from or the same as each other) [Chemical 13] (R ₂₂ is a divalent organic group, R ₂₃ to R ₃₀ are hydrogen atoms, halogen atoms, or monovalent aliphatic groups having 1 to 5 carbon atoms, and they may be the same or different)

In the present invention, it is preferred that V in the above general formula (10) comprises a structure represented by the following general formula (9).

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

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

In the present invention, it is preferred that the polymer having a phenolic hydroxyl group comprises a novolac type phenolic resin.

In the present invention, it is preferred that 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.

In the present invention, it is preferred that when the redistribution layer is observed in cross section, the redistribution layer includes: a first interlayer insulating film layer; a second interlayer insulating film layer; and an intermediate layer, which is a layer different from the first interlayer insulating film layer and the second interlayer insulating film layer, and is arranged between the first interlayer insulating film layer and the second interlayer insulating film layer.

In the present invention, it is preferred that 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 when converted to a thickness of 10 μm.

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

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

In the present invention, it is preferred that the semiconductor device is a fan-out type wafer-level chip scale package type semiconductor device.

In the present invention, it is preferred that the i-ray transmittance of the interlayer insulating film of the redistribution layer is 70% or less when converted to a thickness of 10 μm.

In the present invention, it is preferred that the i-ray transmittance of the interlayer insulating film of the redistribution layer is 60% or less when converted to a thickness of 10 μm.

In the present invention, it is preferred that the i-ray transmittance of the interlayer insulating film of the redistribution layer is 50% or less when converted to a thickness of 10 μm.

In the present invention, it is preferred that the i-ray transmittance of the interlayer insulating film of the redistribution layer is 40% or less when converted to a thickness of 10 μm.

In the present invention, it is preferred that the i-ray transmittance of the interlayer insulating film of the redistribution layer is 30% or less when converted to a thickness of 10 μm.

In the present invention, it is preferred that the i-ray transmittance of the interlayer insulating film of the redistribution layer be 5% or more when converted to a thickness of 10 μm.

In the present invention, the i-ray transmittance of the interlayer insulating film of the redistribution layer may be 10% or more when converted to a thickness of 10 μm.

In the present invention, the i-ray transmittance of the interlayer insulating film of the redistribution layer may be 20% or more when converted to a thickness of 10 μm.

The manufacturing method of the semiconductor device in the present invention is characterized in that it includes: a step of covering a semiconductor chip with a sealing material, and a step of forming a redistribution layer having an area larger than the semiconductor chip in a top view and including an interlayer insulating film, and the i-ray transmittance of the interlayer insulating film is less than 80% when converted to a thickness of 10 μm.

In the present invention, it is preferred that the interlayer insulating film forming step includes forming the interlayer insulating film using a photosensitive resin composition that can form at least one compound of polyimide, polybenzoxazole, and a polymer having a phenolic hydroxyl group.

In the present invention, it is preferred that the interlayer insulating film forming step includes forming the interlayer insulating film using the photosensitive resin composition adjusted with an additive so that the i-ray transmittance of the interlayer insulating film becomes 80% or less based on a thickness of 10 μm.

One aspect of the semiconductor device of the present embodiment is characterized in that it includes: a semiconductor chip, a sealing material covering the semiconductor chip, and a redistribution layer having an area larger than the semiconductor chip when viewed from above, wherein the 5% weight reduction temperature of the interlayer insulating film of the redistribution layer is below 300°C.

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

In one aspect of the semiconductor device of the present invention, it is preferred that the sealing material comprises epoxy resin.

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

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

[Chemistry 15] (In the general formula (1), ^X1 is a tetravalent organic group, ^Y1 is a divalent organic group, and m is an integer greater than or equal to 1)

In one aspect of the semiconductor device of the present invention, preferably, ^X1 in the general formula (1) is a tetravalent organic group containing an aromatic ring, and ^Y1 in the general formula (1) is a divalent organic group containing an aromatic ring.

In one aspect of the semiconductor device of the present invention, it is preferred that ^X1 in the above general formula (1) includes at least one structure represented by the following general formulas (2) to (4).

[Chemistry 16] [Chemistry 17] [Chemistry 18] (In the general formula (4), _R9 is an oxygen atom, a sulfur atom, or a divalent organic group)

In one aspect of the semiconductor device of the present invention, preferably, ^X1 in the above general formula (1) includes a structure represented by the following general formula (5).

[Chemistry 19]

In one aspect of the semiconductor device of the present invention, it is preferred that ^Y1 in the above general formula (1) includes at least one structure represented by the following general formulas (6) to (8).

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

In one aspect of the semiconductor device of the present invention, it is preferred that ^Y1 in the above general formula (1) includes a structure represented by the following general formula (9).

[Chemistry 23]

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

[Chemistry 24] (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 embodiment of the semiconductor device of the present invention, U in the general formula (10) is preferably a chain alkylene group having 1 to 8 carbon atoms and in which a part or all of the hydrogen atoms are substituted by fluorine atoms.

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

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

[Chemistry 25] (R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are hydrogen atoms, monovalent aliphatic groups having 1 to 5 carbon atoms, and may be the same or different) [Chemical 26] (R ₁₄ to R ₂₁ are hydrogen atoms, halogen atoms, or monovalent organic groups having 1 to 5 carbon atoms, and may be different from or the same as each other) [Chemical 27] (R ₂₂ is a divalent group, R ₂₃ to R ₃₀ are hydrogen atoms, halogen atoms, or monovalent aliphatic groups having 1 to 5 carbon atoms, and they may be the same or different)

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

[Chemistry 28]

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

In one aspect of the semiconductor device of the present invention, it is preferred that the polymer having a phenolic hydroxyl group comprises a novolac type phenolic resin.

In one aspect of the semiconductor device of the present invention, it is preferred that 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.

In one embodiment of the semiconductor device of the present invention, it is preferred that when the redistribution layer is observed in cross section, the redistribution layer includes: a first interlayer insulating film layer; a second interlayer insulating film layer; and an intermediate layer, which is a layer different from the first interlayer insulating film layer and the second interlayer insulating film layer, and is arranged 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 preferred that the first interlayer insulating film layer is in contact with the sealing material, and the 5% weight loss temperature of the first interlayer insulating film layer is below 300°C.

In one aspect of the semiconductor device of the present invention, it is preferred 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, it is preferred that 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 preferred that the 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, it is preferred that the 5% weight reduction temperature of the interlayer insulating film of the redistribution layer is below 280°C.

In one aspect of the semiconductor device of the present invention, it is preferred that the 5% weight reduction temperature of the interlayer insulating film of the redistribution layer is below 260°C.

In one aspect of the semiconductor device of the present invention, it is preferred that the 5% weight reduction temperature of the interlayer insulating film of the redistribution layer is below 240°C.

In one aspect of the semiconductor device of the present invention, it is preferred that the 5% weight reduction temperature of the interlayer insulating film of the redistribution layer is below 220°C.

In one aspect of the semiconductor device of the present invention, it is preferred that the 5% weight reduction temperature of the interlayer insulating film of the redistribution layer is below 200°C.

In one aspect of the semiconductor device of the present invention, it is preferred that the 5% weight reduction temperature of the interlayer insulating film of the redistribution layer is above 80°C.

In one aspect of the semiconductor device of the present invention, it is preferred that the 5% weight reduction temperature of the interlayer insulating film of the redistribution layer is below 100°C.

In one aspect of the semiconductor device of the present invention, it is preferred that the 5% weight reduction temperature of the interlayer insulating film of the redistribution layer is 150° C. or less.

In one aspect of the method for manufacturing a semiconductor device of the present invention, it is characterized in that it includes: a step of covering a semiconductor chip with a sealing material, and a step of forming a redistribution layer having an area larger than the semiconductor chip when viewed from above and including an interlayer insulating film, and the 5% weight reduction temperature of the interlayer insulating film is below 300°C.

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

In one aspect of the method for manufacturing a semiconductor device of the present invention, the interlayer insulating film forming step preferably includes forming the interlayer insulating film using the photosensitive resin composition adjusted with an additive in such a manner that the temperature of the interlayer insulating film is reduced to below 300°C by 5% weight.

One aspect of the semiconductor device of the present invention is characterized in that it includes: a semiconductor chip, a sealing material covering the semiconductor chip, and a redistribution layer having an area larger than the semiconductor chip when viewed from above, wherein the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the redistribution layer at a wavelength of 1310 nm is less than 0.0150.

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

In one aspect of the semiconductor device of the present invention, it is preferred that the sealing material comprises epoxy resin.

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

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

[Chemistry 29] (In the general formula (1), ^X1 is a tetravalent organic group, ^Y1 is a divalent organic group, and m is an integer greater than or equal to 1)

In one aspect of the semiconductor device of the present invention, preferably, ^X1 in the general formula (1) is a tetravalent organic group containing an aromatic ring, and ^Y1 in the general formula (1) is a divalent organic group containing an aromatic ring.

In one aspect of the semiconductor device of the present invention, it is preferred that ^X1 in the above general formula (1) includes at least one structure represented by the following general formulas (2) to (4).

[Chemistry 30] [Chemistry 31] [Chemistry 32] (In the general formula (4), _R9 is an oxygen atom, a sulfur atom, or a divalent organic group)

In one aspect of the semiconductor device of the present invention, preferably, ^X1 in the above general formula (1) includes a structure represented by the following general formula (5).

[Chemistry 33]

In one aspect of the semiconductor device of the present invention, it is preferred that ^Y1 in the above general formula (1) includes at least one structure represented by the following general formulas (6) to (8).

[Chemistry 34] (R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are hydrogen atoms, monovalent aliphatic groups having 1 to 5 carbon atoms, or hydroxyl groups, and may be the same or different) [Chemistry 35] (R ₁₄ to R ₂₁ are hydrogen atoms, halogen atoms, monovalent organic groups having 1 to 5 carbon atoms, or hydroxyl groups, and may be different from each other or the same) [Chemical 36] (R ₂₂ is a divalent group, R ₂₃ to R ₃₀ are hydrogen atoms, halogen atoms, monovalent aliphatic groups with 1 to 5 carbon atoms, or hydroxyl groups, which may be the same or different)

In one aspect of the semiconductor device of the present invention, it is preferred that ^Y1 in the above general formula (1) includes a structure represented by the following general formula (9).

[Chemistry 37]

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

[Chemistry 38] (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 embodiment of the semiconductor device of the present invention, U in the general formula (10) is preferably a chain alkylene group having 1 to 8 carbon atoms and in which a part or all of the hydrogen atoms are substituted by fluorine atoms.

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

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

[Chemistry 39] (R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are hydrogen atoms, monovalent aliphatic groups having 1 to 5 carbon atoms, and may be the same or different) [Chemical 40] (R ₁₄ to R ₂₁ are hydrogen atoms, halogen atoms, or monovalent organic groups having 1 to 5 carbon atoms, and may be different from or the same as each other) [Chemical 41] (R ₂₂ is a divalent group, R ₂₃ to R ₃₀ are hydrogen atoms, halogen atoms, or monovalent aliphatic groups having 1 to 5 carbon atoms, and they may be the same or different)

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

[Chemistry 42]

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

In one aspect of the semiconductor device of the present invention, it is preferred that the polymer having a phenolic hydroxyl group comprises a novolac type phenolic resin.

In one aspect of the semiconductor device of the present invention, it is preferred that 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.

