TW202212422A - Semiconductor device and manufacturing method thereof - Google Patents

Abstract

The object of the present invention is to provide a semiconductor device having excellent adhesion between an interlayer insulating film in a rewiring layer and a packaging material and excellent electrical characteristics, and a manufacturing method thereof. The semiconductor device (1) of the present invention is characterized in that: the device is provided with a semiconductor chip (2), a packaging material (3) covering the semiconductor chip, and a rewiring layer (4) having an area larger than the aforementioned semiconductor chip when viewed from above; and the weight loss rate of the interlayer insulating film (6) of the rewiring layer, after heated to 700 DEG C in a speed of 10 DEG C/min in an air atmosphere is 5-95% by weight. According to the present invention, the semiconductor device having excellent adhesion between the interlayer insulating film in the rewiring layer and the packaging material and excellent electrical characteristics, and the manufacturing method thereof can be provided.

Description

Semiconductor device and method of manufacturing the same

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

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

In a fan-out type semiconductor package, by covering the semiconductor chip with a sealing material, a chip seal body larger than the chip size of the semiconductor chip is formed. Furthermore, the rewiring layer which reaches the area|region of a semiconductor wafer and a sealing material is formed. The rewiring layer is formed with a relatively thin film thickness. In addition, since the rewiring layer can be formed up to the region of the sealing material, the number of external connection terminals can be increased.

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

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

[Problems to be Solved by Invention]

The fan-out type semiconductor device is required to have high adhesion between the interlayer insulating film in the rewiring layer and the sealing material. However, in the conventional fan-out type semiconductor device, the adhesion between the interlayer insulating film in the rewiring layer and the sealing material is insufficient. In addition, in the antenna-integrated module or the like, the electrical characteristics tend to be lowered.

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

The semiconductor device of the present invention is characterized by comprising a semiconductor chip, a sealing material covering the semiconductor chip, and a rewiring layer having an area larger than that of the semiconductor chip in plan view, and the interlayer insulating film between the rewiring layers is in an air environment with a thickness of 10 The weight reduction rate after the temperature was raised to 700°C per minute was 5 to 95% by weight. In another aspect, the semiconductor device of the present invention is characterized by comprising a semiconductor chip, a sealing material covering the semiconductor chip, and a rewiring layer having an area larger than that of the semiconductor chip in plan view, and the rewiring layer is When the interlayer insulating film is kept at 100° C. for 60 minutes, the volatile gas per 1 cm ² is 0.2×10 ^-6 to 2.5×10 ^-6 Pa. In yet another aspect, the semiconductor device of the present invention is characterized by comprising a semiconductor chip, a sealing material covering the semiconductor chip, and a rewiring layer having an area larger than that of the semiconductor chip in plan view, and the rewiring layer is When the interlayer insulating film is kept at 100° C. for 60 minutes, the volatile gas per 1 cm ² is 0.4×10 ^-6 to 1.8×10 ^-6 Pa.

In this invention, it is preferable that the said sealing material and the said interlayer insulating film are in direct contact with each other.

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

In the present invention, the interlayer insulating film preferably contains at least one selected from the group consisting of polyimide, polybenzoxazole, and a polymer having a phenolic hydroxyl group.

(通式(1)中，X ¹為4價有機基，Y ¹為2價有機基，m為1以上之整數) In this invention, it is preferable that the said interlayer insulating film contains the polyimide containing the structure of following general formula (1). [hua 1]

(In the general formula (1), X ¹ is a tetravalent organic group, Y ¹ is a divalent organic group, and m is an integer of 1 or more)

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

[化3]

[化4]

(通式(4)中，R ₉為氧原子、硫原子或2價有機基) In the present invention, X ¹ in the above-mentioned general formula (1) preferably contains at least one structure represented by the following general formulae (2) to (4). [hua 2]

[hua 3]

[hua 4]

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

Preferably, X ¹ in the above general formula (1) contains a structure represented by the following general formula (5). [hua 5]

(R ₁₀、R ₁₁、R ₁₂及R ₁₃為氫原子、碳數1～5之1價脂肪族基或羥基，可相同亦可不同) [化7]

(R ₁₄～R ₂₁為氫原子、鹵素原子、碳數1～5之1價有機基或羥基，相互可不同，亦可相同) [化8]

(R ₂₂為2價基，R ₂₃～R ₃₀為氫原子、鹵素原子、碳數1～5之1價脂肪族基或羥基，可相同亦可不同) It is preferable that Y ¹ in the said general formula (1) contains at least 1 type of structure represented by following general formula (6) - general formula (8). [hua 6]

(R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are a hydrogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group, which may be the same or different) [Chemical 7]

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

(R ₂₂ is a divalent group, and 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, which may be the same or different)

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

(通式(10)中，Y ²與Y ³為2價有機基) In this invention, it is preferable that the said polybenzoxazole contains the polybenzoxazole of the structure containing the following general formula (10). [Chemical 10]

(In the general formula (10), Y ² and Y ³ are divalent organic groups)

In the present invention, it is preferable that Y ² of the general formula (10) is a divalent organic group having 1 to 30 carbon atoms.

In the present invention, Y ² of the general formula (10) is preferably a chain alkylene group having 1 to 8 carbon atoms and a part or all of hydrogen atoms substituted with fluorine atoms.

In this invention, it is preferable that Y ³ of the said general formula (10) is a divalent organic group containing an aromatic group.

(R ₁₀、R ₁₁、R ₁₂及R ₁₃為氫原子、碳數1～5之1價脂肪族基，可相同亦可不同) [化12]

(R ₁₄～R ₂₁為氫原子、鹵素原子、碳數1～5之1價有機基，相互可不同，亦可相同) [化13]

(R ₂₂為2價基，R ₂₃～R ₃₀為氫原子、鹵素原子、碳數1～5之1價脂肪族基，可相同亦可不同) In the present invention, it is preferable that Y ³ of the above general formula (10) contains at least one structure represented by the following general formulae (6) to (8). [Chemical 11]

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

(R ₁₄ to R ₂₁ are a hydrogen atom, a halogen atom, and a monovalent organic group having 1 to 5 carbon atoms, which may be different from each other or the same.) [Chemical 13]

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

It is preferable that Y ³ of the above-mentioned general formula (10) contains a structure represented by the following general formula (9). [Chemical 14]

In the present invention, it is preferable that Y ³ of the general formula (10) is a divalent organic group having 1 to 40 carbon atoms.

In the present invention, it is preferable that Y ³ of the above-mentioned general formula (10) is a divalent chain aliphatic group having 1 to 20 carbon atoms.

In this invention, it is preferable that the said polymer which has a phenolic hydroxyl group contains a novolac-type phenol resin.

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

In this invention, it is preferable that the said interlayer insulating film contains a filler.

In this invention, it is preferable that the said filler is an inorganic filler.

In this invention, it is preferable that the shape of the said filler is a particle shape.

In this invention, it is preferable that the shape of the said filler is spherical.

In the present invention, it is preferable that the primary particle size of the above-mentioned filler is 5 nm to 1 μm.

In the present invention, the rewiring layer preferably contains a first interlayer insulating film layer, a second interlayer insulating film layer, and the first interlayer insulating film layer and the above-mentioned rewiring layer when viewed in cross-section. The second interlayer insulating film layer is different and is provided in an intermediate layer between the first interlayer insulating film layer and the second interlayer insulating film layer.

In the present invention, it is preferable that the first interlayer insulating film layer is in contact with the sealing material, and the weight reduction rate of the first interlayer insulating film layer in an air environment at 10°C/min to 700°C is 5. ~95 wt%.

In this invention, it is preferable that the said 2nd interlayer insulating film layer is a composition different from the said 1st interlayer insulating film layer.

In the present invention, it is preferable that the weight reduction rate of the above-mentioned second interlayer insulating film layer in an air environment at a temperature of 10° C./min to 700° C. is the same as that of the above-mentioned first interlayer insulating film layer in an air environment at a temperature of 10° C. The weight loss rate after the temperature was raised to 700°C per minute was different.

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

In the present invention, the interlayer insulating film of the rewiring layer preferably has a weight reduction rate of 10 to 95% by weight after the temperature is raised to 700° C. at 10° C./min in an air environment.

In the present invention, the interlayer insulating film of the rewiring layer preferably has a weight reduction rate of 20 to 95% by weight after the temperature is raised to 700° C. at 10° C./min in an air environment.

In the present invention, the interlayer insulating film of the rewiring layer preferably has a weight reduction rate of 30 to 90% by weight after the temperature is raised to 700° C. at 10° C./min in an air environment.

In the present invention, the interlayer insulating film of the rewiring layer preferably has a weight reduction rate of 40 to 90% by weight after the temperature is raised to 700° C. at 10° C./min in an air environment.

In the present invention, the interlayer insulating film of the rewiring layer preferably has a weight reduction rate of 40 to 85% by weight after the temperature is raised to 700° C. at 10° C./min in an air environment.

In the present invention, the interlayer insulating film of the rewiring layer preferably has a weight reduction rate of 40 to 80 wt % after the temperature is raised to 700° C. at 10° C./min in an air environment.

In the present invention, the interlayer insulating film of the rewiring layer preferably has a weight reduction rate of 40 to 75 wt % after the temperature is raised to 700° C. at 10° C./min in an air environment.

In the present invention, the interlayer insulating film of the rewiring layer preferably has a weight reduction rate of 40 to 70 wt % after the temperature is raised to 700° C. at 10° C./min in an air environment. Furthermore, in another aspect of the present invention, the following contents are preferred.

In this invention, it is preferable that the said sealing material and the said interlayer insulating film are in direct contact with each other.

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

In the present invention, the interlayer insulating film preferably contains at least one selected from the group consisting of polyimide, polybenzoxazole, and a polymer having a phenolic hydroxyl group.

(通式(1)中，X ¹為4價有機基，Y ¹為2價有機基，m為1以上之整數) In this invention, it is preferable that the said interlayer insulating film contains the polyimide containing the structure of following general formula (1). [Chemical 15]

(In the general formula (1), X ¹ is a tetravalent organic group, Y ¹ is a divalent organic group, and m is an integer of 1 or more)

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

[化17]

[化18]

(通式(4)中，R ₉為氧原子、硫原子或2價有機基) In the present invention, X ¹ in the above-mentioned general formula (1) preferably contains at least one structure represented by the following general formulae (2) to (4). [Chemical 16]

[Chemical 17]

[Chemical 18]

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

Preferably, X ¹ in the above general formula (1) contains a structure represented by the following general formula (5). [Chemical 19]

(R ₁₀、R ₁₁、R ₁₂及R ₁₃為氫原子、碳數1～5之1價脂肪族基或羥基，可相同亦可不同) [化21]

(R ₁₄～R ₂₁為氫原子、鹵素原子、碳數1～5之1價有機基或羥基，相互可不同，亦可相同) [化22]

(R ₂₂為2價基，R ₂₃～R ₃₀為氫原子、鹵素原子、碳數1～5之1價脂肪族基或羥基，可相同亦可不同) It is preferable that Y ¹ in the said general formula (1) contains at least 1 type of structure represented by following general formula (6) - general formula (8). [hua 20]

(R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are a hydrogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group, which may be the same or different) [Chemical 21]

(R ₁₄ to R ₂₁ are a hydrogen atom, a halogen atom, a monovalent organic group having 1 to 5 carbon atoms, or a hydroxyl group, which may be different from each other or the same) [Chemical 22]

(R ₂₂ is a divalent group, and 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, which may be the same or different)

In the present invention, Y ¹ in the above general formula (1) preferably has a structure represented by the following general formula (9). [Chemical 23]

(通式(10)中，Y ²與Y ³為2價有機基) In this invention, it is preferable that the said polybenzoxazole contains the polybenzoxazole of the structure containing the following general formula (10). [Chemical 24]

(In the general formula (10), Y ² and Y ³ are divalent organic groups)

In the present invention, it is preferable that Y ² of the general formula (10) is a divalent organic group having 1 to 30 carbon atoms.

In the present invention, Y ² of the general formula (10) is preferably a chain alkylene group having 1 to 8 carbon atoms and a part or all of hydrogen atoms substituted with fluorine atoms.

In this invention, it is preferable that Y ³ of the said general formula (10) is a divalent organic group containing an aromatic group.

(R ₁₀、R ₁₁、R ₁₂及R ₁₃為氫原子、碳數1～5之1價脂肪族基，可相同亦可不同) [化26]

(R ₁₄～R ₂₁為氫原子、鹵素原子、碳數1～5之1價有機基，相互可不同，亦可相同) [化27]

(R ₂₂為2價基，R ₂₃～R ₃₀為氫原子、鹵素原子、碳數1～5之1價脂肪族基，可相同亦可不同) In the present invention, it is preferable that Y ³ of the above general formula (10) contains at least one structure represented by the following general formulae (6) to (8). [Chemical 25]

(R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are hydrogen atoms and monovalent aliphatic groups having 1 to 5 carbon atoms, which may be the same or different) [Chem. 26]

(R ₁₄ to R ₂₁ are a hydrogen atom, a halogen atom, and a monovalent organic group having 1 to 5 carbon atoms, which may be different from each other or the same.) [Chemical 27]

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

It is preferable that Y ³ of the above-mentioned general formula (10) contains a structure represented by the following general formula (9). [Chemical 28]

In the present invention, it is preferable that Y ³ of the general formula (10) is a divalent organic group having 1 to 40 carbon atoms.

In the present invention, it is preferable that Y ³ of the above-mentioned general formula (10) is a divalent chain aliphatic group having 1 to 20 carbon atoms.

In this invention, it is preferable that the said polymer which has a phenolic hydroxyl group contains a novolac-type phenol resin.

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

In the present invention, the rewiring layer preferably contains a first interlayer insulating film layer, a second interlayer insulating film layer, and the first interlayer insulating film layer and the above-mentioned rewiring layer when viewed in cross-section. The second interlayer insulating film layer is different and is provided in an intermediate layer between the first interlayer insulating film layer and the second interlayer insulating film layer.

In the present invention, it is preferable that the first interlayer insulating film layer is in contact with the sealing material, and the volatile gas of the first interlayer insulating film layer when kept at 100° C. for 60 minutes is 0.2×10 per 1 cm ² . ^-6 to 2.5×10 ^-6 Pa. In the present invention, it is more preferable that the first interlayer insulating film layer is in contact with the sealing material, and the volatile gas of the first interlayer insulating film layer when kept at 100° C. for 60 minutes is 0.4×10 per 1 cm ² . ^-6 to 1.8×10 ^-6 Pa.

In this invention, it is preferable that the said 2nd interlayer insulating film layer is a composition different from the said 1st interlayer insulating film layer.

In the present invention, the volatile gas when the second interlayer insulating film is kept at 100°C for 60 minutes is preferably different from the volatile gas when the first interlayer insulating film is kept at 100°C for 60 minutes.

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

In the present invention, when the interlayer insulating film of the rewiring layer is kept at 100° C. for 60 minutes, the volatile gas is preferably 0.2×10 ^-6 to 2.5×10 ^-6 Pa per 1 cm ² . In the present invention, more preferably, the volatile gas per 1 cm ² is 0.6×10 ^-6 to 1.8×10 ^-6 Pa when the interlayer insulating film of the rewiring layer is kept at 100° C. for 60 minutes.

In the present invention, it is further preferable that the volatile gas when the interlayer insulating film of the rewiring layer is kept at 100° C. for 60 minutes is 0.6×10 ⁻⁶ to 1.6×10 ⁻⁶ Pa per 1 cm ² .

In the present invention, more preferably, the volatile gas per 1 cm ² of the interlayer insulating film of the rewiring layer is 0.6×10 ^-6 to 1.4×10 ^-6 Pa when kept at 100° C. for 60 minutes.

In the present invention, the interlayer insulating film preferably contains a thermal crosslinking agent.

In the present invention, the interlayer insulating film preferably contains a volatilization modifier.

In the present invention, the interlayer insulating film preferably contains a thermal crosslinking agent and a volatilization modifier.

In this invention, it is preferable that the said rewiring layer contains the inorganic film in contact with the said interlayer insulating film.

In this invention, it is preferable that the said inorganic film has the reaction layer which the volatile gas contained in the said interlayer insulating film and the component of the said inorganic film react with.

The method of manufacturing a semiconductor device of the present invention is characterized by comprising a step of covering a semiconductor wafer with a sealing material, and a step of forming a rewiring layer having an area larger than the semiconductor wafer in plan view and including an interlayer insulating film, and the interlayer insulating film is in the air. The weight reduction rate after raising the temperature to 700°C at 10°C/min under the environment is 5 to 95% by weight. The method of manufacturing a semiconductor device of the present invention is characterized by comprising the steps of covering a semiconductor wafer with a sealing material, and forming a rewiring layer having an area larger than the semiconductor wafer in plan view and including an interlayer insulating film, and the interlayer insulating film is formed at 100°C. The volatile gas when kept at ℃ for 60 minutes is 0.2×10 ^-6 to 2.5×10 ^-6 Pa per 1 cm ² . Preferably, the method for manufacturing a semiconductor device of the present invention is characterized by comprising a step of covering a semiconductor wafer with a sealing material, and a step of forming a rewiring layer having an area larger than the semiconductor wafer in plan view and including an interlayer insulating film, and the interlayer insulating layer When the film was kept at 100°C for 60 minutes, the volatile gas per 1 cm ² was 0.4×10 ^-6 to 1.8×10 ^-6 Pa.

In the present invention, it is preferable to include the following step of forming an interlayer insulating film: forming the above-mentioned photosensitive resin composition using a photosensitive resin composition capable of forming at least one compound of polyimide, polybenzoxazole, and a polymer having a phenolic hydroxyl group. interlayer insulating film.

In the present invention, it is preferable that the above-mentioned interlayer insulating film forming step includes the following steps: using the above-mentioned interlayer insulating film in an air environment, the weight reduction rate after the temperature is raised to 700° C. at 10° C./min becomes 5 to 95% by weight. The said photosensitive resin composition adjusted with the filler forms the said interlayer insulating film. In the present invention, it is preferable to include the following step of forming an interlayer insulating film: forming the above-mentioned photosensitive resin composition using a photosensitive resin composition capable of forming at least one compound of polyimide, polybenzoxazole, and a polymer having a phenolic hydroxyl group. interlayer insulating film.

In the present invention, it is preferable that the step of forming the interlayer insulating film includes the following steps: using the method that the volatile gas when the interlayer insulating film is kept at 100° C. for 60 minutes becomes 0.2×10 ⁻⁶ to 2.5×10 ⁻⁶ Pa The adjusted said photosensitive resin composition forms the said interlayer insulating film. In the present invention, it is more preferable that the above-mentioned interlayer insulating film forming step includes the following step: using the method that the volatile gas when the above-mentioned interlayer insulating film is kept at 100° C. for 60 minutes becomes 0.4×10 ⁻⁶ to 1.8×10 ⁻⁶ Pa The adjusted said photosensitive resin composition forms the said interlayer insulating film.

In the present invention, it is preferable that the step of forming the interlayer insulating film includes the following steps: using the method that the volatile gas when the interlayer insulating film is kept at 100° C. for 60 minutes becomes 0.2×10 ⁻⁶ to 2.5×10 ⁻⁶ Pa The above-mentioned photosensitive resin composition adjusted with a thermal crosslinking agent and/or a volatilization modifier forms the above-mentioned interlayer insulating film. In the present invention, it is more preferable that the above-mentioned interlayer insulating film forming step includes the following step: using the method that the volatile gas when the above-mentioned interlayer insulating film is kept at 100° C. for 60 minutes becomes 0.4×10 ⁻⁶ to 1.8×10 ⁻⁶ Pa The above-mentioned photosensitive resin composition adjusted with a thermal crosslinking agent and/or a volatilization modifier forms the above-mentioned interlayer insulating film. [Effect of invention]

ADVANTAGE OF THE INVENTION According to this invention, the adhesiveness of the interlayer insulating film in the rewiring layer and the sealing material is excellent, and the semiconductor device which is excellent in electrical measurement, and its manufacturing method can be provided.