In one embodiment of the semiconductor device of the present invention, it is preferred that when the redistribution layer is observed in cross section, the redistribution layer includes a first interlayer insulating film layer; a second interlayer insulating film layer; and an intermediate layer, which is a layer different from the first interlayer insulating film layer and the second interlayer insulating film layer, and is arranged 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 preferred that the first interlayer insulating film layer is in contact with the sealing material, and the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the first interlayer insulating film layer is less than 0.0150.

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

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

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

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

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

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

In one aspect of the semiconductor device of the present invention, it is preferred that the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the redistribution layer is greater than or equal to 0.0005.

In one aspect of the semiconductor device of the present invention, it is preferred that the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the redistribution layer is greater than or equal to 0.0010.

In one aspect of the semiconductor device of the present invention, it is preferred that the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the redistribution layer is greater than or equal to 0.0015.

One aspect of the method for manufacturing a semiconductor device of the present invention is characterized in that it includes: a step of covering a semiconductor chip with a sealing material, and a step of forming a redistribution layer having an area larger than the semiconductor chip when viewed from above and including an interlayer insulating film, and the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film is less than 0.0150.

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

In one embodiment of the method for manufacturing a semiconductor device of the present invention, the interlayer insulating film forming step preferably includes the step of forming the interlayer insulating film using the photosensitive resin composition adjusted with an additive in such a manner that the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film is less than 0.0150. [Effect of the invention]

The present invention can provide a semiconductor device having excellent adhesion between an interlayer insulating film in a redistribution layer and a sealing material, and a method for manufacturing the same.

Hereinafter, an embodiment of the semiconductor device of the present invention (hereinafter referred to as "embodiment") is described in detail with reference to the drawings. In addition, the present invention is not limited to the following embodiment, and can be implemented with various modifications within the scope of the gist thereof.

(Semiconductor device) As shown in FIG1 , a semiconductor device (semiconductor IC) 1 includes: a semiconductor chip 2, a sealing material (molding resin) 3 covering the semiconductor chip 2, and a redistribution layer 4 in close contact with the semiconductor chip 2 and the sealing material 3.

As shown in FIG. 1 , the sealing material 3 covers the surface of the semiconductor chip 2 and is formed to have an area larger than the area of the semiconductor chip 2 in a plan view (viewed along the arrow A).

The redistribution layer 4 has a plurality of wirings 5 electrically connected to a plurality of terminals 2a provided on the semiconductor chip 2, and an interlayer insulating film 6 filling the gaps between the wirings 5. The plurality of terminals 2a provided on the semiconductor chip 2 are electrically connected to the wirings 5 in the redistribution layer 4. One end of the wiring 5 is connected to the terminal 2a, 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 with the interlayer insulating film 6 over the entire surface.

As shown in FIG. 1 , in a top view (viewed along the arrow A), the redistribution layer 4 is formed larger than the semiconductor chip 2. 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 interlayer insulating film 6 in the redistribution layer 4 is in close contact not only with the semiconductor chip 2 but also with the sealing material 3. The semiconductor chip 2 includes a semiconductor such as silicon and has a circuit formed therein.

(Rewiring layer) The rewiring layer 4 mainly includes wiring 5 and an interlayer insulating film 6 covering the periphery of the wiring 5. From the perspective of preventing undesired conduction with the wiring 5, the interlayer insulating film 6 is preferably a member with higher insulation.

Here, the so-called "rewiring layer 4" in this embodiment is a thin film layer having wiring 5 and interlayer insulating film 6 as described above, and does not include an interposer or printed wiring board. FIG4 is a comparison diagram of flip chip BGA and fan-out (Fan-Out) type WLCSP. The semiconductor device (semiconductor IC) 1 (refer to FIG1) uses the rewiring layer 4, so as shown in FIG4, it is thinner than the semiconductor device using the interposer such as flip chip BGA.

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

When the semiconductor device 1 is viewed from above (viewed along the arrow A), it becomes as shown in the following Fig. 2. Fig. 2 is a schematic diagram of the semiconductor device of this embodiment when viewed from above. In addition, the sealing material 3 is omitted.

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

Furthermore, the shapes of the semiconductor chip 2 and the redistribution layer 4 may be the same or different. In FIG2 , the shapes of the semiconductor chip 2 and the redistribution layer 4 are both rectangular, but the shapes may be other than rectangular.

The redistribution layer 4 may be a single layer or may be a plurality of layers of two or more. The redistribution layer 4 includes the wiring 5 and the interlayer insulating film 6 filling the wiring 5, but the redistribution layer 4 may include a layer consisting only of the interlayer insulating film 6 or a layer consisting only of the wiring 5.

The wiring 5 is not particularly limited as long as it is a member with high electrical conductivity, and copper is generally used.

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

As shown in Fig. 1, the sealing material 3 is preferably in direct contact with the semiconductor chip 2 and the redistribution layer 4. This can effectively improve the sealing performance from the surface of the semiconductor chip 2 to the surface of the redistribution layer 4.

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

(Interlayer insulation film) In the first aspect of the present embodiment, the transmittance of the interlayer insulation film 6 for i-rays (wavelength of 365 nm) is less than 80%. Furthermore, the transmittance is the value when the film thickness of the interlayer insulation film 6 is converted to 10 μm. In addition, when the film thickness is not 10 microns (assuming it is y microns), the transmittance converted to 10 microns is calculated by using {(transmittance/100) ^10/y }×100 for the measured transmittance. The reason why the interlayer insulating film 6 in the wiring layer 4 has excellent adhesion to the sealing material 3 when the i-ray (wavelength: 365 nm) transmittance of the interlayer insulating film 6 is 80% or less is not yet determined, but the inventors of the present invention speculate as follows.

In the manufacturing process of a fan-out semiconductor device, in order to form a redistribution layer 4, a photosensitive resin composition is applied to a chip seal body including a semiconductor chip 2 and a sealing material 3. Then, the photosensitive resin composition is exposed to light including i-rays. Thereafter, the photosensitive resin composition is developed and cured to selectively form a portion having a cured photosensitive resin composition and a portion having no cured photosensitive resin composition. The cured photosensitive resin composition becomes an interlayer insulating film 6. Furthermore, wiring 5 is formed in the portion having no cured photosensitive resin composition. Usually, the redistribution layer 4 is a multi-layered layer in most cases. That is, a photosensitive resin composition is further coated on the interlayer insulating film 6 and the wiring 5, and a redistribution layer is further formed on the redistribution layer through exposure, development, and curing steps.

When exposure is performed to form the first redistribution layer or when exposure is performed to form the second redistribution layer, if the i-ray (wavelength is 365 nm) transmittance of the interlayer insulating film is high, the sealing material 3 is decomposed and degraded by the i-ray. Therefore, the adhesion between the interlayer insulating film and the sealing material 3 is reduced. In particular, epoxy resin is easily decomposed and degraded by i-ray. Therefore, when epoxy resin is used in the sealing material 3, the epoxy resin is decomposed and degraded by the i-ray, which promotes the reduction of the adhesion between the interlayer insulating film and the sealing material 3.

The interlayer insulating film 6 of this embodiment has an i-ray transmittance as low as 80% or less. Therefore, it is estimated that in this embodiment, it is difficult for the sealing material 3 to be decomposed or deteriorated by the i-ray, and the adhesion between the interlayer insulating film 6 and the sealing material 3 can be improved. Furthermore, when using an interlayer insulating film with a high i-ray (wavelength of 365 nm) transmittance, the i-ray (wavelength of 365 nm) transmittance can be reduced by making the interlayer insulating film thicker. However, this has the disadvantage of making the semiconductor device thicker as a whole. The semiconductor device of this embodiment can reduce the transmittance of i-rays (wavelength is 365 nm) without making the semiconductor device as a whole thicker, and the interlayer insulating film in the wiring layer and the sealing material have excellent adhesion.

As for the transmittance of i-ray (wavelength of 365 nm) of the interlayer insulating film 6, from the viewpoint of the close contact between the interlayer insulating film in the redistribution layer and the sealing material, it is preferably 80% or less, preferably 78% or less, preferably 76% or less, preferably 74% or less, preferably 72% or less, preferably 70% or less, preferably 68% or less, preferably 66% or less, preferably 64% or less, preferably 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. % 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% or less, preferably 32% or less, preferably 30% or less, preferably 28% or less, preferably 26% or less, preferably 24% or less, preferably 22% or less, preferably 20% or less, preferably 18% or less, preferably 16% or less, preferably 14% or less, preferably 12% or less.

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

In addition, there is no particular limitation on the lower limit of the transmittance of i-rays (wavelength of 365 nm) of the interlayer insulating film 6, but from the viewpoint of making the pattern shape of the interlayer insulating film 6 good, it is preferably 0.1% or 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, and preferably 40% or more.

Furthermore, the interlayer insulating film 6 in the redistribution layer 4 may also be a plurality of layers. That is, when the redistribution layer 4 is observed in cross section, the redistribution layer 4 may include a first interlayer insulating film layer; a second interlayer insulating film layer; and an intermediate layer, which is a layer different from the first interlayer insulating film layer and the second interlayer insulating film layer, and is disposed between the first interlayer insulating film layer and the second interlayer insulating film layer. The 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 different compositions. The first interlayer insulating film layer and the second interlayer insulating film layer may have the same i-ray transmittance or different i-ray transmittances. The first interlayer insulating film layer and the second interlayer insulating film layer may have the same film thickness or different film thicknesses. If the first interlayer insulating film layer and the second interlayer insulating film layer have different compositions or different i-ray transmittances or different film thicknesses, each interlayer insulating film layer may have different properties, which is preferred.

When the interlayer insulating film 6 is a multi-layer film, the i-ray transmittance of at least one layer among the multiple layers is 80% or less, and preferably the i-ray transmittance of the interlayer insulating film layer (the first interlayer insulating film layer) in contact with the sealing material 3 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 efficiently absorbed, and the deterioration of the sealing material can be prevented. The range of the preferred i-ray transmittance of each interlayer insulating film layer is the same as the range of the preferred 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 less. Hereinafter, "5% weight reduction temperature" is referred to as "weight reduction temperature". If the weight reduction temperature is 300°C or less, the interlayer insulating film 6 and the sealing material 3 have excellent adhesion during high temperature treatment. The reason is not yet certain, but the inventors of the present invention speculate as follows.

In the manufacturing process of the fan-out semiconductor device 1 (refer to Figure 1), in order to form a redistribution layer 4, a photosensitive resin composition is applied on a chip seal body including a semiconductor chip 2 and a sealing material 3. Then, the photosensitive resin composition is exposed to light including i-rays. Thereafter, the photosensitive resin composition is developed and cured to selectively form a portion having a cured photosensitive resin composition and a portion having no cured photosensitive resin composition. The cured photosensitive resin composition becomes an interlayer insulating film 6. Furthermore, wiring 5 is formed in a portion having no cured photosensitive resin composition. Normally, the redistribution layer 4 is often multi-layered. That is, a photosensitive resin composition is further applied on the interlayer insulating film 6 and the wiring 5, and then exposed, developed, and cured.

However, 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. If the sealing material 3 is heated for a long time, there is a possibility that gas is generated from the sealing material 3. When the density of the interlayer insulating film 6 is large, that is, when the weight reduction temperature of the interlayer insulating film 6 is high, the gas generated from the sealing material 3 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 become easy to peel off. In particular, epoxy resin is easy to generate gas. Therefore, when epoxy resin is used in the sealing material 3, the adhesion between the interlayer insulating film 6 and the sealing material 3 is reduced.

The weight loss temperature of the interlayer insulating film 6 of this embodiment is as low as below 300° C. Therefore, it is inferred that in this 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 interlayer insulating film 6 and the sealing material 3 are less peeled off, and the adhesion during high temperature treatment is higher.

As for the weight reduction temperature of the interlayer insulating film 6, from the viewpoint of the close adhesion between the interlayer insulating film 6 and the sealing material 3 after high temperature treatment, it is preferably below 300°C, preferably below 295°C, preferably below 290°C, preferably below 285°C, preferably below 280°C, preferably below 275°C, preferably below 270°C, preferably below 260°C, preferably below 250°C, preferably below 240°C, preferably below 230°C.

In addition, there is no particular lower limit on the weight reduction temperature of the interlayer insulating film 6, and it can be above 80°C, above 100°C, above 120°C, or above 150°C.

Furthermore, the interlayer insulating film 6 in the redistribution layer 4 may also be a plurality of layers. That is, when the redistribution layer 4 is observed in cross section, the redistribution layer 4 may include: a first interlayer insulating film layer; a second interlayer insulating film layer; and an intermediate layer, which is a layer different from the first interlayer insulating film layer and the second interlayer insulating film layer, and is disposed between the first interlayer insulating film layer and the second interlayer insulating film layer. The 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 different compositions. The first interlayer insulating film layer and the second interlayer insulating film layer may have the same weight reduction temperature or different weight reduction temperatures. The first interlayer insulating film layer and the second interlayer insulating film layer may have the same film thickness or different film thicknesses. If the first interlayer insulating film layer and the second interlayer insulating film layer have different compositions or different weight reduction temperatures or different film thicknesses, each interlayer insulating film layer may have different properties, which is preferred.

In the case where the interlayer insulating film 6 is a multi-layer film, the weight loss temperature of at least one of the multiple layers is 300°C or less. However, the sealing material 3 and the interlayer insulating film layer are easily separated by gas, so it is preferable that the weight loss temperature of the interlayer insulating film 6 of the interlayer insulating film layer in contact with the sealing material 3 is 300°C or less. If the weight loss temperature of the interlayer insulating film 6 of the interlayer insulating film layer in contact with the sealing material 3 is 300°C or less, the gas generated in the sealing material 3 can be efficiently released. The preferred weight reduction temperature of each interlayer insulating film layer is the same as the preferred weight reduction temperature of the interlayer insulating film 6.

In the third aspect of the present implementation, 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 so-called in-plane refractive index is the average value of the refractive index of the interlayer insulating film 6 with thickness z, width x, and length y in the x-direction and y-direction at a wavelength of 1310 nm. The so-called out-of-plane refractive index is the refractive index of the z-direction at a wavelength of 1310 nm. 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 taken 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 Figure 2, the so-called length y direction is the plane direction of the interlayer insulating film 6 in Figure 2 and is perpendicular to the width x direction, and the so-called thickness z direction is the direction perpendicular to the width x direction and the length y direction.

If the refractive index difference is less than 0.0150, the interlayer insulating film 6 and the sealing material 3 have excellent adhesion during high temperature treatment. The reason is not clear, but the inventors of the present invention speculate as follows.

In the manufacturing process of the fan-out semiconductor device 1 (refer to Figure 1), in order to form a redistribution layer 4, a photosensitive resin composition is applied on a chip seal body including a semiconductor chip 2 and a sealing material 3. Then, the photosensitive resin composition is exposed to light including i-rays. Thereafter, the photosensitive resin composition is developed and cured to selectively form a portion having a cured photosensitive resin composition and a portion having no cured photosensitive resin composition. The cured photosensitive resin composition becomes an interlayer insulating film 6. Furthermore, wiring 5 is formed in a portion having no cured photosensitive resin composition. Normally, the redistribution layer 4 is often multi-layered. That is, a photosensitive resin composition is further applied on the interlayer insulating film 6 and the wiring 5, and then exposed, developed, and cured.

However, 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 become easy to peel off. In particular, epoxy resin is easy to generate gas due to high temperature thermal history. Therefore, when epoxy resin is used in the sealing material 3, the adhesion between the interlayer insulating film 6 and the sealing material 3 is reduced.

The refractive index difference of the interlayer insulating film 6 of this embodiment is as small as less than 0.0150, and the molecular chain of the interlayer insulating film 6 is highly random. Therefore, it is estimated that in this embodiment, even under the condition that the gas easily escapes from the interlayer insulating film and the gas is easily generated from the sealing material 3, the interlayer insulating film 6 and the sealing material 3 are less peeled off and the adhesion is also high.

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

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.

Furthermore, the interlayer insulating film 6 in the redistribution layer 4 may also be a plurality of layers. That is, when the redistribution layer 4 is observed in cross section, the redistribution layer 4 may include: a first interlayer insulating film layer; a second interlayer insulating film layer; and an intermediate layer, which is a layer different from the first interlayer insulating film layer and the second interlayer insulating film layer, and is disposed between the first interlayer insulating film layer and the second interlayer insulating film layer. The 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 different compositions. The first interlayer insulating film layer and the second interlayer insulating film layer may have the same refractive index difference or different refractive index differences. The first interlayer insulating film layer and the second interlayer insulating film layer may have the same film thickness or different film thicknesses. 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 may have different properties, which is preferred.

In the case where the interlayer insulating film 6 is a multi-layer film, it is sufficient if the refractive index difference of at least one interlayer insulating film 6 among the multiple layers is less than 0.0150. Since the sealing material 3 and the interlayer insulating film layer are easily separated by gas, it is preferable that the refractive index difference of the interlayer insulating film 6 of the interlayer insulating film layer in contact with the sealing material 3 is less than 0.0150. If the refractive index difference of the interlayer insulating film 6 of the interlayer insulating film layer in contact with the sealing material 3 is less than 0.0150, the gas generated in the sealing material 3 can escape efficiently.

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

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

(Resin composition for forming interlayer insulating film) The resin composition used in forming the interlayer insulating film 6 is not particularly limited if it is a photosensitive resin composition, but is preferably a photosensitive resin composition containing at least one compound selected from polyimide precursors, polybenzoxazole precursors, or polymers having phenolic hydroxyl groups. The resin composition used in forming the interlayer insulating film 6 may be in a liquid state or in a film state. In addition, the resin composition used in forming the interlayer insulating film 6 may be a negative photosensitive resin composition or a positive photosensitive resin composition.

In this embodiment, the pattern formed by exposing and developing the photosensitive resin composition is called a relief pattern, and the relief pattern formed by heating and curing is called a hardened relief pattern. The hardened relief pattern becomes the interlayer insulating film 6.

<Polyimide precursor composition> (A) Photosensitive resin As the photosensitive resin used in the polyimide precursor composition, polyamide, polyamic acid ester, etc. can be listed. 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.

[Chemistry 43] ^R1 and ^R2 are independently a hydrogen atom, a saturated aliphatic group having 1 to 30 carbon atoms, an aromatic group, a monovalent organic group having a carbon-carbon unsaturated double bond, or a monovalent ion having a carbon-carbon unsaturated double bond. ^X1 is a tetravalent organic group, ^Y1 is a divalent organic group, and m is an integer greater than 1. m is preferably greater than 2, and more preferably greater than 5.

When ^R1 and ^R2 in the above general formula (11) exist as monovalent cations, O has a negative charge (exists as ^-O- ). In addition, ^X1 and ^Y1 may also contain a hydroxyl group.

More preferably, ^R1 and ^R2 in the general formula (11) have an ammonium ion at the terminal of a monovalent organic group represented by the following general formula (12) or a monovalent organic group represented by the following general formula (13).

[Chemistry 44] (In general formula (12), R ₃ , R ₄ and R ₅ are independently a hydrogen atom or an organic group having 1 to 5 carbon atoms, and m ₁ is an integer of 1 to 20)

[Chemistry 45] (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. In addition, polyamic acid esters obtained by copolymerizing the polyamic acid esters represented by the general formula (11) may be used.

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

[Chemistry 46]

[Chemistry 47]

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

_R9 in the general formula (4) is, for example, a divalent organic group or a halogen atom having 1 to 40 carbon atoms. _R9 may also contain a hydroxyl group.

From the viewpoint of the adhesion between the interlayer insulating film 6 and the sealing material 3, ^X1 is particularly preferably a tetravalent organic group having a structure represented by the following general formula (5).

[Chemistry 49]

^Y1 is not particularly limited, but is preferably a divalent organic group containing an aromatic group from the viewpoint of ^the adhesion between the interlayer insulating film 6 and the sealing material 3. Specifically, ^Y1 is preferably a divalent organic group containing at least one structure represented by the following general formulae (6) to (8).

[Chemistry 50] (R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are hydrogen atoms, monovalent aliphatic groups having 1 to 5 carbon atoms, and may be the same or different)

[Chemistry 51] (R ₁₄ to R ₂₁ are hydrogen atoms, halogen atoms, or monovalent organic groups having 1 to 5 carbon atoms, and may be different from or the same as each other)

[Chemistry 52] (R ₂₂ is a divalent organic group, R ₂₃ to R ₃₀ are hydrogen atoms, halogen atoms, or monovalent aliphatic groups having 1 to 5 carbon atoms, and they 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, ^Y1 is particularly preferably a divalent organic group having a structure represented by the following general formula (9).

[Chemistry 53]

In the above polyamic acid ester, ^X1 in the repeating unit is derived from tetracarboxylic dianhydride used as a raw material, and ^Y1 is derived from diamine used as a raw material.

Examples of the tetracarboxylic dianhydride used as a raw material include pyromellitic dianhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenylsulfone-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 the present invention is not limited thereto. These may be used alone or in combination of two or more.

Examples of the diamines used as the raw materials include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, Diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 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]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl) )benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl)propane, 2,2-bis[4-(4-aminophenoxy)phenyl)hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, o-toluidine sulfide, 9,9-bis(4-aminophenyl)fluorene, etc. In addition, some of the hydrogen atoms on the benzene rings may be substituted. In addition, these may be used alone or in combination of two or more.

In the synthesis of the polyamic acid ester (A), a method of directly subjecting a tetracarboxylic acid diester obtained by an esterification reaction of a tetracarboxylic dianhydride described below to a condensation reaction with a diamine is usually preferably used.

The alcohol used in the esterification reaction of the tetracarboxylic dianhydride is an alcohol having an olefinic double bond. Specifically, 2-hydroxyethyl methacrylate, 2-methacryloyloxyethanol, glycerol diacrylate, glycerol dimethacrylate, etc. can be cited, but it is not limited to these. These alcohols can be used alone or in combination of two or more.

Regarding the specific synthesis method of the polyamic acid ester (A) used in the present embodiment, a previously known method can be adopted. Regarding the synthesis method, for example, the method shown in the specification of International Publication No. 00/43439 can be cited. That is, a method of converting a tetracarboxylic acid diester into a tetracarboxylic acid diester diacylate chloride once, and subjecting the tetracarboxylic acid diester diacylate to a condensation reaction with a diamine in the presence of an alkaline compound to produce a polyamic acid ester (A) can be cited. In addition, a method of producing a polyamic acid ester (A) by subjecting a tetracarboxylic acid diester to a condensation reaction with a diamine in the presence of an organic dehydrating agent can be cited.