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

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

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

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

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

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

Here, the "rewiring layer 4" in this embodiment refers to a layer having a thin film of the wiring 5 and the interlayer insulating film 6 as described above, and does not include an interposer or a printed wiring board. Since the semiconductor device (semiconductor IC) 1 uses the rewiring layer 4, as shown in FIG. 4, it is thinner than a semiconductor device using an interposer such as a flip chip BGA.

In this embodiment, the film thickness of the rewiring layer 4 can be set to about 3 to 30 μm. The film thickness of the rewiring layer 4 may be 1 μm or more, 5 μm or more, or 10 μm or more. Moreover, the film thickness of the rewiring layer 4 may be 40 μm or less, 30 μm or less, or 20 μm or less. When the semiconductor device 1 is viewed in plan (viewed in the direction of arrow A), it becomes the following FIG. 2 . In addition, the sealing material 3 is abbreviate|omitted.

The semiconductor device 1 shown in FIG. 2 is configured such that the area S1 of the rewiring layer 4 is larger than the area S2 of the semiconductor wafer 2 . The area S1 of the redistribution layer 4 is not particularly limited, but 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 the area S2 of the semiconductor chip 2, preferably 1.1 times or more, more preferably 1.2 times or more, particularly preferably 1.3 times or more. The upper limit is not particularly limited, and the area S1 of the rewiring layer 4 may be 50 times or less, 25 times or less, 10 times or less, or 5 times or less of the area S2 of the semiconductor wafer 2 . Furthermore, in FIG. 2 , the area of the portion of the redistribution layer 4 covered by the semiconductor wafer 2 is also included in the area S1 of the redistribution layer 4 .

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

The rewiring layer 4 may be one layer, or may be a multilayer of two or more layers. The rewiring layer 4 includes the wirings 5 and the interlayer insulating film 6 burying the wirings 5 .

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

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

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

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

(Interlayer insulating film) The present embodiment is characterized in that the weight reduction rate of the interlayer insulating film 6 is 5 to 95 wt % after the temperature is raised to 700° C. at 10° C./min in an air environment. Hereinafter, the weight reduction rate after the temperature is raised to 700° C. at 10° C./min in an air environment is simply referred to as “weight reduction rate”.

If the weight reduction ratio is 5 to 95% by weight, the interlayer insulating film 6 and the sealing material 3 have excellent adhesion during high temperature treatment. The reason for this is not certain, but the inventors of the present invention speculate as follows.

In the manufacturing process of the fan-out type semiconductor device, in order to form the rewiring layer 4 , the photosensitive resin composition is coated on the chip sealing body including the semiconductor wafer 2 and the sealing material 3 . Next, the photosensitive resin composition is exposed to light. Then, the photosensitive resin composition is developed and hardened, thereby selectively forming a portion having a cured product of the photosensitive resin composition and a portion having no cured product of the photosensitive resin composition. The cured product of the photosensitive resin composition becomes the interlayer insulating film 6 . Moreover, the wiring 5 is formed in the part which does not have the hardened|cured material of the photosensitive resin composition. In general, the rewiring layer 4 is often multi-layered. That is, the photosensitive resin composition is further coated, exposed, developed, and cured on the interlayer insulating film 6 and the wiring 5 .

In addition, in the step of forming the interlayer insulating film 6 and the wiring 5, depending on the manufacturing method, a reflow step may be included. On the other hand, since the interlayer insulating film 6 needs to be patterned as described above, it usually contains a polar resin or an additive in many cases, and tends to contain moisture. It is presumed that the insulating film undergoes a temporary high temperature thermal history such as reflow, so that volatilized water is generated at the interface between the sealing material and the insulating film, and thus the adhesiveness is degraded. When the resin content of the interlayer insulating film 6 is low, that is, when the weight reduction rate of the interlayer insulating film 6 is within a certain range, the volatilization of moisture tends to be suppressed, so it exists between the sealing material 3 and the interlayer insulating film 6 . The interface is less likely to accumulate gas, and the sealing material 3 and the interlayer insulating film 6 tend not to be easily peeled off. Moreover, in the case where the weight reduction rate of the interlayer insulating film 6 falls within a specific range, the resin content rate is sufficiently high, so that the adhesiveness with the sealing material can be sufficiently secured.

The interlayer insulating film 6 of the present embodiment preferably has a weight reduction rate of 5 to 95% by weight after the temperature is raised to 700° C. at 10° C./min in an air environment. Therefore, in this embodiment, the adhesion between the interlayer insulating film 6 and the sealing material 3 is good, and the amount of water volatilized from the interlayer insulating film 6 during the thermal history is small, so the adhesion after the thermal history is also good.

From the viewpoint of the initial adhesion between the interlayer insulating film and the sealing material 3, the weight loss rate of the interlayer insulating film 6 is preferably 95% by weight or less, more preferably 90% by weight or less, and more preferably 85% by weight or less. , more preferably 80% by weight or less, particularly preferably 75% by weight or less.

The weight loss rate of the interlayer insulating film 6 may be 70 wt % or less, 65 wt % or less, 60 wt % or less, 55 wt % or less, 50 wt % or less, or 45 wt % or less, 40 wt % or less, 35 wt % or less, 30 wt % or less, 25 wt % or less, or 20 wt % or less.

From the viewpoint of the adhesiveness after the thermal history between the interlayer insulating film and the sealing material 3, the weight loss rate of the interlayer insulating film 6 is preferably 5% by weight or more, more preferably 10% by weight or more, and more preferably 15% by weight % or more, more preferably 20 wt % or more, particularly preferably 25 wt % or more, particularly preferably 30 wt % or more, still more preferably 35 wt % or more, and most preferably 40 wt % or more.

The weight loss rate of the interlayer insulating film 6 may be 45 wt % or more, 50 wt % or more, 55 wt % or more, 60 wt % or more, 65 wt % or more, or 70% by weight or more, 75% by weight or more, or 80% by weight or more.

In the case where the weight reduction rate of the interlayer insulating film 6 of the present embodiment is within a specific range, for example, when it is made into an antenna-integrated module, the electrical characteristics become favorable. The reason has not been identified, but the inventors of the present invention consider it as follows.

That is, when the weight reduction rate is small, it becomes an interlayer insulating film containing a material that is not easily reduced in weight, such as a large amount of inorganic fillers, and these tend to have a low dielectric loss tangent. Therefore, for example, compared with the antenna alone, the deviation tends to be smaller when the antenna-integrated module is manufactured. When the weight reduction rate is large, the interlayer insulating film contains more components such as resin, so the uniformity of the components contained in the interlayer insulating film is good, and the ripples of the signal sent to the antenna or sent from the antenna ( The disorder of the waveform) tends to be suppressed. In the case where the weight reduction rate of the interlayer insulating film 6 is in a specific range, these tendencies can be combined, and the electrical characteristics can be improved.

(Interlayer insulating film) In another aspect of the present embodiment, the interlayer insulating film 6 is characterized in that the volatile gas per 1 cm ² is 0.2×10 ⁻⁶ to 2.5×10 ⁻ when the interlayer insulating film 6 is kept at 100° C. for 60 minutes. ⁶ Pa. In yet another aspect of the present embodiment, the volatile gas when the interlayer insulating film 6 is kept at 100° C. for 60 minutes is 0.4×10 ⁻⁶ to 1.8×10 ⁻⁶ Pa per 1 cm ² . Hereinafter, the volatile gas at the time of holding at 100° C. for 60 minutes is simply referred to as “volatile gas pressure”.

If the volatile gas when the interlayer insulating film 6 is kept at 100° C. for 60 minutes is in the above range, the adhesion between the interlayer insulating film 6 and the inorganic film 8 is excellent. The reason for this is not certain, but the inventors of the present invention speculate as follows.

In the manufacturing process of the fan-out type semiconductor device, in order to form the rewiring layer 4 , the photosensitive resin composition is coated on the chip sealing body including the semiconductor wafer 2 and the sealing material 3 . Next, the photosensitive resin composition is exposed to light. Then, the photosensitive resin composition is developed and hardened, thereby selectively forming a portion having a cured product of the photosensitive resin composition and a portion having no cured product of the photosensitive resin composition. The cured product of the photosensitive resin composition becomes the interlayer insulating film 6 . Moreover, the wiring 5 is formed in the part which does not have the hardened|cured material of the photosensitive resin composition. In general, the rewiring layer 4 is often multi-layered. That is, on the interlayer insulating film 6 and the wiring 5, the photosensitive resin composition is further coated, exposed, developed, and cured.

In addition, in the step of forming the interlayer insulating film 6 and the wiring 5, depending on the manufacturing method, there is a case where a step of sputtering an inorganic film such as titanium is included. On the other hand, since the interlayer insulating film 6 needs to be patterned as described above, it usually contains a polar resin or an additive in many cases, and tends to contain moisture. The contained moisture or components that are easily volatilized in vacuum volatilize a certain amount during sputtering, thereby forming a layer between the interlayer insulating film 6 and the inorganic film 8 in which the inorganic film reacts with the volatile components. When the inorganic film 8 is titanium, a layer containing titanium oxide is formed. By this reaction layer, the adhesion between the interlayer insulating film 6 and the inorganic film 8 can be improved. However, when there are too many volatile components, there is a possibility that the adhesion between the interlayer insulating film 6 and the inorganic film 8 may decrease due to the volatile components.

The interlayer insulating film 6 of the present embodiment preferably has a volatile gas of 0.4×10 ^-6 to 1.8×10 ^-6 Pa per 1 cm ² when kept at 100° C. for 60 minutes. Therefore, in this embodiment, the adhesion between the interlayer insulating film 6 and the inorganic film is good.

From the viewpoint of the adhesion between the interlayer insulating film and the inorganic film, the volatile gas pressure when the interlayer insulating film 6 is kept at 100° C. for 60 minutes is preferably 0.4×10 ^-6 Pa or more, more preferably 0.6×10 ^-6 Pa or more, more preferably 0.8×10 ^-6 Pa or more, still more preferably 1.0×10 ^-6 Pa or more.

The volatile gas pressure when the interlayer insulating film 6 is kept at 100° C. for 60 minutes is not limited as long as it is 1.8×10 ⁻⁶ or less per 1 cm ² . It is preferably 1.8×10 ^-6 or less, more preferably 1.6×10 ^-6 or less, particularly preferably 1.4×10 ^-6 or less.