Examples of the organic dehydrating agent include dicyclohexylcarbodiimide (DCC), diethylcarbodiimide, diisopropylcarbodiimide, ethylcyclohexylcarbodiimide, diphenylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, and 1-cyclohexyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride.

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

(B1) Photoinitiator When the resin composition used in forming the interlayer insulating film 6 is a negative photosensitive resin, a photoinitiator is added. As the photoinitiator, for example, benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and benzophenone derivatives such as fluorenone, acetophenone derivatives such as 2,2'-diethoxyacetophenone and 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexylphenyl ketone, 9-thiothiophenone, etc. are used. , 2-methyl-9-oxosulfuron , 2-isopropyl-9-oxysulfide , and diethyl-9-oxysulfide 9-Oxysulfuron derivatives, benzoyl derivatives such as benzoyl dimethyl ketone and benzoyl-β-methoxyethyl acetal, benzoin derivatives such as benzoin methyl ether, 2,6-bis(4'-diazolidine benzylmethylene)-4-methylcyclohexanone and 2,6'-bis(4'-diazolidine benzylmethylene)cyclohexanone, 1-phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenylpropanedione-2-(O-methoxycarbonyl)oxime, Oxime, such as 1-phenylpropanedione-2-(O-ethoxycarbonyl)oxime, 1-phenylpropanedione-2-(O-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(O-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2-(O-benzoyl)oxime, N-arylglycine such as N-phenylglycine, peroxides such as benzoyl peroxide, aromatic biimidazoles, and titanocene. Among them, the above oximes are preferred in terms of photosensitivity.

The amount of the photoinitiator added is preferably 1 to 40 parts by mass, more preferably 2 to 20 parts by mass, relative to 100 parts by mass of the polyamide (A). By adding 1 part by mass or more of the photoinitiator relative to 100 parts by mass of the polyamide (A), the photosensitivity is excellent. In addition, by adding 40 parts by mass or less, the thick film curability is excellent.

(B2) Photoacid generator When the resin composition used in forming the interlayer insulating film 6 is a positive photosensitive resin, a photoacid generator is added. By containing the photoacid generator, acid is generated in the ultraviolet light exposure area, and the solubility of the exposed area in the alkaline aqueous solution increases. Thus, it can be used as a positive photosensitive resin composition.

As the photoacid generator, there can be listed quinone diazide compounds, coronium salts, phosphonium salts, diazonium salts, iodonium salts, etc. Among them, quinone diazide compounds can be preferably used in view of showing an excellent dissolution inhibition effect and obtaining a positive photosensitive resin composition with high sensitivity. In addition, two or more photoacid generators may be contained.

(C) Additives The i-ray transmittance of the interlayer insulating film in the first embodiment of the present invention can be adjusted by the amount of the additive. As additives for reducing the i-ray transmittance, for example, 2-(5-chloro-2H-benzotriazole-2-yl)-6-tert-butyl-4-methylphenol, 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-trisinium, etc. can be used.

In the second aspect of this embodiment, the weight reduction temperature of the interlayer insulating film 6 can be adjusted by the type or amount of the additive. By using an easily volatile additive, the density of the interlayer insulating film can be reduced, and the weight reduction temperature can be reduced. As an additive that reduces the weight reduction temperature, for example, polyethylene glycol, polypropylene glycol, etc. can be used. The amount of the additive 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 reduced by reducing the temperature of the heat curing of the embossed 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 becomes disordered. Due to the disordered arrangement of the polymer molecular chains, the intermolecular forces between the polymer molecular chains are reduced, and the molecular chains become easy to be arranged irregularly in the in-plane direction and the out-of-plane direction, which can reduce the difference between the in-plane refractive index and the out-of-plane refractive index. As an additive with a fluffy structure, for example, an additive with a bicyclic structure can be listed. As an additive that reduces the refractive index difference, for example, bicyclooctane, diamond, etc. can be used. The amount of additive can 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 be reduced by changing the temperature during the thermal curing of the relief pattern.

(D) Solvent As long as it is a solvent that can dissolve or disperse each component, there is no particular limitation. For example, N-methyl-2-pyrrolidone, γ-butyrolactone, acetone, methyl ethyl ketone, dimethyl sulfoxide, etc. can be listed. Such solvents can be used in a range of 30 to 1500 parts by mass relative to 100 parts by mass of (A) photosensitive resin according to the coating film thickness and viscosity.

(E) Others The polyimide precursor composition may also contain a crosslinking agent. As a crosslinking agent, it can be used to crosslink the (A) photosensitive resin when the polyimide precursor composition is exposed and developed, and then heat-cured, or the crosslinking agent itself can form a crosslinked network. By using a crosslinking agent, the heat resistance and chemical resistance of the cured film (interlayer insulating film) can be further enhanced.

In addition, a sensitizer for improving photosensitivity and an adhesion promoter for improving adhesion to a substrate may also be included.

(Development) After the polyimide precursor composition is exposed, the useless part is washed out with a developer. There is no particular limitation on the developer used. In the case of a polyimide precursor composition developed with a solvent, good solvents such as N,N-dimethylformamide, dimethylsulfoxide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, cyclopentanone, γ-butyrolactone, acetates, etc., and mixed solvents of these good solvents and poor solvents such as lower alcohols, water, and aromatic hydrocarbons can be used. After development, washing with a poor solvent can be performed as needed.

In the case of a polyimide precursor composition developed with an alkaline aqueous solution, 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, cyclohexylamine, ethylenediamine, hexamethylenediamine and the like are used.

(Thermal curing) The polyimide precursor composition after development and exposure is heated to close the ring of the polyimide precursor to form polyimide. The polyimide becomes a hardened relief pattern, i.e., an interlayer insulating film 6.

In the first and second aspects of this embodiment, the heating temperature is not particularly limited. From the perspective of the impact on other components, the heating temperature is preferably a lower temperature, preferably below 250°C, more preferably below 230°C, more preferably below 200°C, and particularly preferably below 180°C.

In the third aspect of the present embodiment, the heating temperature for thermally curing the polyimide precursor composition is not particularly limited. Generally, there is a tendency that the lower the thermal curing temperature, the smaller the refractive index difference. From the perspective of the refractive index difference of the present embodiment, which is less than 0.0150, the heating temperature is preferably below 200°C, preferably below 180°C, and preferably below 160°C.

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

[Chemistry 54]

^X1 , ^{Y1 and} m in the general formula (1) are the same as X1, ^Y1 and m in the general formula (11), ^X1 is a tetravalent organic group, ^Y1 is a divalent organic group, and m is an integer greater than 1. Preferred ^X1 , ^Y1 and m in the general formula (11) are also preferred in the polyimide of the general formula (1) for the same reasons.

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

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

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

From the viewpoint of the close 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 the hydrogen atom of the chain alkylene group may also be substituted by a halogen atom), and particularly preferably a chain alkylene group having 1 to 8 carbon atoms and the hydrogen atom being substituted by a fluorine atom.

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

[Chemistry 56] (R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are hydrogen atoms, monovalent aliphatic groups having 1 to 5 carbon atoms, and may be the same or different)

[Chemistry 57] (R ₁₄ to R ₂₁ are hydrogen atoms, halogen atoms, or monovalent organic groups having 1 to 5 carbon atoms, and may be different from or the same as each other)

[Chemistry 58] (R ₂₂ is a divalent organic group, R ₂₃ to R ₃₀ are hydrogen atoms, halogen atoms, or monovalent aliphatic groups having 1 to 5 carbon atoms, and they 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 having a structure represented by the following general formula (9).

[Chemistry 59]

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

The polybenzoxazole precursor can generally be synthesized from a dicarboxylic acid derivative and a diamine containing a hydroxyl group. Specifically, the precursor can be synthesized by converting the dicarboxylic acid derivative into a dihalide derivative and then reacting the diamine. The dihalide derivative is preferably a dichloride derivative.

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

The dichloride derivative can be synthesized by a method of reacting a dicarboxylic acid derivative with the above-mentioned halogenating agent in a solvent, a method of reacting the derivative in an excess halogenating agent and then removing the excess component by distillation, etc.

Examples of the dicarboxylic acid used in the dicarboxylic acid derivative include isophthalic acid, terephthalic acid, 2,2-bis(4-carboxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 4,4'-dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxytetraphenylsilane, bis(4-carboxyphenyl)sulfone, 2,2-bis(p-carboxyphenyl)propane, 5-tert-butyl Isophthalic 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-methyl 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid, 3-methyladipic acid, octafluoroadipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorosuberic acid, azelaic acid, sebacic acid, hexadecanoic acid, 1,9-nonanediacid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, triacontanedioic acid, hexacontanedioic acid, dotriaconedioic acid, diglycolic acid, and the like. These may also be used in combination.

Examples of the diamine containing a hydroxyl group 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)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, and 2,2-bis(4-amino-3-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane. These may be used in combination.

(B2) Photoacid generator The photoacid generator has the function of increasing the solubility of the alkaline aqueous solution in the light-irradiated part. Examples of the photoacid generator include naphthoquinone diazide compounds, aryl diazonium salts, diaryl iodonium salts, triaryl stibnium salts, etc. Among them, naphthoquinone diazide compounds have high sensitivity and are preferred.

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

(D) Solvent As long as it is a solvent that can dissolve or disperse each component, there is no particular limitation.

(E) Others The polybenzoxazole precursor composition may include a crosslinking agent, a sensitizer, a bonding agent, a thermal acid generator, etc.

(Development) After the polybenzoxazole precursor composition is exposed, the useless part is washed out with a developer. The developer used is not particularly limited, and alkaline aqueous solutions of sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide, etc. are preferably listed.

In the above description, the positive-type polybenzoxazole precursor composition is mainly used for the description, but a negative-type polybenzoxazole precursor composition may also be used.

(Thermal curing) After development, the polybenzoxazole precursor composition is heated to close the polybenzoxazole precursor ring to form polybenzoxazole. The polybenzoxazole becomes a hardened relief pattern, i.e., an interlayer insulating film 6.

The heating temperature for thermally curing the polybenzophenone precursor composition is not particularly limited, but a lower heating temperature is preferred from the viewpoint of the influence on other components. The heating temperature is preferably below 250°C, more preferably below 230°C, more preferably below 200°C, and particularly preferably below 180°C.

<Polybenzoxazole> The structure of the hardened relief pattern formed by the above-mentioned polybenzoxazole precursor composition is the following general formula (10).

[Chemistry 60]

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

<Polymers with phenolic hydroxyl groups> (A) Photosensitive resins Resins with phenolic hydroxyl groups in their molecules are soluble in alkali. Specific examples include vinyl polymers containing monomer units with phenolic hydroxyl groups such as poly(hydroxystyrene), phenol resins, poly(hydroxyamides), poly(hydroxyphenylene) ethers, and polynaphthols.

Among these, phenolic resins are preferred, and novolac-type phenolic resins are particularly preferred, from the viewpoint of low cost or small volume shrinkage during hardening.

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

Examples of phenol derivatives include phenol, cresol, ethylphenol, propylphenol, butylphenol, pentylphenol, benzylphenol, adamantanephenol, benzyloxyphenol, xylenol, catechol, resorcinol, ethylresorcinol, hexylresorcinol, hydroquinone, ophthalmol, phloroglucinol, 1,2,4-trihydroxybenzene, rhodamine, biphenol, bisphenol A, bisphenol AF, bisphenol B, bisphenol F, bisphenol S, dihydroxydiphenylmethane ... 1,2,4-trihydroxybenzene, 1,2,4-trihydroxybenzene, 1,2,4-trihydroxybenzene, 1,2,4-trihydroxybenzene, 1,2,4-trihydroxybenzene, 1,2,4-trihydroxybenzene, 1,2,4-trihydroxybenzene, 1,2,4-trihydroxybenzene, 1,2,4-trihydroxybenzene, 1,2,4-trihydroxybenzene, 1,2 1-bis(4-hydroxyphenyl)cyclohexane, 1,4-bis(3-hydroxyphenoxybenzene), 2,2-bis(4-hydroxy-3-methylphenyl)propane, α,α'-bis(4-hydroxyphenyl)-1,4-diisopropylbenzene, 9,9-bis(4-hydroxy-3-methylphenyl)fluorene, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2,2-bis(2-hydroxy-5-biphenyl)propane, dihydroxybenzoic acid, etc.

Examples of aldehyde compounds include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, pivalaldehyde, butyraldehyde, valeraldehyde, hexanal, trioxane, glyoxal, cyclohexylaldehyde, diphenylacetaldehyde, ethylbutyraldehyde, benzaldehyde, glyoxylic acid, 5-norbutene-2-carboxaldehyde, malondialdehyde, succinic dialdehyde, glutaraldehyde, salicylic acid, naphthaldehyde, terephthalaldehyde, and the like.

Preferably, component (A) comprises (a) a phenolic resin having no unsaturated hydrocarbon group and (b) a modified phenolic resin having an unsaturated hydrocarbon group. Component (b) is more preferably a phenolic resin further modified by reaction of a phenolic hydroxyl group with a polyacid anhydride.

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

(b) The modified phenolic resin having an unsaturated hydrocarbon group is generally a condensation product of a reaction product of phenol or its derivatives with a compound having an unsaturated hydrocarbon group (preferably one having 4 to 100 carbon atoms) (hereinafter referred to as "the compound containing an unsaturated hydrocarbon group") and aldehydes, or a reaction product of a phenolic resin and a compound containing an unsaturated hydrocarbon group.

The phenol derivatives used herein may be the same phenol derivatives as those mentioned above as the raw materials of the phenol resin as the component (A).

From the viewpoint of the adhesion of the anti-corrosion pattern and the heat shock resistance, it is preferred that the unsaturated hydrocarbon group of the compound containing an unsaturated hydrocarbon group contains two or more unsaturated hydrocarbon groups. Furthermore, from the viewpoint of the compatibility when preparing a resin composition and the flexibility of the cured film, the compound containing an unsaturated hydrocarbon group preferably has 8 to 80 carbon atoms, and more preferably has 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, linalool, oleyl alcohol, unsaturated fatty acids, and unsaturated fatty acid esters. Examples of suitable unsaturated fatty acids include butyric acid, myristic acid, palmitic acid, oleic acid, elaidic acid, isoleic acid, squalane acid, erucic acid, lignoceric acid, linolenic acid, α-linolenic acid, eleostearic acid, octadecatetraenoic acid, arachidonic acid, eicosapentaenoic acid, herringic acid, and docosahexaenoic acid. Among them, esters of unsaturated fatty acids having 8 to 30 carbon atoms and monovalent to trivalent alcohols having 1 to 10 carbon atoms are particularly preferred, and esters of unsaturated fatty acids having 8 to 30 carbon atoms and glycerol as a trivalent alcohol are particularly preferred.

Esters of unsaturated fatty acids having 8 to 30 carbon atoms and glycerol can be commercially obtained in the form of vegetable oils. Vegetable oils include non-drying oils having an iodine value of less than 100, semi-drying oils having an iodine value of more than 100 and less than 130, or drying oils having an iodine value of more than 130. Examples of non-drying oils include olive oil, ginkgo seed oil, Polygonum multiflorum seed oil, tea 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 seed oil, perilla seed oil, and mustard oil. In addition, processed vegetable oils obtained by processing these vegetable oils can also be used.

Among the above-mentioned vegetable oils, non-drying oils are preferably used from the viewpoint of preventing gelation accompanying excessive reaction in the reaction between phenol or its derivatives or phenolic resins and vegetable oils and improving the yield. On the other hand, drying oils are preferably used from the viewpoint of improving the adhesion, mechanical properties and heat shock resistance of the anti-corrosion pattern. Among the drying oils, tung oil, linseed oil, soybean oil, walnut oil and safflower oil are more preferably used, and tung oil and linseed oil are more preferably used, because the effects of the present invention can be more effectively and reliably exerted.

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

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

The unsaturated hydrocarbon-modified phenol derivative produced by the above reaction is subjected to condensation polymerization with aldehydes to produce a phenol resin modified with a compound containing an unsaturated hydrocarbon group. The aldehydes used to obtain the phenol resin may be the same aldehydes as those described above.

The reaction of the aldehydes and the unsaturated alkyl-modified phenol derivatives is a polycondensation reaction, and the previously known synthesis conditions of 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. Examples of the acid catalyst include hydrochloric acid, sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid, and oxalic acid. The acid catalysts can be used alone or in combination of two or more.

It is usually preferred to carry out the above reaction at a reaction temperature of 100-120°C. Moreover, the reaction time varies depending on the type or amount of the catalyst used, but is usually 1-50 hours. After the reaction is completed, the reaction product is decompressed and dehydrated at a temperature below 200°C to obtain a phenolic resin modified by a compound containing an unsaturated alkyl group. Furthermore, solvents such as toluene, xylene, and methanol can be used in the reaction.

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

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

As the unsaturated hydrocarbon group-containing compound to be reacted with the phenolic resin, the same unsaturated hydrocarbon group-containing compound as mentioned above can be used.

The reaction of the phenol resin and the compound containing an unsaturated hydrocarbon group is preferably carried out at 50 to 130° C. In view of improving the flexibility of the cured film (corrosion resistant pattern), the reaction ratio of the phenol resin and the compound containing an unsaturated hydrocarbon group is preferably 1 to 100 parts by mass of the compound containing an unsaturated hydrocarbon group relative to 100 parts by mass of the phenol resin, more preferably 2 to 70 parts by mass, and further preferably 5 to 50 parts by mass. If the unsaturated hydrocarbon group-containing compound is less than 1 part by mass, the flexibility of the cured film tends to decrease, and if it exceeds 100 parts by mass, the possibility of gelation during the reaction tends to increase, and the heat resistance of the cured film tends to decrease. At this time, p-toluenesulfonic acid, trifluoromethanesulfonic acid, etc. may be used as a catalyst as needed. Furthermore, solvents such as toluene, xylene, methanol, tetrahydrofuran, etc. may be used in the reaction.

Furthermore, the polybasic acid anhydride is reacted with the phenolic hydroxyl groups remaining in the phenolic resin modified with the compound containing an unsaturated alkyl group produced by the above method. In this way, the acid-modified phenolic resin can also be used as the (b) component. By introducing carboxyl groups through acid modification with the polybasic acid anhydride, the solubility of the (b) component in the alkaline aqueous solution (developer) 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 carboxyl groups of a polybasic acid having a plurality of carboxyl groups. Examples of the polyacid anhydride include dibasic acid anhydrides such as phthalic anhydride, succinic anhydride, octenylsuccinic anhydride, penta(dodecenyl)succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, nalidric anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride and trimellitic anhydride, and aromatic tetrabasic acid dianhydrides such as biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, pyromellitic dianhydride and benzophenonetetracarboxylic dianhydride. These can be used alone or in combination of two or more. Among these, the polyanhydride is preferably a dianhydride, and more preferably one or more selected from the group consisting of tetrahydrophthalic anhydride, succinic anhydride and hexahydrophthalic anhydride. In this case, there is an advantage that an anti-corrosion pattern having a good shape can be formed.

The alkaline soluble resin having a phenolic hydroxyl group (A) may further contain a phenolic resin modified with an acid by reacting a polybasic acid anhydride. By making the component (A) contain a phenolic resin modified with an acid by a polybasic acid anhydride, the solubility of the component (A) in an alkaline aqueous solution (developer) can be further improved.

Examples of the polybasic acid anhydride include dibasic acid anhydrides such as phthalic anhydride, succinic anhydride, octenylsuccinic anhydride, penta(dodecenyl)succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, naphthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride, and trimellitic anhydride; and aliphatic and aromatic tetrabasic acid dianhydrides such as biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, pyromellitic dianhydride, and benzophenonetetracarboxylic dianhydride. These can be used alone or in combination of two or more. Among these, the polybasic acid anhydride is preferably a dibasic acid anhydride, and more preferably one or more selected from the group consisting of tetrahydrophthalic anhydride, succinic anhydride and hexahydrophthalic anhydride.

(B2) Photoacid generators As photoacid generators, naphthoquinone diazide compounds, aryl diazonium salts, diaryl iodonium salts, triaryl stibnium salts, etc. can be listed. Among them, naphthoquinone diazide compounds have high sensitivity and are better.

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

(D) Solvent As long as it is a solvent that can dissolve or disperse each component, there is no particular limitation.

(E) Others May include thermal crosslinking agents, sensitizers, bonding aids, dyes, surfactants, dissolution promoters, crosslinking promoters, etc. Among them, by containing a thermal crosslinking agent, when the photosensitive resin film after pattern formation is heated and hardened, the thermal crosslinking agent component reacts with the (A) component to form a bridge structure. This makes it possible to harden at a low temperature, which can prevent the brittleness of the film or the melting of the film. As a 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 used as a preferred one.

(Development) After exposing the polymer having a phenolic hydroxyl group, the useless part is washed out with a developer. There is no particular limitation on the developer used, and for example, alkaline aqueous solutions of sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, tetramethylammonium hydroxide (TMAH), etc. can be suitably used.

(Thermal curing) After development, the polymers having phenolic hydroxyl groups are heated to thermally crosslink the polymers having phenolic hydroxyl groups. The crosslinked polymers become a hardened relief pattern, i.e., an interlayer insulating film 6.

There is no particular limitation on the heating temperature for thermally curing the polymer having a phenolic hydroxyl group, but a lower heating temperature is preferred from the viewpoint of the influence on other components. The heating temperature is preferably 250°C or less, more preferably 230°C or less, more preferably 200°C or less, and particularly preferably 180°C or less.

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

Next, a mold resin 12 is applied from the semiconductor chip 2 to the support 11, and mold sealing is performed as shown in FIG3D. Next, the support 11 is peeled off, and the mold resin 12 is reversed (refer to FIG3E). As shown in FIG3E, the semiconductor chip 2 and the mold resin 12 appear in approximately the same plane. Next, a photosensitive resin composition 13 is applied on the semiconductor chip 2 and the mold resin 12 by the step shown in FIG3F. Next, the applied photosensitive resin composition 13 is exposed and developed to form a relief pattern (relief pattern forming step). Furthermore, the photosensitive resin composition 13 can be either positive or negative. Then, the embossed pattern is heated to form a hardened embossed pattern (interlayer insulating film forming step). Then, wiring is formed in the portion where the hardened embossed pattern is not formed (wiring forming step).

Furthermore, in this embodiment, the above-mentioned embossed pattern forming step, interlayer insulating film forming step, and wiring forming step are combined as a redistribution layer forming step for forming a redistribution layer connected to the semiconductor chip 2.