When the volatile gas pressure when the interlayer insulating film 6 of the present embodiment is kept at 100° C. for 60 minutes is within a specific range, for example, when an antenna-integrated module is produced, the electrical characteristics become favorable. The reason is not certain, but the inventors of the present invention consider it as follows.

That is, when the volatile gas pressure is low when kept at 100° C. for 60 minutes, it becomes an interlayer insulating film containing more non-volatile materials such as polymers, and these tend to have a low dielectric loss tangent. Therefore, for example, compared with the antenna alone, when the antenna-integrated module is manufactured, the deviation tends to be smaller.

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

The first interlayer insulating film layer and the second interlayer insulating film layer may have the same composition or different compositions. The first interlayer insulating film layer and the second interlayer insulating film layer may have the same volatile gas pressure, or may have different volatile gas pressures. The first interlayer insulating film layer and the second interlayer insulating film layer may have the same film thickness, or may have different film thicknesses. If the first interlayer insulating film layer and the second interlayer insulating film layer have different compositions, different volatile gas pressures or different film thicknesses, each interlayer insulating film layer can have different properties, which is preferable.

When the interlayer insulating film 6 is multi-layered, the volatile gas pressure of at least one layer of the interlayer insulating film 6 when kept at 100° C. for 60 minutes is 0.2×10 ⁻⁶ per 1 cm ² of the plurality of layers present. ～2.5×10 ^-6 Pa is sufficient. Preferably, when the interlayer insulating film 6 is multi-layered, among the multiple layers present, at least one layer of the interlayer insulating film 6 is kept at 100° C. for 60 minutes when the volatile gas pressure is 0.4× per 1 cm ² . 10 ^-6 to 1.8×10 ^-6 Pa is sufficient.

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

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

In the case where the interlayer insulating film 6 is multi-layered, the weight reduction rate of the interlayer insulating film 6 in at least one of the multiple layers may be 5 to 95% by weight, but between the sealing material 3 and the interlayer insulating film layer Since it is easy to be peeled off by gas, the weight reduction rate of the interlayer insulating film 6 between the interlayer insulating film layers in contact with the sealing material 3 is preferably 10 to 95% by weight. When the weight reduction rate of the interlayer insulating film 6 between the interlayer insulating film layers in contact with the sealing material 3 is 10 to 95% by weight, the adhesiveness between the sealing material 3 and the interlayer insulating film 6 is excellent.

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

(Resin composition for forming interlayer insulating film) The resin composition for forming the interlayer insulating film 6 is not particularly limited as long as it is a photosensitive resin composition, and preferably contains a polyimide precursor, a polybenzoxazole precursor, or a phenolic one. A photosensitive resin composition of at least one compound in a polymer of hydroxyl groups. The resin composition for forming the interlayer insulating film 6 may be liquid or film. In addition, the resin composition for forming the interlayer insulating film 6 may be a negative-type photosensitive resin composition or a positive-type photosensitive resin composition.

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

In this embodiment, it is preferable that the photosensitive resin composition of the interlayer insulating film 6 contains a filler. The filler in the present embodiment is not limited as long as it is an inert substance added for the purpose of improving strength and various properties.

The filler is preferably in the form of particles from the viewpoint of suppressing an increase in viscosity when it is prepared as a resin composition. Examples of the particle shape include needle shape, plate shape, spherical shape, and the like, and the filler is preferably spherical from the viewpoint of suppressing an increase in viscosity at the time of preparing the resin composition.

As acicular fillers, wollastonite, potassium titanate, wollastonite, aluminum borate, acicular calcium carbonate, etc. are mentioned.

As a plate-like filler, talc, mica, sericite, glass flakes, montmorillonite, boron nitride, plate-like calcium carbonate, etc. are mentioned.

As spherical fillers, calcium carbonate, silicon oxide, aluminum oxide, titanium oxide, clay, hydrotalcite, magnesium hydroxide, zinc oxide, barium titanate, etc. are mentioned. Among these, silicon oxide, aluminum oxide, titanium oxide, and barium titanate are preferable, and silicon oxide and aluminum oxide are more preferable from the viewpoint of electrical properties and storage stability when used as a resin composition.

As the size of the filler, in the case of spherical shape, the primary particle size is defined as the size, and in the case of plate shape or needle shape, the length of the long side is defined as the size, preferably 5 nm to 1000 nm, more preferably 10 nm nm～1000 nm. When it is 10 nm or more, there exists a tendency for it to become fully uniform when used as a resin composition, and when it is 1000 nm or less, photosensitivity can be provided. From the viewpoint of imparting photosensitivity, it is preferably 800 nm or less, more preferably 600 nm or less, and still more preferably 300 nm or less. From the viewpoint of adhesiveness or uniformity of the resin composition, it is preferably 15 nm or more, more preferably 30 nm or more, and still more preferably 50 nm or more.

In another aspect of this embodiment, it is preferable that the photosensitive resin composition of the interlayer insulating film 6 contains a thermal crosslinking agent or a volatilization regulator. The photosensitive resin composition is not particularly limited, and may be a photosensitive resin composition containing at least one compound selected from a polyimide precursor, a polybenzoxazole precursor, or a polymer having a phenolic hydroxyl group. As the thermal crosslinking accelerator, for example, epoxy compounds, oxetane compounds, oxazoline compounds, aldehydes, aldehyde-modified compounds, isocyanate compounds, unsaturated bond-containing compounds, polyol compounds, polyol compounds can be preferably used. Amine compounds, melamine compounds, metal chelating agents, C-methylol compounds, N-methylol compounds, and the like.

As a volatility modifier, polyethylene glycol, polypropylene glycol, etc. are mentioned.

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

R ¹及R ²分別獨立為氫原子、碳數1～30之飽和脂肪族基、芳香族基、具有碳碳不飽和雙鍵之一價有機基、或具有碳碳不飽和雙鍵之一價離子。X ¹為4價有機基，Y ¹為2價有機基，m為1以上之整數。m較佳為2以上，更佳為5以上。 [Chemical 29]

R ¹ and R ² are each independently a hydrogen atom, a saturated aliphatic group having 1 to 30 carbon atoms, an aromatic group, a valent organic group having a carbon-carbon unsaturated double bond, or a valence having a carbon-carbon unsaturated double bond ion. X ¹ is a tetravalent organic group, Y ¹ is a divalent organic group, and m is an integer of 1 or more. m is preferably 2 or more, more preferably 5 or more.

When R ¹ and R ² of the above general formula (11) exist as monovalent cations, O has a negative charge (exists as ^-O- ). Moreover, X ¹ and Y ¹ may contain a hydroxyl group.

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

(通式(12)中，R ₃、R ₄及R ₅分別獨立為氫原子或碳數1～5之有機基，並且m ₁為1～20之整數) [Chemical 30]

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

(通式(13)中，R ₆、R ₇及R ₈分別獨立為氫原子或碳數1～5之有機基，並且m ₂為1～20之整數)。 [Chemical 31]

(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).

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

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

[Chemical 32]

[Chemical 33]

(通式(4)中，R ₉為氧原子、硫原子、2價有機基之任一者) [Chemical 34]

(In the general formula (4), R ₉ is any one of an oxygen atom, a sulfur atom, and a divalent organic group)

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

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

[Chemical 35]

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

(R ₁₀、R ₁₁、R ₁₂及R ₁₃為氫原子、碳數1～5之1價脂肪族基，可相同亦可不同) [Chemical 36]

(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～R ₂₁為氫原子、鹵素原子、碳數1～5之1價有機基，相互可不同，亦可相同) [Chemical 37]

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

(R ₂₂為2價基，R ₂₃～R ₃₀為氫原子、鹵素原子、碳數1～5之1價脂肪族基，可相同亦可不同) [Chemical 38]

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

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

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

[Chemical 39]

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

Examples of the tetracarboxylic dianhydride used as a raw material include pyromellitic dianhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, and benzophenone-3,3 ',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenyl-3,3',4,4'-tetracarboxylic acid Anhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride) propane, 2,2-bis(3,4 -phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, etc., but not limited to these. In addition, these may be used individually or in mixture of 2 or more types.

Examples of diamines used as raw materials include p-phenylenediamine, m-phenylenediamine, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diamine -Diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4 '-Diaminodiphenyl, 3,4'-diaminodiphenyl, 3,3'-diaminodiphenyl, 4,4'-diaminobiphenyl, 3,4'-diphenyl Aminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone Benzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis( 4-Aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-amine) phenoxy) phenyl] bismuth, bis[4-(3-aminophenoxy)phenyl] bismuth, 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, bi-o-toluidine, 9,9 -Bis(4-aminophenyl) fluoride etc. Moreover, a part of hydrogen atoms on these benzene rings may be substituted. In addition, these may be used individually or in mixture of 2 or more types.

In the synthesis of the polyamic acid ester (A), the following method can be preferably used: the tetracarboxylic acid diester obtained by performing the esterification reaction of the following tetracarboxylic dianhydride is directly subjected to condensation with diamine. reaction.

The alcohol used for the esterification reaction of the said tetracarboxylic dianhydride is the alcohol which has an olefinic double bond. Specific examples thereof include, but are not limited to, 2-hydroxyethyl methacrylate, 2-methacryloyloxyethanol, glycerin diacrylate, and glycerol dimethacrylate. These alcohols may be used alone or in combination of two or more.

As for the specific synthesis method of the polyamic acid ester (A) used in this embodiment, a conventionally known method can be adopted. As a synthesis method, the method shown in the specification of International Publication No. 00/43439 can be mentioned, for example. That is, a method of temporarily converting a tetracarboxylic acid diester into a tetracarboxylic acid diester diacid chloride, and subjecting the tetracarboxylic acid diester diacid chloride and a diamine to condensation in the presence of a basic compound can be used. The reaction is carried out to produce a polyamic acid ester (A). Moreover, the method of producing a polyamic acid ester (A) by the method of subjecting a tetracarboxylic-acid diester and a diamine to a condensation reaction in presence of an organic dehydrating agent is mentioned.

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

The weight average molecular weight of the polyamic acid ester (A) used in the present embodiment is preferably 6,000 to 150,000, more preferably 7,000 to 50,000, and more preferably 7,000 to 20,000.