The interlayer insulating film in the redistribution layer may also be a plurality of layers. Therefore, the redistribution layer forming step may also include a plurality of embossed pattern forming steps, a plurality of interlayer insulating film forming steps, and a plurality of wiring forming steps.

Furthermore, in FIG3G, a plurality of external connection terminals 7 (forming bumps) corresponding to each semiconductor chip 2 are formed, and the semiconductor chips 2 are cut into pieces. Thus, a semiconductor device (semiconductor IC) 1 can be obtained as shown in FIG3H. In this embodiment, a plurality of fan-out semiconductor devices 1 can be obtained by the manufacturing method shown in FIG3.

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

In this embodiment, it is preferred that in the above-mentioned interlayer insulating film forming step, the interlayer insulating film is formed by a photosensitive resin composition that can form at least one compound of polyimide, polybenzoxazole, and a polymer having a phenolic hydroxyl group.

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

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

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

In this embodiment, it is preferred that in the above-mentioned interlayer insulating film forming step, the interlayer insulating film is formed by a photosensitive resin composition that can form at least one compound of polyimide, polybenzoxazole, and a polymer having a phenolic hydroxyl group. [Example]

Hereinafter, an example of an embodiment carried out to clarify the effect of the present invention will be described. In the example, the following materials and measurement methods are used. [Example] Hereinafter, an example of an embodiment carried out to clarify the effect of the present invention will be described.

(Polymer A-1: Synthesis of polyimide precursor) 4,4'-oxydiphthalic acid dianhydride (ODPA) as tetracarboxylic dianhydride was placed in a 2-liter separable flask. 2-Hydroxyethyl methacrylate (HEMA) and γ-butyrolactone were then added and stirred at room temperature. Pyridine was added while stirring to obtain a reaction mixture. After the exotherm generated by the reaction ended, the mixture was cooled to room temperature and left for 16 hours.

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

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

(Synthesis of polymers A-2 to A-4) The tetracarboxylic dianhydride and diamine were changed as shown in Table 1 below, and the reaction was carried out in the same manner as described in the above polymer A-1 to obtain polyimide precursors (polymers A-2 to A-4).

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

(Synthesis of polymers B-2 to B-3) The dicarboxylic acid and diaminophenol were changed as shown in Table 1 below, and the reaction was carried out in the same manner as described in the above polymer B-1 to obtain polybenzoxazole precursors (polymers B-2 to B-3).

(Polymer C-1: Synthesis of phenolic resin) Prepare a phenolic resin containing 85 g of the C1 resin shown below and 15 g of the C2 resin shown below as polymer C-1. C1: Cresol novolac resin (cresol/formaldehyde novolac resin, m-cresol/p-cresol (molar ratio) = 60/40, polystyrene-equivalent weight average molecular weight = 12,000, manufactured by Asahi Organic Materials Industries, trade name "EP4020G")

C2: C2 was synthesized as follows. ＜C2: Synthesis of phenolic resin modified by a compound having an unsaturated alkyl group with 4 to 100 carbon atoms＞ 100 parts by mass of phenol, 43 parts by mass of linseed oil and 0.1 parts by mass of trifluoromethanesulfonic acid were mixed and 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 stirred at 90°C for 3 hours. Next, the temperature was raised to 120°C and stirred for 3 hours under reduced pressure, and then 29 g of succinic anhydride and 0.3 g of triethylamine were added to the reaction solution and stirred at 100°C for 1 hour under atmospheric pressure. The reaction liquid was cooled to room temperature, and a phenolic resin (hereinafter referred to as "C2 resin") modified by a compound having an unsaturated hydrocarbon group with a carbon number of 4 to 100 was obtained as a reaction product (acid value of 120 mgKOH/g).

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

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

[Examples 1 to 11, Comparative Examples 1 to 2] The solution of the photosensitive resin composition was prepared as shown in Table 2 below. The unit in Table 2 is mass part.

The photosensitive resin compositions of Examples 1 to 11 and Comparative Examples 1 to 2 were prepared using the compounds listed in Table 2 and the formulation amounts listed in Table 3 and Table 4.

The prepared photosensitive resin composition was subjected to (1) a test for measuring the transmittance of an i-ray, (2) a test for the degradation of a sealing material, and (3) a test for the adhesion to a sealing material. The results of each test are shown in Table 3 below.

(1) I-ray transmittance measurement test A fan-out type wafer-level chip size package type semiconductor device was manufactured using the photosensitive resin composition prepared in each embodiment and each comparative example. An interlayer insulating film with a thickness of 10 μm was removed as thoroughly as possible from the manufactured semiconductor device. The removed interlayer insulating film was measured using a UV-1800 device manufactured by Shimadzu Corporation at a medium scanning speed and a sampling interval of 0.5 nm to measure the i-ray transmittance.

(2) Sealing material degradation test As an epoxy sealing material, R4000 series manufactured by Nagase Chemicals Co., Ltd. was prepared. Next, the sealing material was spin-coated on an aluminum sputter-plated silicon wafer to a thickness of about 150 μm, and the epoxy sealing material was cured by heat curing at 130°C. The photosensitive resin composition prepared in each of the examples and comparative examples was coated on the epoxy cured film to a final film thickness of 10 μm. The entire surface of the coated photosensitive resin composition was exposed at 200 mJ/ ^cm2 in Examples 1 to 4, 10 and Comparative Example 1, at 500 mJ/cm2 in Examples 5 to 7, 11 and Comparative Example ² , and at 700 mJ/ ^cm2 in Examples 8 and 9. Thereafter, thermal curing was performed at 200°C for 2 hours to form a first layer of cured film with a thickness of 10 μm.

The photosensitive resin composition used in forming the first cured film was applied on the first cured film, and the entire surface was exposed under the same conditions as when the first cured film was prepared, and then thermally cured to prepare a second cured film with a thickness of 10 μm.

After the second layer of the cured film was formed, the cross section of the test piece was cut out using a FIB device (JIB-4000, manufactured by JEOL Ltd.) to check for the presence of pores in the epoxy portion to evaluate the degree of degradation. A score of ○ was given if no pores were found, and a score of × was given if even one pore was found.

(3) Adhesion test with sealing material A probe was placed on the sample produced in the sealing material degradation test, and a traction tester (Sebastian 5 model, manufactured by Quad Group) was used to conduct the adhesion test. That is, the adhesion between the epoxy-based sealing material and the hardened embossed pattern made of the photosensitive resin composition produced in each embodiment and each comparative example was tested. Evaluation: Adhesion strength is 70 MPa or more... Adhesion ◎ 50 MPa or more and less than -70 MPa... Adhesion ○ 30 MPa or more and less than -50 MPa... Adhesion △ Less than 30 MPa... Adhesion ×

[Table 2] Photoinitiator D-1 Photoacid generator D-2 Crosslinking agent E-1 iRadiation transmittance adjuster F-1 2-(5-Chloro-2H-benzotriazol-2-yl)-6-tert-butyl-4-methylphenol F-2 2,4,6-Tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-tris(2-hydroxy-4-hexyloxy-3-methylphenyl) Solvent G-1 γ-Butyrolactone G-2 Dimethyl sulfoxide G-3 Propylene glycol monomethyl ether acetate G-4 Ethyl lactate

[table 3] Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5 Embodiment 6 Embodiment 7 Embodiment 8 Embodiment 9 polymer A-1 100 A-2 100 A-3 100 A-4 100 B-1 100 B-2 100 B-3 100 C-1 100 C-2 100 Photoinitiator D-1 2 2 2 2 Photoacid generator D-2 10 10 10 15 15 Crosslinking agent E-1 15 15 iRadiation transmittance adjuster F-1 2 2 2 1 4 4 4 3 3 F-2 Solvent G-1 160 160 160 160 225 225 225 G-2 40 40 40 40 G-3 25 25 25 G-4 120 120 iRadiation transmittance (%) 10 20 twenty three 65 18 15 30 25 41 Sealing material degradation test ○ ○ ○ ○ ○ ○ ○ ○ ○ Adhesion test with sealing materials ◎ ○ ○ △ ○ ○ △ ○ △

[Table 4] Embodiment 10 Embodiment 11 Comparison Example 1 Comparison Example 2 polymer A-1 100 A-2 A-3 A-4 100 B-1 100 B-2 B-3 100 C-1 C-2 Photoinitiator D-1 2 2 Photoacid generator D-2 10 10 Crosslinking agent E-1 iRadiation transmittance adjuster F-1 F-2 2 4 Solvent G-1 160 225 160 225 G-2 40 40 G-3 25 25 G-4 iRadiation transmittance (%) 8 twenty two 85 88 Deterioration of sealing materials ○ ○ × × Adhesion to sealing materials ◎ ○ × ×

A fan-out type wafer-level chip scale package semiconductor device containing epoxy resin in a mold resin was manufactured using the photosensitive resin composition described in Examples 1 to 11, and the device was able to operate without any problem.

(Polymer H-1: Synthesis of polyimide precursor) 4,4'-oxydiphthalic dianhydride (ODPA) as tetracarboxylic dianhydride was placed in a 2-liter separable flask. 2-Hydroxyethyl methacrylate (HEMA) and γ-butyrolactone were then added and stirred at room temperature. Pyridine was added while stirring to obtain a reaction mixture. After the exotherm generated by the reaction ended, the mixture was cooled to room temperature and left for 16 hours.

Next, under ice cooling, a solution of dicyclohexylcarbodiimide (DCC) dissolved in γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Next, a solution of 4,4'-diaminodiphenyl ether (DADPE) suspended in γ-butyrolactone as a diamine was added over 60 minutes while stirring. After stirring at room temperature for 2 hours, ethanol was added and stirred for 1 hour, and then γ-butyrolactone was added. The precipitate produced in the reaction mixture was removed by filtration to obtain a reaction solution.

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

(Synthesis of polymers H-2 to H-4) The tetracarboxylic dianhydride and diamine were changed as shown in Table 5 below, and the reaction was carried out in the same manner as described in the above polymer H-1 to obtain polyimide precursors (polymers H-2 to H-4).

(Polymer I-1: Synthesis of polybenzoxazole precursor) In a 0.5-liter flask equipped with a stirrer and a thermometer, 15.48 g of 4,4'-diphenyl ether dicarboxylic acid and N-methylpyrrolidone as dicarboxylic acid were placed. After cooling the flask to 5°C, sulfinyl chloride was added dropwise and reacted for 30 minutes to obtain a solution of dicarboxylic acid chloride. Next, N-methylpyrrolidone was placed in a 0.5-liter flask equipped with a stirrer and a thermometer. 18.30 g of bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 2.18 g of meta-aminophenol as diaminophenol were stirred and dissolved, and then pyridine was added. Then, while maintaining the temperature at 0-5°C, the dicarboxylic acid chloride solution was added dropwise over 30 minutes, and the mixture was stirred for 30 minutes. The solution was poured into 3 liters of water, and the precipitate was recovered and washed with pure water three times, and then dried under reduced pressure to obtain a polymer (polybenzoxazole precursor (polymer I-1)). The mass of the compounds used in polymer I-1 is shown in Table 5 below.