、2-甲基-9-氧硫𠮿

、2-異丙基-9-氧硫𠮿

及二乙基-9-氧硫𠮿

等9-氧硫𠮿

衍生物、苯偶醯、苯偶醯二甲基縮酮及苯偶醯-β-甲氧基乙基縮醛等苯偶醯衍生物、安息香甲醚等安息香衍生物、2,6-二(4'-二疊氮苯亞甲基)-4-甲基環己酮及2,6'-二(4'-二疊氮苯亞甲基)環己酮等疊氮類、1-苯基-1,2-丁二酮-2-(O-甲氧基羰基)肟、1-苯基丙二酮-2-(O-甲氧基羰基)肟、1-苯基丙二酮-2-(O-乙氧基羰基)肟、1-苯基丙二酮-2-(O-苯甲醯基)肟、1,3-二苯基丙三酮-2-(O-乙氧基羰基)肟、1-苯基-3-乙氧基丙三酮-2-(O-苯甲醯基)肟等肟類、N-苯基甘胺酸等N-芳基甘胺酸類、過氧化苯甲醯等過氧化物類、芳香族聯咪唑類、以及二茂鈦類等。該等之中，就光敏度之方面而言，較佳為上述肟類。 (B1) Photoinitiator When the resin composition used for formation of the interlayer insulating film 6 is a negative-type photosensitive resin, a photoinitiator is added. As the photoinitiator, for example, dibenzophenone, methyl o-benzoic acid benzoate, 4-benzyl-4'-methylbenzophenone, dibenzyl ketone, and fenone can be used. Acetophenone derivatives, acetophenone derivatives such as 2,2'-diethoxyacetophenone and 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, 9-oxythiophenone

, 2-methyl-9-oxothio

, 2-isopropyl-9-oxothio

and diethyl-9-oxothioate

Wait for 9-oxysulfur 𠮿

Derivatives, benzil derivatives such as benzil, benzil dimethyl ketal and benzil-β-methoxyethyl acetal, benzoin derivatives such as benzoin methyl ether, 2,6-bis( Azides such as 4'-diazidebenzylidene)-4-methylcyclohexanone and 2,6'-bis(4'-diazidebenzylidene)cyclohexanone, 1-phenyl -1,2-Butanedione-2-(O-methoxycarbonyl)oxime, 1-phenylpropanedione-2-(O-methoxycarbonyl)oxime, 1-phenylpropanedione-2 -(O-ethoxycarbonyl) oxime, 1-phenylpropanedione-2-(O-benzyl) oxime, 1,3-diphenylglycerol-2-(O-ethoxy Carbonyl) oximes, oximes such as 1-phenyl-3-ethoxyglycerol-2-(O-benzyl) oxime, N-arylglycines such as N-phenylglycine, Peroxides such as benzyl oxide, aromatic biimidazoles, and titanocenes, etc. Among them, the above-mentioned oximes are preferred in terms of photosensitivity.

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

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

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

<How to adjust the weight reduction rate> If an inorganic filler is added to the resin composition used for formation of the interlayer insulating film 6, the weight reduction rate can be adjusted. As the inorganic filler, the above-mentioned fillers can be used. <How to adjust the amount of volatilized gas> If a thermal crosslinking agent or a volatilization modifier is added to the resin composition used for the formation of the interlayer insulating film 6 , the amount of volatilized gas when kept at 100° C. for 60 minutes can be adjusted. As the thermal cross-linking agent, the polymer forming the interlayer insulating film 6 reacts with the thermal cross-linking agent to cross-link, or the thermal cross-linking agent is cross-linked with each other. The thermal cross-linking agent is not limited. A compound of a functional group above the functional group (epoxy group, methacryloyl group, acryl group, etc.).

The volatilization modifier is not limited as long as the volatilization temperature and the volatilization pressure can be adjusted. Among them, polyethylene glycol, polypropylene glycol, etc. are exemplified from the viewpoint of having a site capable of hydrogen bonding with the polar functional group of the polymer and having no adverse effect during development.

By using these compounds in combination in an appropriate amount, the amount of volatile gas can be appropriately adjusted.

As a polymer which can be preferably combined with the above-mentioned thermal crosslinking agent or volatilization regulator, for example, a polyimide precursor, a polybenzoxazole precursor, or a polymer having a phenolic hydroxyl group can be mentioned.

(D) Solvent There is no particular limitation as long as it is a solvent in which each component can be dissolved or dispersed. For example, N-methyl-2-pyrrolidone, γ-butyrolactone, acetone, methyl ethyl ketone, dimethyl sulfoxide, etc. are mentioned. These solvents can be used within a range of 30 to 1500 parts by mass with respect to 100 parts by mass of the (A) photosensitive resin, depending on the coating film thickness and viscosity.

(E) Other A crosslinking agent may be included in the polyimide precursor composition. As the cross-linking agent, a cross-linking agent that can cross-link the (A) photosensitive resin when the polyimide precursor composition is exposed to light and heat-hardened after development, or the cross-linking agent itself can form a cross-linked network structure the crosslinking agent. By using a crosslinking agent, the heat resistance and chemical resistance of the cured film (interlayer insulating film) can be further strengthened.

In addition, a sensitizer for enhancing photosensitivity, an adhesive adjuvant for enhancing adhesion to a substrate, and the like may be contained.

(development) After exposing the polyimide precursor composition to light, the unneeded portion is rinsed with a developer. The developer to be used is not particularly limited, and in the case of a polyimide precursor composition for development with a solvent, N,N-dimethylformamide, dimethylsulfoxide, N ,N-dimethylacetamide, N-methyl-2-pyrrolidone, cyclopentanone, γ-butyrolactone, acetates and other good solvents, these good solvents and lower alcohols, water, aromatic Mixed solvents of poor solvents such as hydrocarbons, etc. After development, rinse with a poor solvent or the like as necessary.

In the case of a polyimide precursor composition developed with an alkaline aqueous solution, it is preferably an aqueous solution of tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, carbonic acid Sodium, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine, ethylene glycol Aqueous solutions of compounds showing basicity such as amine and hexamethylenediamine.

(heat hardening) After development, the polyimide precursor is ring-closed by heating to form polyimide. This polyimide becomes the hardened relief pattern, that is, the interlayer insulating film 6 .

The heating temperature is not particularly limited, but generally, the lower the heat curing temperature, the smaller the refractive index difference tends to be. From the viewpoint of showing less than 0.0150, which is the refractive index difference of the present embodiment, it is preferably 200°C or lower, preferably 180°C or lower, and more preferably 160°C or lower.

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

[Chemical 40]

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

In the case of alkali-soluble polyimide, the terminal of the polyimide can be made into a hydroxyl group.

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

(通式(14)中，Y ²與Y ³為2價有機基) [Chemical 41]

(In the general formula (14), Y ² and Y ³ are divalent organic groups)

From the viewpoint of the adhesion between the interlayer insulating film 6 and the sealing material 3, Y ² 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 may be substituted with a halogen atom), particularly preferably a chain alkylene having 1 to 8 carbon atoms and a hydrogen atom substituted with a fluorine atom.

In addition, from the viewpoint of the adhesion between the interlayer insulating film 6 and the sealing material 3, Y ³ preferably contains a divalent organic group containing an aromatic group, and more preferably contains the following general formulas (6) to (8) A divalent organic group representing at least one structure.

(R ₁₀、R ₁₁、R ₁₂及R ₁₃為氫原子、碳數1～5之1價脂肪族基，可相同亦可不同) [Chemical 42]

(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～R ₂₁為氫原子、鹵素原子、碳數1～5之1價有機基，相互可不同，亦可相同) [Chemical 43]

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

(R ₂₂為2價基，R ₂₃～R ₃₀為氫原子、鹵素原子、碳數1～5之1價脂肪族基，可相同亦可不同) [Chemical 44]

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

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

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

[Chemical 45]

From the viewpoint of the adhesion between the interlayer insulating film 6 and the sealing material 3, Y ³ 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, Particularly preferred is a divalent chain aliphatic group having 1 to 20 carbon atoms.

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

Dichloride derivatives can be synthesized by reacting a halogenating agent with a dicarboxylic acid derivative. As the halogenating agent, thionyl chloride, phosphonium chloride, phosphorus oxychloride, phosphorus pentachloride and the like used in the chlorination reaction of common carboxylic acids can be used.

As a method of synthesizing a dichloride derivative, a method of reacting a dicarboxylic acid derivative with the above-mentioned halogenating agent in a solvent, a method of reacting with an excess halogenating agent, and then distilling off the excess part can be used. synthesis.

As the dicarboxylic acid used for the dicarboxylic acid derivative, for example, isophthalic acid, terephthalic acid, 2,2-bis(4-carboxyphenyl)-1,1,1,3,3, 3-Hexafluoropropane, 4,4'-dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxytetraphenylsilane, bis(4-carboxyphenyl) bismuth, 2 ,2-bis(p-carboxyphenyl)propane, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6 - Naphthalene dicarboxylic acid, malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, 2-methylglutaric acid, 3- Methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoroadipic acid , 3-methyladipic acid, octafluoroadipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorooctanedioic acid, azelaic acid, decane Diacid, hexadecanedioic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid Alkanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, eicosanedioic acid, docosanedioic acid, tetracosanedioic acid, tetracosanedioic acid, Pentacosanedioic acid, Hexadecanedioic acid, Heptacosanedioic acid, Hecosanedioic acid, Hecosanedioic acid, Triacosanedioic acid, Triacosanedioic acid, Thirty Dioxanedioic acid, oxydiacetic acid, etc. These may be used in combination.

As the hydroxyl group-containing diamine, for example, 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl)propane, bis(4-amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)propane, bis(4-amino) -3-Hydroxyphenyl) bismuth, 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4 -amino-3-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, etc. These may be used in combination.

(B2) Photoacid generator The photoacid generator has the function of increasing the solubility of the alkaline aqueous solution of the light-irradiated part. As a photoacid generator, a naphthoquinone diazonium compound, an aryldiazonium salt, a diaryl iodonium salt, a triaryl perionium salt, etc. are mentioned. Among them, the diazonaphthoquinone compound is preferred because of its higher sensitivity.