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

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

J2: J2 was synthesized as follows. <J2: Synthesis of phenolic resin modified by a compound having an unsaturated alkyl group with 4 to 100 carbon atoms> 100 parts by mass of phenol, 43 parts by mass of linseed oil and 0.1 parts by mass of trifluoromethanesulfonic acid were mixed and 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 stirred at 90°C for 3 hours. Next, the temperature was raised to 120°C and stirred under reduced pressure for 3 hours, and then 29 g of succinic anhydride and 0.3 g of triethylamine were added to the reaction solution and stirred at 100°C for 1 hour under atmospheric pressure. The reaction liquid was cooled to room temperature, and a phenolic resin modified by a compound having an unsaturated hydrocarbon group with a carbon number of 4 to 100 (hereinafter referred to as "J2 resin") was obtained as a reaction product (acid value of 120 mgKOH/g).

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

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

[Examples 12 to 22, Comparative Examples 3 to 4] The solution of the photosensitive resin composition was prepared as shown in Table 6 below. The unit in Table 6 is mass part.

The compounds listed in Table 6 were used in the amounts listed in Table 7 and Table 8 to prepare the photosensitive resin compositions of Examples 12 to 22 and Comparative Examples 3 to 4.

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

(4) 5% weight loss temperature measurement test A fan-out type wafer-level chip scale package type semiconductor device was manufactured using the photosensitive resin composition prepared in the embodiment and the comparative example. An interlayer insulating film with a thickness of 10 μm was removed as completely as possible from the manufactured semiconductor device. The removed interlayer insulating film was measured at a heating rate of 10°C/min in a nitrogen atmosphere using a DTG-60A device manufactured by Shimadzu Corporation to measure the 5% weight loss temperature.

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

The photosensitive resin composition prepared in Examples and Comparative Examples was applied on the epoxy cured film so that the final film thickness became 10 μm. The applied photosensitive resin composition was exposed to light at 200 mJ/cm 2 in Examples 12 to 15, 21, and Comparative Example 3, at 500 mJ/cm ² in Examples 16 to 18, 22, and Comparative Example ⁴ , and at 700 mJ/cm ² in Examples 19 and 20, and then thermally cured at 180°C for 2 hours to prepare a first layer cured film with a thickness of 10 μm.

The photosensitive resin composition used in forming the first cured film was applied on the first cured film, and the entire surface was exposed under the same conditions as when the first cured film was formed, and then thermally cured to form a second cured film with a thickness of 10 μm.

After the second layer of hardened film was formed, the test piece was heated to a peak temperature of 260°C in a nitrogen atmosphere under simulated reflow conditions using a mesh belt continuous baking furnace (manufactured by Koyo Thermo Systems, model 6841-20AMC-36). The so-called simulated reflow conditions are standardized based on the reflow conditions described in Item 7.6 of IPC/JEDEC J-STD-020A, a standard specification of the US semiconductor industry group related to the evaluation method of semiconductor devices, assuming that the melting point of the solder is a high temperature of 220°C.

After cutting a cross section of the cured film treated under the above simulated reflow conditions using a FIB device (JIB-4000, manufactured by JEOL Ltd.), the presence or absence of pores in the epoxy portion was confirmed to evaluate the degree of deterioration. A score of ○ was given if no pores were found, and a score of × was given if even one pore was found.

(6) Adhesion test with sealing material A probe was placed on the photosensitive resin cured film of the sample produced in the test of (5), and a traction tester (Sebastian 5, manufactured by Quad Group) was used to conduct the adhesion test. Evaluation: Adhesion strength is 70 MPa or more... Adhesion strength ◎ 50 MPa or more and less than -70 MPa... Adhesion strength ○ 30 MPa or more and less than -50 MPa... Adhesion strength △ Less than 30 MPa... Adhesion strength ×

[Table 6] Photoinitiator K-1 Photoacid generator K-2 Crosslinking agent L-1 Weight Reducing Temperature Regulator M-1 Polyethylene glycol 3000 M-2 Polypropylene glycol 3000 Solvent N-1 γ-Butyrolactone N-2 Dimethyl sulfoxide N-3 Propylene glycol monomethyl ether acetate N-4 Ethyl lactate

[Table 7] Embodiment 12 Embodiment 13 Embodiment 14 Embodiment 15 Embodiment 16 Embodiment 17 Embodiment 18 Embodiment 19 Embodiment 20 polymer H-1 100 H-2 100 H-3 100 H-4 100 I-1 100 I-2 100 I-3 100 J-1 100 J-2 100 Photoinitiator K-1 2 2 2 2 Photoacid generator K-2 10 10 10 15 15 Crosslinking agent L-1 15 15 Weight Reducing Temperature Regulator M-1 15 15 15 15 12 12 12 16 16 M-2 Solvent N-1 160 160 160 160 225 225 225 N-2 40 40 40 40 N-3 25 25 25 N-4 120 120 Weight reduction temperature 285 290 292 296 293 293 298 291 296 Reflow resistance test ○ ○ ○ ○ ○ ○ ○ ○ ○ Adhesion test with sealing materials ◎ ○ ○ △ ○ ○ △ ○ △

[Table 8] Embodiment 21 Embodiment 22 Comparison Example 3 Comparison Example 4 polymer H-1 100 H-2 H-3 H-4 100 I-1 100 I-2 I-3 100 J-1 J-2 Photoinitiator K-1 2 2 Photoacid generator K-2 10 10 Crosslinking agent L-1 Weight Reducing Temperature Regulator M-1 M-2 15 12 Solvent N-1 160 225 160 225 N-2 40 40 N-3 25 25 N-4 Weight reduction temperature 286 290 308 310 Reflow resistance test ○ ○ × × Adhesion test with sealing materials ◎ ○ × ×

According to Tables 7 and 8, the results of the tests (4) to (6) conducted on the photosensitive resin compositions of Examples 12 to 22 confirmed that when the 5% weight loss temperature was below 300°C, no voids were found in the epoxy portion in the reflow resistance test of the sealing material, and that the adhesion test with the sealing material was evaluated as any of ◎, ○, and △.

On the other hand, it can be seen from Tables 7 and 8 that the results of the tests (4) to (6) conducted on the photosensitive resin compositions of Comparative Examples 3 and 4 confirmed that when the 5% weight loss temperature exceeded 300°C, pores were found in the epoxy portion in the reflow resistance test of the sealing material, and the adhesion test with the sealing material was evaluated as ×.

A fan-out type wafer-level chip scale package semiconductor device containing epoxy resin in a mold resin was manufactured using the photosensitive resin composition of Examples 12 to 22, and the device could operate without any problem.

(Polymer O-1: Synthesis of polyimide precursor) 4,4'-oxydiphthalic acid dianhydride (ODPA) as tetracarboxylic dianhydride was placed in a 2-liter separable flask. 2-Hydroxyethyl methacrylate (HEMA) and γ-butyrolactone were then added and stirred at room temperature. Pyridine was added while stirring to obtain a reaction mixture. After the exotherm generated by the reaction ended, the mixture was cooled to room temperature and left for 16 hours.

Next, under ice cooling, a solution of dicyclohexylcarbodiimide (DCC) dissolved in γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Next, a solution of 4,4'-diaminodiphenyl ether (DADPE) suspended in γ-butyrolactone as a diamine was added over 60 minutes while stirring. After stirring at room temperature for 2 hours, ethanol was added and stirred for 1 hour, and then γ-butyrolactone was added. The precipitate produced in the reaction mixture was removed by filtration to obtain a reaction solution.

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

(Synthesis of polymers O-2 to O-4) The tetracarboxylic dianhydride and diamine were changed as shown in Table 9 below, and the reaction was carried out in the same manner as described in the above polymer O-1 to obtain polyimide precursors (polymers O-2 to O-4).

(Polymer P-1: Synthesis of polybenzoxazole precursor) In a 0.5-liter flask equipped with a stirrer and a thermometer, 15.48 g of 4,4'-diphenylether dicarboxylic acid and N-methylpyrrolidone as dicarboxylic acid were placed. After cooling the flask to 5°C, sulfinyl chloride was added dropwise and reacted for 30 minutes to obtain a solution of dicarboxylic acid chloride. Next, N-methylpyrrolidone was placed in a 0.5-liter flask equipped with a stirrer and a thermometer. 18.30 g of bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 2.18 g of meta-aminophenol as bisaminophenol were stirred and dissolved, and then pyridine was added. Then, while maintaining the temperature at 0-5°C, the dicarboxylic acid chloride solution was added dropwise over 30 minutes, and the mixture was stirred for 30 minutes. The solution was poured into 3 liters of water, and the precipitate was recovered and washed with pure water three times, and then dried under reduced pressure to obtain a polymer (polybenzoxazole precursor (polymer P-1)). The mass of the compounds used in polymer P-1 is shown in Table 9 below.

(Synthesis of polymers P-2 to P-3) The dicarboxylic acid and diaminophenol were changed as shown in Table 9 below, and the reaction was carried out in the same manner as described in the above polymer P-1 to obtain polybenzoxazole precursors (polymers P-2 to P-3).

(Polymer Q-1: Synthesis of phenolic resin) Prepare a phenolic 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 novolac resin (cresol/formaldehyde novolac resin, m-cresol/p-cresol (molar ratio) = 60/40, polystyrene-equivalent weight average molecular weight = 12,000, manufactured by Asahi Organic Materials Industries, trade name "EP4020G")

Q2: Q2 was synthesized as follows. ＜Q2: Synthesis of phenolic resin modified by a compound having an unsaturated alkyl group with 4 to 100 carbon atoms＞ 100 parts by mass of phenol, 43 parts by mass of linseed oil and 0.1 parts by mass of trifluoromethanesulfonic acid were mixed and 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 stirred at 90°C for 3 hours. Next, the temperature was raised to 120°C and stirred for 3 hours under reduced pressure, and then 29 g of succinic anhydride and 0.3 g of triethylamine were added to the reaction solution and stirred at 100°C for 1 hour under atmospheric pressure. The reaction liquid was cooled to room temperature, and a phenolic resin modified by a compound having an unsaturated hydrocarbon group with a carbon number of 4 to 100 (hereinafter referred to as "Q2 resin") was obtained as a reaction product (acid value of 120 mgKOH/g).

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

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

[Examples 23 to 33, Comparative Examples 5 to 6] The solution of the photosensitive resin composition was prepared as shown in Table 10 below. The units in Table 10 are parts by mass.

The photosensitive resin compositions of Examples 23 to 33 and Comparative Examples 5 to 6 were prepared using the compounds listed in Table 10 and the formulation amounts listed in Table 11 and Table 12.

The prepared photosensitive resin composition was subjected to (7) a refractive index difference measurement test, (8) a sealing material reflow resistance test, and (9) a sealing material adhesion test. The results of each test are shown in Table 11 below.

(7) Refractive index difference measurement test A fan-out type wafer-level chip scale package type semiconductor device was manufactured using the photosensitive resin composition prepared in the embodiment and the comparative example. An interlayer insulating film with a thickness of 10 μm was removed as completely as possible from the manufactured semiconductor device. For the removed 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 prism coupler device (PC-2010) manufactured by METRICON.

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

The photosensitive resin composition prepared in Examples and Comparative Examples was applied on the epoxy cured film so that the final film thickness was 10 μm. The applied photosensitive resin composition was exposed to light at 200 mJ/cm2 in Examples 23 to 26, 32, and Comparative Example ⁵ , and at 500 mJ/ ^cm2 in Examples 27 to 29, 33, and Comparative Example 6, and then thermally cured at 150°C for 4 hours to form a first layer cured film with a thickness of 10 μm.