(D) Solvent It will not be specifically limited if it is a solvent which can dissolve or disperse each component.

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

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

In the above, the description has been centered on the positive-type polybenzoxazole precursor composition, but a negative-type polybenzoxazole precursor composition may also be used.

(heat hardening) After development, the polybenzoxazole precursor is ring-closed by heating to form polybenzoxazole. This polybenzoxazole becomes the hardened relief pattern, that is, the interlayer insulating film 6 .

The heating temperature is not particularly limited, but from the viewpoint of influence on other members, the heating temperature is preferably lower. It is preferably 250 degrees or less, more preferably 230 degrees or less, more preferably 200 degrees or less, and still more preferably 180 degrees or less.

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

[Chemical 46]

Y ² and Y ³ in the general formula (10) are the same as Y ² and Y ³ in the general formula (14). Preferred Y ² and Y ³ in the general formula (14) are also preferred in the polybenzoxazole of the general formula (10) for the same reason.

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

Among them, a phenol resin is preferable, and a novolak-type phenol resin is particularly preferable in terms of low cost and small volume shrinkage at the time of hardening.

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

Examples of phenol derivatives include phenol, cresol, ethylphenol, propylphenol, butylphenol, amylphenol, benzylphenol, adamantanephenol, benzyloxyphenol, xylenol, and phthalate. Phenol, resorcinol, ethyl resorcinol, hexyl resorcinol, hydroquinone, pyrogallol, phloroglucinol, 1,2,4-trihydroxybenzene, rosin acid, Phenol, Bisphenol A, Bisphenol AF, Bisphenol B, Bisphenol F, Bisphenol S, Dihydroxydiphenylmethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,4-bis (3-hydroxyphenoxybenzene), 2,2-bis(4-hydroxy-3-methylphenyl)propane, α,α'-bis(4-hydroxyphenyl)-1,4-diisopropyl Benzene, 9,9-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2,2-bis(2-hydroxyl) -5-biphenyl) propane, dihydroxybenzoic acid, etc.

Examples of the aldehyde compound include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, pivalaldehyde, butyraldehyde, valeraldehyde, hexanal, triacetaldehyde, glyoxal, cyclohexanal, diphenylacetaldehyde, Ethyl butyraldehyde, benzaldehyde, glyoxylic acid, 5-nor alkene-2-carbaldehyde, malondialdehyde, succinaldehyde, glutaraldehyde, salialdehyde, naphthalene formaldehyde, terephthalaldehyde, etc.

The component (A) preferably contains (a) a phenol resin not having an unsaturated hydrocarbon group and (b) a modified phenol resin having an unsaturated hydrocarbon group. It is more preferable that the said (b) component is modified|denatured by the reaction of a phenolic hydroxyl group and a polybasic acid anhydride.

In addition, as the component (b), it is preferable to use a compound having an unsaturated hydrocarbon group having 4 to 100 carbon atoms to further improve the mechanical properties (elongation at break, elastic modulus and residual stress). Sexual phenolic resin.

(b) Modified phenol resins having unsaturated hydrocarbon groups are usually phenol or derivatives thereof and compounds having unsaturated hydrocarbon groups (preferably those having 4 to 100 carbon atoms) (hereinafter, sometimes simply referred to as "unsaturated hydrocarbon group-containing resins") A polycondensation product of a reaction product (hereinafter referred to as "unsaturated hydrocarbon group-modified phenol derivative") and an aldehyde, or a reaction product of a phenol resin and an unsaturated hydrocarbon group-containing compound.

The phenol derivative here is the same as the phenol derivative described above about the raw material of the phenol resin as the component (A).

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

Examples of the unsaturated hydrocarbon group-containing compound include unsaturated hydrocarbons having 4 to 100 carbon atoms, polybutadiene having a carboxyl group, epoxidized polybutadiene, linolenic alcohol, oleyl alcohol, unsaturated fatty acids and unsaturated fatty acids ester. Preferred unsaturated fatty acids include crotonic acid, myristic acid, palmitoleic acid, oleic acid, elaidic acid, oleic acid, codoleic acid, sinapic acid, tetracosenoic acid, and linseed oil acid, alpha-linolenic acid, eleric acid, stearidonic acid, arachidonic acid, eicosapentaenoic acid, herring acid and docosahexaenoic acid. Among them, esters of unsaturated fatty acids having 8 to 30 carbon atoms and monohydric to trihydric alcohols having 1 to 10 carbon atoms are particularly preferred, and unsaturated fatty acids having 8 to 30 carbon atoms and trihydric alcohols are particularly preferred. of glycerol esters.

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

Among the above 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 phenol resin and vegetable oil and improving yield. On the other hand, from the viewpoint of improving the adhesion, mechanical properties, and thermal shock resistance of the photoresist pattern, it is preferable to use a drying oil. Among the drying oils, tung oil, linseed oil, soybean oil, walnut oil, and safflower oil are preferable, and tung oil and linseed oil are more preferable in that the effects of the present invention can be more effectively and surely exhibited.

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

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

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

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

The above-mentioned reaction is usually preferably carried out at a reaction temperature of 100 to 120°C. In addition, the reaction time varies depending on the type and amount of the catalyst used, but is usually 1 to 50 hours. After the reaction is completed, the reaction product is dehydrated under reduced pressure at a temperature below 200° C., thereby obtaining a phenolic resin modified with an unsaturated hydrocarbon group-containing compound. In addition, solvents, such as toluene, xylene, and methanol, can be used for the reaction.

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

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

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

The reaction of the phenol resin with the unsaturated hydrocarbon group-containing compound is usually preferably carried out at 50 to 130°C. Moreover, regarding the reaction ratio of the phenol resin and the unsaturated hydrocarbon group-containing compound, from the viewpoint of improving the flexibility of the cured film (resist pattern), the unsaturated hydrocarbon group-containing compound is preferable with respect to 100 parts by mass of the phenol resin. It is 1-100 mass parts, More preferably, it is 2-70 mass parts, More preferably, it is 5-50 mass parts. When the amount of the unsaturated hydrocarbon group-containing compound is less than 1 part by mass, the flexibility of the cured film tends to decrease, and when it exceeds 100 parts by mass, the possibility of gelation during the reaction tends to increase, and the Tendency to decrease heat resistance. At this time, p-toluenesulfonic acid, trifluoromethanesulfonic acid, or the like can be used as a catalyst as needed. In addition, solvents, such as toluene, xylene, methanol, and tetrahydrofuran, can be used for the reaction.

Furthermore, the polybasic acid anhydride is reacted with the phenolic hydroxyl group remaining in the phenolic resin modified with the unsaturated hydrocarbon group-containing compound produced by the above method. Thereby, the acid-modified phenol resin can also be used as (b) component. By carrying out acid modification with a polybasic acid anhydride and introducing a carboxyl group, the solubility of the component (b) in an alkaline aqueous solution (developing solution) is further improved.

The polybasic acid anhydride is not particularly limited as long as it has an acid anhydride group formed by dehydration condensation of the carboxyl group of a polybasic acid having a plurality of carboxyl groups. Examples of polybasic acid anhydrides include phthalic anhydride, succinic anhydride, octenyl succinic anhydride, pentadecenyl succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, Hydrogen phthalic anhydride, methyl tetrahydro phthalic anhydride, methyl hexahydro phthalic anhydride, terrestrial anhydride, 3,6-endomethylene tetrahydro phthalic anhydride, methyl endo Dibasic acid anhydrides such as methylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride and trimellitic anhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, diphenyl ether tetracarboxylic acid Aromatic tetrabasic acid dianhydrides such as anhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, pyromellitic dianhydride, and benzophenone tetracarboxylic dianhydride. These can be used alone or in combination of two or more. Among these, the polybasic acid anhydride is preferably a dibasic acid anhydride, 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 a photoresist pattern having a better shape can be formed.

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

As said polybasic acid anhydride, for example, phthalic anhydride, succinic anhydride, octenyl succinic anhydride, pentadecenyl succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, Hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, terresin, 3,6-endomethylenetetrahydrophthalic anhydride, methyl Dibasic acid anhydrides such as endomethylene tetrahydrophthalic anhydride, tetrabromophthalic anhydride, trimellitic anhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, diphenyl ether tetracarboxylic acid Aliphatic and aromatic tetrabasic acid dianhydrides such as dianhydrides, butane tetracarboxylic dianhydrides, cyclopentane tetracarboxylic dianhydrides, pyromellitic dianhydrides, benzophenone tetracarboxylic dianhydrides, and the like. These can be used alone or in combination of two or more. Among these, the polybasic acid anhydride is preferably a dibasic acid anhydride, for example, more preferably one or more selected from the group consisting of tetrahydrophthalic anhydride, succinic anhydride, and hexahydrophthalic anhydride.

(B2) Photoacid generator As a photoacid generator, a naphthoquinone diazonium compound, an aryldiazonium salt, a diaryl iodonium salt, a triaryl perionium salt, etc. are mentioned. Among them, the nitrogen naphthoquinone compound is preferred because of its higher sensitivity.

As the thermal crosslinking accelerator, for example, epoxy compounds, oxetane compounds, oxazoline compounds, aldehydes, aldehyde-modified compounds, isocyanate compounds, unsaturated bond-containing compounds, polyol compounds, polyol compounds can be preferably used. Amine compounds, melamine compounds, metal chelating agents, C-methylol compounds, N-methylol compounds, and the like.

(D) Solvent It will not be specifically limited if it is a solvent which can dissolve or disperse each component.

(E) Other A thermal crosslinking agent, a sensitizer, an adjuvant, a dye, a surfactant, a dissolution accelerator, a crosslinking accelerator, etc. may be contained. However, when the photosensitive resin film after pattern formation is heat-hardened by containing a thermal crosslinking agent, a thermal crosslinking agent component and (A) component react to form a crosslinked structure. Thereby, it can be hardened at low temperature, and the embrittlement of a film or the melting of a film can be prevented. As the thermal crosslinking agent component, specifically, a compound having a phenolic hydroxyl group, a compound having a methylolamine group, and a compound having an epoxy group can be preferably used.

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

(heat hardening) After the development, the polymers having phenolic hydroxyl groups are thermally cross-linked by heating. The cross-linked polymer becomes a hardened relief pattern, that is, the interlayer insulating film 6 .