The photosensitive resin composition used in forming the first cured film was applied on the first cured film, and the entire surface was exposed under the same conditions as when the first cured film was formed, and then thermally cured to form a second cured film with a thickness of 10 μm.

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

After cutting a cross section of the cured film treated under the above simulated reflow conditions using a FIB device (JIB-4000, manufactured by JEOL Ltd.), the presence or absence of pores in the epoxy portion was confirmed to evaluate the degree of deterioration. A score of ○ was given if no pores were found, and a score of × was given if even one pore was found.

(9) Adhesion test with sealing material A probe was placed on the photosensitive resin cured film of the sample produced in the test of (8), and a traction tester (Sebastian 5, manufactured by Quad Group) was used to conduct the adhesion test. Evaluation: Adhesion strength is 70 MPa or more... Adhesion strength ◎ 50 MPa or more and less than -70 MPa... Adhesion strength ○ 30 MPa or more and less than -50 MPa... Adhesion strength △ Less than 30 MPa... Adhesion strength ×

[Table 10] Photoinitiator R-1 Photoacid generator R-2 Crosslinking agent S-1 Refractive index difference adjuster T-1 Biscyclooctane T-2 Diamond T-3 N-(4-Bromophenyl)phthalimide Solvent U-1 γ-Butyrolactone U-2 Dimethyl sulfoxide U-3 Propylene glycol monomethyl ether acetate U-4 Ethyl lactate

[Table 11] Embodiment 23 Embodiment 24 Embodiment 25 Embodiment 26 Embodiment 27 Embodiment 28 Embodiment 29 Embodiment 30 Embodiment 31 polymer O-1 100 O-2 100 O-3 100 O-4 100 P-1 100 P-2 100 P-3 100 Q-1 100 Q-2 100 Photoinitiator R-1 2 2 2 2 Photoacid generator R-2 10 10 10 15 15 Crosslinking agent S-1 15 15 Refractive index difference adjuster T-1 10 10 10 10 8 8 8 12 12 T-2 T-3 Solvent U-1 160 160 160 160 225 225 225 U-2 40 40 40 40 U-3 25 25 25 U-4 120 120 Refractive index difference 0.0140 0.0142 0.0144 0.0148 0.0142 0.0143 0.0147 0.0143 0.0148 Reflow resistance test ○ ○ ○ ○ ○ ○ ○ ○ ○ Adhesion test with sealing materials ◎ ○ ○ △ ○ ○ △ ○ △

[Table 12] Embodiment 32 Embodiment 33 Comparison Example 5 Comparative Example 6 polymer O-1 100 O-2 O-3 O-4 100 P-1 100 P-2 P-3 100 Q-1 Q-2 Photoinitiator R-1 2 2 Photoacid generator R-2 10 10 Crosslinking agent S-1 Refractive index difference adjuster T-1 T-2 10 8 T-3 30 30 Solvent U-1 160 225 160 225 U-2 40 40 U-3 25 25 U-4 Refractive index difference 0.0141 0.0143 0.0163 0.0166 Reflow resistance test ○ ○ × × Adhesion test with sealing materials ◎ ○ × ×

According to Tables 11 and 12, the results of the tests (7) to (9) conducted on the photosensitive resin compositions of Examples 23 to 33 confirmed that when the refractive index difference was less than 0.0150, no voids were found in the epoxy portion in the reflow resistance test of the sealing material, and that the adhesion was evaluated as ◎, ○, or △ in the adhesion test with the sealing material.

On the other hand, it can be seen from Tables 11 and 12 that the results of the tests (7) to (9) conducted on the photosensitive resin compositions of Comparative Examples 5 and 6 confirmed that when the refractive index difference exceeded 0.0150, pores were found in the epoxy portion in the reflow resistance test of the sealing material, and the adhesion was evaluated as × in the adhesion test with the sealing material.

Furthermore, a fan-out type wafer-level chip scale package semiconductor device containing epoxy resin in a mold resin was manufactured using the photosensitive resin composition of Examples 23 to 33, and the result was that it could operate without any problem. [Industrial Applicability]

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

1: Semiconductor device 2: Semiconductor chip 2a: Terminal 3: Sealing material 4: Rewiring layer 5: Wiring 6: Interlayer insulation film 7: External connection terminal 8: Flip chip BGA 9: Fan-out type WLCSP 10: Wafer 11: Support 12: Mold resin 13: Photosensitive resin composition 14: Sealing resin 15: Solder bump 16: Solder ball 17: Interlayer A: Arrow S1: Area of the rewiring layer S2: Area of the semiconductor chip

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

1:Semiconductor devices

2: Semiconductor chip

2a: Terminal

3: Sealing material

4: Rewiring layer

5: Wiring

6: Interlayer insulation film

7: External connection terminal

A: Arrow

Claims (35)

A semiconductor device, characterized in that it comprises: a semiconductor chip, a sealing material, and a redistribution layer whose area is larger than the semiconductor chip when viewed from above, and the sealing material has a portion directly in contact with the interlayer insulating film of the redistribution layer, and the 5% weight loss temperature of the interlayer insulating film of the redistribution layer is below 300°C. A semiconductor device as claimed in claim 1, wherein the sealing material comprises epoxy resin. The semiconductor device of claim 1 or 2, wherein the interlayer insulating film comprises a material selected from polyimide, polybenzoic acid,

At least one of azole, and a polymer having a phenolic hydroxyl group. The semiconductor device of claim 3, wherein the interlayer insulating film comprises a polyimide having a structure of the following general formula (1):

(In the general formula (1), ^X1 is a tetravalent organic group, ^Y1 is a divalent organic group, and m is an integer greater than or equal to 1). A semiconductor device as claimed in claim 4, wherein ^X1 in the general formula (1) is a tetravalent organic group containing an aromatic ring, and ^Y1 in the general formula (1) is a divalent organic group containing an aromatic ring. The semiconductor device of claim 4, wherein ^X1 in the above general formula (1) comprises at least one structure represented by the following general formulas (2) to (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 6, wherein ^X1 in the above general formula (1) comprises a structure represented by the following general formula (5), [Chemical 19]

The semiconductor device of claim 4, wherein ^Y1 in the above general formula (1) comprises 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 with 1 to 5 carbon atoms, or hydroxyl groups, and 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, and may be different or the same) [Chemical 22]

(R ₂₂ is a divalent organic group or an oxygen atom, R ₂₃ to R ₃₀ are a hydrogen atom, a halogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group, and may be the same or different). The semiconductor device of claim 8, wherein ^Y1 in the above general formula (1) comprises a structure represented by the following general formula (9),

The semiconductor device of claim 3, wherein the polyphenylene oxide

The azole includes a polybenzoic acid having a structure of the following general formula (10):

Azoles,

(In the general formula (10), U and V are divalent organic groups). As in claim 10, the semiconductor device, wherein U in the above general formula (10) is a divalent organic group with 1 to 30 carbon atoms. As in claim 11, the semiconductor device, wherein U in the above general formula (10) is a chain-like alkylene group having 1 to 8 carbon atoms and in which part or all of the hydrogen atoms are replaced by fluorine atoms. As in claim 10, the semiconductor device, wherein V in the above general formula (10) is a divalent organic group containing an aromatic group. The semiconductor device of claim 13, wherein V of the general formula (10) comprises 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 having 1 to 5 carbon atoms, and may be the same or different)

(R ₁₄ to R ₂₁ are hydrogen atoms, halogen atoms, or monovalent organic groups having 1 to 5 carbon atoms, and may be different or the same.)

(R ₂₂ is a divalent organic group or an oxygen atom, R ₂₃ to R ₃₀ are a hydrogen atom, a halogen atom, or a monovalent aliphatic group having 1 to 5 carbon atoms, and may be the same or different). The semiconductor device of claim 14, wherein V of the above general formula (10) comprises a structure represented by the following general formula (9),

As in claim 10, the semiconductor device, wherein V in the above general formula (10) is a divalent organic group with 1 to 40 carbon atoms. As in claim 16, the semiconductor device, wherein V in the above general formula (10) is a divalent chain aliphatic group having 1 to 20 carbon atoms. As in claim 3, the semiconductor device, wherein the polymer having a phenolic hydroxyl group comprises a novolac-type phenolic resin. A semiconductor device as claimed in claim 3, wherein the polymer having a phenolic hydroxyl group comprises a phenolic resin without an unsaturated hydrocarbon group and a modified phenolic resin having an unsaturated hydrocarbon group. A semiconductor device as claimed in claim 1 or 2, wherein when the redistribution layer is observed in cross section, the redistribution layer includes: a first interlayer insulating film layer; a second interlayer insulating film layer; and an intermediate layer, which is a layer different from the first interlayer insulating film layer and the second interlayer insulating film layer, and is disposed between the first interlayer insulating film layer and the second interlayer insulating film layer. As in claim 20, the semiconductor device, wherein the first interlayer insulating film layer is in contact with the sealing material, and the 5% weight reduction temperature of the first interlayer insulating film layer is below 300°C. A semiconductor device as claimed in claim 20, wherein the composition of the second interlayer insulating film layer is different from that of the first interlayer insulating film layer. A semiconductor device as claimed in claim 20, wherein 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. A semiconductor device as claimed in claim 1 or 2, wherein the semiconductor device is a fan-out type wafer-level chip scale package type semiconductor device. A semiconductor device as claimed in claim 1 or 2, wherein the 5% weight loss temperature of the interlayer insulating film of the redistribution layer is below 280°C. A semiconductor device as claimed in claim 25, wherein the 5% weight reduction temperature of the interlayer insulating film of the redistribution layer is below 260°C. A semiconductor device as claimed in claim 25, wherein the 5% weight reduction temperature of the interlayer insulating film of the redistribution layer is below 240°C. A semiconductor device as claimed in claim 25, wherein the 5% weight reduction temperature of the interlayer insulating film of the redistribution layer is below 220°C. A semiconductor device as claimed in claim 25, wherein the 5% weight reduction temperature of the interlayer insulating film of the redistribution layer is below 200°C. A semiconductor device as claimed in claim 1 or 2, wherein the 5% weight reduction temperature of the interlayer insulating film of the redistribution layer is above 80°C. A semiconductor device as claimed in claim 30, wherein the 5% weight reduction temperature of the interlayer insulating film of the redistribution layer is below 100°C. A semiconductor device as claimed in claim 30, wherein the 5% weight reduction temperature of the interlayer insulating film of the redistribution layer is below 150°C. A method for manufacturing a semiconductor device, characterized by comprising: a step of forming a chip sealing body with a semiconductor chip and a sealing material, and a step of forming a redistribution layer having an area larger than the semiconductor chip in top view and including an interlayer insulating film, wherein the sealing material has a portion directly in contact with the interlayer insulating film of the redistribution layer, and the 5% weight reduction temperature of the interlayer insulating film is below 300°C. A method for manufacturing a semiconductor device as claimed in claim 33, comprising using a polyimide, a polybenzoic acid

The interlayer insulating film forming step comprises forming the interlayer insulating film with a photosensitive resin composition containing at least one compound of azole and a polymer having a phenolic hydroxyl group. A method for manufacturing a semiconductor device as claimed in claim 34, wherein the interlayer insulating film forming step includes forming the interlayer insulating film using the photosensitive resin composition adjusted with an additive in such a manner that the temperature of the interlayer insulating film is reduced to below 300°C by 5% weight of the interlayer insulating film.