The heating temperature is not particularly limited, but from the viewpoint of influence on other members, the heating temperature is preferably lower. It is preferably 250 degrees or less, more preferably 230 degrees or less, more preferably 200 degrees or less, and still more preferably 180 degrees or less.

(Manufacturing method of semiconductor device) The manufacturing method of the semiconductor device of this embodiment is demonstrated using FIG. 3. FIG. In FIG. 3A, the wafer 10 after the previous steps are prepared. In addition, in FIG. 3B , the wafer 10 after the previous step is diced to form a plurality of semiconductor chips 2 . The semiconductor wafer 2 may also be a purchased item. The semiconductor wafer 2 thus prepared is attached to the support 11 at predetermined intervals as shown in FIG. 3C .

Next, the molding resin 12 is applied all over the semiconductor wafer 2 to the support 11, and molding sealing is performed as shown in FIG. 3D. Next, the support body 11 is peeled off, and the mold resin 12 is turned over (see FIG. 3E ). As shown in FIG. 3E , the semiconductor wafer 2 and the molding resin 12 are present on substantially the same plane. Then, in the step shown in FIG. 3F , the photosensitive resin composition 13 is coated on the semiconductor wafer 2 and the molding resin 12 . At this time, the photosensitive resin composition 13 is preferably adjusted with a filler. Then, the applied photosensitive resin composition 13 is exposed and developed to form a relief pattern (relief pattern forming step). In addition, the photosensitive resin composition 13 may be either positive type or negative type. Furthermore, the relief pattern is heated to form a hardened relief pattern (interlayer insulating film forming step). Furthermore, wiring is formed in the site|part where the hardened relief pattern is not formed (wiring formation process).

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

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

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

In this embodiment, the weight reduction rate of the hardened relief pattern (interlayer insulating film) formed through the above steps may be 5 to 95% by weight. In another aspect of this embodiment, the volatile gas per 1 cm ² of the hardened relief pattern (interlayer insulating film) formed by the above steps may be 0.2×10 ^-6 to 2.5 when kept at 100° C. for 60 minutes. ×10 ^-6 Pa. In yet another form of this embodiment, the volatile gas per 1 cm ² of the hardened relief pattern (interlayer insulating film) formed by the above steps may be 0.4×10 ^-6 to 1.8 when kept at 100° C. for 60 minutes. ×10 ^-6 Pa.

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

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

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

(Polymer A-1: Synthesis of Polyimide Precursor) 4,4'-Oxydiphthalic dianhydride (ODPA) as a tetracarboxylic dianhydride was added to a 2-liter separable flask. Furthermore, 2-hydroxyethyl methacrylate (HEMA) and γ-butyrolactone were added and stirred at room temperature, and pyridine was added while stirring to obtain a reaction mixture. After the heat generation caused by the reaction was completed, it was cooled to room temperature and left to stand 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. Then, it added over 60 minutes, stirring and suspending the 4,4'- diamine diphenyl ether (DADPE) which is a diamine in (gamma)-butyrolactone. Furthermore, after stirring at room temperature for 2 hours, ethanol was added and stirred for 1 hour, and then γ-butyrolactone was added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution.

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

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

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

(Synthesis of Polymer B-2) A polybenzoxazole precursor (polymer B-2) was obtained by reacting in the same manner as the method described in the above-mentioned polymer B-1 except that the dicarboxylic acid was changed as shown in Table 1 below.

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

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

(Synthesis of polymer C-2) 100 g of the following C1 resin was prepared 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'-bisdimethyl-4,4'-diaminobiphenyl (m-TB) 98.5 polymer 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 Cresol Novolak Resin (E) Mass of E (g) Modified Phenolic Resin (F) Mass of F (g) Phenolic resin Polymer C-1 C1 resin 85 C2 resin 15 Polymer C-2 C1 resin 100 C2 resin 0

[Examples 1 to 7, Comparative Examples 1 to 2] It prepared as shown in following Table 2, and obtained the solution of the photosensitive resin composition.

That is, each of the photosensitive resin compositions of Examples 1 to 7 and Comparative Examples 1 to 2 was prepared by using the compounds described in Table 2 below and the compounding amounts described in Table 3 below. In addition, the unit of Table 3 is mass part.

The produced photosensitive resin composition was subjected to (1) measurement of the weight reduction rate in an air environment, and (2) an adhesion test with a sealing material. In addition, (3) the electrical characteristics after the antenna-type module was fabricated were evaluated. The results of each test are shown in Table 3 below.

(1) Measurement of weight loss rate Using the photosensitive resin compositions prepared in Examples and Comparative Examples, a fan-out type wafer-level chip-scale package type semiconductor device was produced. The self-fabricated semiconductor device is taken out as complete as possible with a thickness of 10 μm of the interlayer insulating film. About 10 mg of the interlayer insulating film taken out was put into a platinum pan, and the weight reduction rate after the temperature was raised to 700° C. at a heating rate of 10° C./min under an air flow rate of 50 ml/min was measured.

(2) Adhesion test with sealing material R4000 series manufactured by Nagase ChemteX was prepared as an epoxy-based sealing material. Next, the sealing material was spin-coated on the silicon wafer of aluminum sputtering so that the thickness would be about 150 μm, and thermal curing was performed at 130° C. to harden the epoxy-based sealing material. The photosensitive resin composition produced in the Example and the comparative example was apply|coated on the said epoxy-type cured film so that a final film thickness might become 10 micrometers. The coated photosensitive resin composition was exposed to the entire surface under the exposure conditions of 200 mJ/cm ² in Examples 1 to 5, and 500 mJ/cm ² in Examples 6 and 7 and Comparative Examples 1 and 2. , at 230 ℃ for 2 hours for thermal curing, to produce a first layer of cured film with a thickness of 10 microns.

The photosensitive resin composition used for the formation of the cured film of the first layer was applied on the cured film of the first layer, and the entire surface was exposed under the same conditions as in the preparation of the cured film of the first layer. Thermal curing to produce a second layer of cured film with a thickness of 10 microns.

Using a mesh belt continuous calcining furnace (manufactured by Koyo Thermo Systems, model name 6841-20AMC-36), under simulated reflow conditions, the test piece after the formation of the cured film of the second layer was heated to The peak temperature is 260℃. The so-called simulated reflow conditions refer to the reflow conditions described in IPC/JEDEC J-STD-020A, Item 7.6, which is the standard specification of the American semiconductor industry group related to the evaluation method of semiconductor devices. It is normalized by assuming a high temperature of 220°C.

Pins were erected on the photosensitive resin cured films of the samples before reflow and after reflow produced above, and an adhesion test was performed using a pull tester (manufactured by Quad Group, SEBASTIAN 5 type). Evaluation: Adhesion strength 70 MPa or more・・・Adhesion ◎ 50 MPa or more - less than 70 MPa・・・Adhesion ○ 30 MPa or more - less than 50 MPa・・・Adhesion △ Less than 30 MPa・・・Adhesion ×

(3) Evaluation of antenna-integrated modules (electrical characteristics) Using the photosensitive resin compositions prepared in Examples and Comparative Examples, an antenna-integrated module in which a fan-out wafer-level chip-scale packaged semiconductor device and an antenna were integrated was fabricated. The photosensitive resin compositions prepared in Examples and Comparative Examples were used as interlayer insulating films for semiconductor devices. In addition, the photosensitive resin compositions produced in Examples and Comparative Examples were also used as an insulating member between an antenna and a ground (reference potential). The thickness of the insulating member affects the radiation rate of the antenna, so it is set to the thickness that can obtain the maximum radiation effect.

Also, the antenna-integrated module is designed to operate at 300 GHz.

The reflection characteristics (electrical characteristics) were evaluated, and the deviation from 300 GHz of the antenna alone was less than 5 GHz as ○, 5 GHz or more and less than 10 GHz as △, and 10 GHz or more as ×. In addition, those with visible ripples were set as ×, and those with no visible ripples were set as ○. Furthermore, the so-called reflection characteristic here refers to the ratio of the electric power reflected by the antenna and returned to the input port to the input power of the input port opposite to the input power to the antenna.

光酸產生劑 D-2

交聯劑 E-1

填料 F-1 氧化矽填料(Admatechs公司製造，粒徑100 nm) 溶劑 G-1 γ-丁內酯 G-2 二甲基亞碸 G-3 丙二醇單甲醚乙酸酯 G-4 乳酸乙酯 [Table 2] photoinitiator D-1

photoacid generator D-2

cross-linking agent E-1

filler F-1 Silica filler (manufactured by Admatechs, particle size 100 nm) solvent G-1 gamma-butyrolactone G-2 dimethyl sulfoxide G-3 Propylene Glycol Monomethyl Ether Acetate G-4 Ethyl lactate

[table 3] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Comparative Example 1 Comparative Example 2 polymer A-1 100 100 A-2 100 B-1 100 B-2 100 B-3 C-1 100 100 100 C-2 100 photoinitiator D-1 2 2 2 photoacid generator D-2 10 10 15 15 15 15 cross-linking agent E-1 15 15 15 15 filler F-1 200 300 200 200 200 200 200 1 3000 solvent G-1 160 160 160 225 225 G-2 40 40 40 G-3 25 25 G-4 120 120 hardening temperature 230℃ 230℃ 230℃ 230℃ 230℃ 230℃ 230℃ 230℃ 230℃ Weight loss rate 33% 25% 33% 35% 35% 39% 39% 99% 4% Adhesion (before reflow) ◎ ◎ 〇 〇 〇 △ △ △ × Adhesion (after reflow) 〇 ◎ 〇 △ △ △ △ × × Electrical characteristics △ 〇 △ △ △ △ △ × △ Ripple 〇 〇 〇 〇 〇 〇 〇 △ ×

[Examples 8 to 14, Comparative Example 3] It prepared as shown in following Table 4, and obtained the solution of the photosensitive resin composition.

That is, each of the photosensitive resin compositions of Examples 8 to 14 and Comparative Example 3 was prepared by using the compounds described in Table 4 below and in the compounding amounts described in Table 5 below. In addition, the unit of Table 5 is mass part.

The produced photosensitive resin composition was subjected to (1) volatile gas measurement at 100° C. for 60 minutes, and (2) an adhesion test with an inorganic film. In addition, (3) the electrical characteristics after the antenna-type module was fabricated were evaluated. The results of each test are shown in Table 5 below.

(1) Measurement of volatile gas at 100° C. for 60 minutes Using the photosensitive resin compositions prepared in Examples and Comparative Examples, a fan-out type wafer-level chip-scale package type semiconductor device was produced. The self-fabricated semiconductor device is taken out as complete as possible with a thickness of 10 μm of the interlayer insulating film. The taken out interlayer insulating film was cut out to a size of 1 cm ² , and the measurement was performed using a temperature-increasing desorption measuring apparatus (manufactured by Electronic Science Co., Ltd., EMD-WA1000S). After the temperature was raised to 100°C at a temperature increase rate of 10°C/min, the pressure after holding at 100°C for 60 minutes was used as the volatile gas pressure.

(2) Adhesion Test with Inorganic Film The photosensitive resin compositions prepared in Examples and Comparative Examples were applied on a silicon wafer so that the final film thickness would be 10 μm. For the coated photosensitive resin composition, under the exposure conditions of 200 mJ/cm ² in Examples 8 to 12, and 500 mJ/cm ² in Examples 13, 14 and Comparative Example 3, the entire surface was exposed to light. Thermal curing was performed at 230° C. for 2 hours to produce a cured film with a thickness of 10 μm.

Using a sputtering apparatus (L-440S-FHL manufactured by CANON ANELVA), a titanium layer of 2000 Å was sputtered on the obtained cured film, and then a copper layer of 4000 Å was sputtered.

A pin was erected on the photosensitive resin cured film of the sample prepared above, and the adhesion test was performed using a pull tester (manufactured by Quad Group, SEBASTIAN 5 type). Evaluation: Adhesion strength 70 MPa or more・・・Adhesion ◎ 50 MPa or more - less than 70 MPa・・・Adhesion ○ 30 MPa or more - less than 50 MPa・・・Adhesion △ Less than 30 MPa・・・Adhesion ×

(3) Evaluation of antenna-integrated modules (electrical characteristics) Using the photosensitive resin compositions prepared in Examples and Comparative Examples, an antenna-integrated module in which a fan-out wafer-level chip-scale packaged semiconductor device and an antenna were integrated was fabricated. The photosensitive resin compositions prepared in Examples and Comparative Examples were used as interlayer insulating films for semiconductor devices. In addition, the photosensitive resin compositions produced in Examples and Comparative Examples were also used as an insulating member between the antenna and the ground (reference potential). The thickness of the insulating member affects the radiation rate of the antenna, so it is set to the thickness that can obtain the maximum radiation effect.

Also, the antenna-integrated module is designed to operate at 300 GHz.

The reflection characteristics (electrical characteristics) were evaluated, and the deviation from 300 GHz of the antenna alone was less than 5 GHz as ○, 5 GHz or more and less than 10 GHz as △, and 10 GHz or more as ×. Furthermore, the so-called reflection characteristic here refers to the ratio of the electric power reflected by the antenna and returned to the input port to the input power of the input port opposite to the input power to the antenna.

光酸產生劑 D-2

交聯劑 E-1

熱交聯劑、揮發調整劑 H-1 二季戊四醇四丙烯酸酯 H-2 異氰尿酸三縮水甘油酯 H-3 聚乙二醇900 溶劑 G-1 γ-丁內酯 G-2 二甲基亞碸 G-3 丙二醇單甲醚乙酸酯 G-4 乳酸乙酯 [Table 4] photoinitiator D-1

photoacid generator D-2

cross-linking agent E-1

Thermal crosslinking agent, volatilization regulator H-1 dipentaerythritol tetraacrylate H-2 Triglycidyl isocyanurate H-3 polyethylene glycol 900 solvent G-1 gamma-butyrolactone G-2 dimethyl sulfoxide G-3 Propylene Glycol Monomethyl Ether Acetate G-4 Ethyl lactate

[table 5] Example 8 Example 9 Example 10 Example 11 Example 12 Example 13 Example 14 Comparative Example 3 polymer A-1 100 100 A-2 100 B-1 100 B-2 100 B-3 C-1 100 100 C-2 100 photoinitiator D-1 2 2 2 photoacid generator D-2 10 10 15 15 15 cross-linking agent E-1 15 15 15 Thermal crosslinking agent, volatilization regulator H-1 10 10 10 H-2 10 10 5 5 H-3 15 solvent G-1 160 160 160 225 225 G-2 40 40 40 G-3 25 25 G-4 120 120 120 hardening temperature 230℃ 230℃ 230℃ 230℃ 230℃ 230℃ 230℃ 230℃ Volatile gas pressure (Pa) 0.8× ^10-6 0.7× ^10-6 0.8× ^10-6 1× ^10-6 1.2× ^10-6 1.4× ^10-6 1.4× ^10-6 3× ^10-6 tightness ◎ ◎ 〇 〇 〇 △ △ × Electrical characteristics △ 〇 △ △ △ △ △ ×

Using the photosensitive resin compositions described in Examples 1 to 14, a fan-out type wafer-level chip-scale package type semiconductor device containing an epoxy resin in a mold resin can be operated without problems. [Industrial Availability]

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

1: Semiconductor device 2: Semiconductor wafer 2a: Terminal 3: Sealing material 4: Rewiring layer 5: Wiring 6: Interlayer insulating film 7: External connection terminal 10: Wafer 11: Support body 12: Molding resin 13: Photosensitive resin composition 21: Solder Balls 22: Solder bumps 23: Sealing resin 24: Intermediary layer

FIG. 1 is a schematic cross-sectional view of the semiconductor device of the present embodiment. FIG. 2 is a schematic plan view of the semiconductor device of the present embodiment. 3A to 3H are examples of manufacturing steps of the semiconductor device of the present embodiment. FIG. 4 is a comparison diagram of a flip chip BGA (Ball Grid Array, ball grid array) and a fan-out (Fan-Out) type WLCSP.

1: Semiconductor device

2: Semiconductor wafer

2a: Terminal

3: Sealing material

4: Rewiring layer

5: Wiring

6: Interlayer insulating film

7: External connection terminal

Claims (38)

A semiconductor device comprising a semiconductor wafer, a sealing material covering the semiconductor wafer, and a rewiring layer having an area larger than the semiconductor wafer in plan view, and an interlayer insulating film between the rewiring layers is maintained at 100° C. for 60 minutes The volatilized gas is 0.2×10 ^-6 to 2.5×10 ^-6 Pa per 1 cm ² . A semiconductor device comprising a semiconductor wafer, a sealing material covering the semiconductor wafer, and a rewiring layer having an area larger than the semiconductor wafer in plan view, and an interlayer insulating film between the rewiring layers is maintained at 100° C. for 60 minutes The volatilized gas is 0.4×10 ^-6 to 1.8×10 ^-6 Pa per 1 cm ² . The semiconductor device according to claim 1 or 2, wherein the sealing material and the interlayer insulating film are in direct contact with each other. The semiconductor device according to any one of claims 1 to 3, wherein the sealing material contains an epoxy resin. The semiconductor device according to any one of claims 1 to 4, wherein the interlayer insulating film contains at least one selected from the group consisting of polyimide, polybenzoxazole, and a polymer having a phenolic hydroxyl group. The semiconductor device of claim 5, wherein the interlayer insulating film contains a polyimide having a structure of the following general formula (1);

(In the general formula (1), X ¹ is a tetravalent organic group, Y ¹ is a divalent organic group, and m is an integer of 1 or more). The semiconductor device according to claim 6, wherein X ¹ in the general formula (1) is a tetravalent organic group containing an aromatic ring, and Y ¹ in the general formula (1) is a divalent organic group containing an aromatic ring . The semiconductor device according to claim 6 or 7, wherein X ¹ in the above general formula (1) contains at least one structure represented by the following general formula (2) to general formula (4);

[hua 3]

[hua 4]

(In the general formula (4), R ₉ is an oxygen atom, a sulfur atom or a divalent organic group). The semiconductor device according to claim 8, wherein X ¹ in the above general formula (1) contains a structure represented by the following general formula (5);

. The semiconductor device according to any one of claims 6 to 9, wherein Y ¹ in the general formula (1) contains at least one structure represented by the following general formulas (6) to (8);

(R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are a hydrogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group, which may be the same or different) [Chemical 7]

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

(R ₂₂ is a divalent group, and 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, which may be the same or different). The semiconductor device according to claim 10, wherein Y ¹ in the above general formula (1) contains a structure represented by the following general formula (9);

. The semiconductor device according to claim 5, wherein the above-mentioned polybenzoxazole contains a polybenzoxazole having the structure of the following general formula (10); [Chemical 10]

(In the general formula (10), Y ² and Y ³ are divalent organic groups). The semiconductor device according to claim 12, wherein Y ² of the general formula (10) is a divalent organic group having 1 to 30 carbon atoms. The semiconductor device according to claim 13, wherein Y ² in the general formula (10) is a chain alkylene group having 1 to 8 carbon atoms and a part or all of hydrogen atoms are substituted with fluorine atoms. The semiconductor device according to any one of claims 12 to 14, wherein Y ³ of the above general formula (10) is a divalent organic group containing an aromatic group. The semiconductor device of claim 15, wherein Y ³ of the general formula (10) contains at least one structure represented by the following general formulas (6) to (8);

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

(R ₁₄ to R ₂₁ are a hydrogen atom, a halogen atom, and a monovalent organic group having 1 to 5 carbon atoms, which may be different from each other or the same.) [Chemical 13]

(R ₂₂ is a divalent group, and R ₂₃ to R ₃₀ are a hydrogen atom, a halogen atom, and a monovalent aliphatic group having 1 to 5 carbon atoms, which may be the same or different). The semiconductor device of claim 16, wherein Y ³ of the above general formula (10) contains a structure represented by the following general formula (9);

. The semiconductor device according to any one of claims 12 to 14, wherein Y ³ of the general formula (10) is a divalent organic group having 1 to 40 carbon atoms. The semiconductor device according to claim 18, wherein Y ³ of the general formula (10) is a divalent chain aliphatic group having 1 to 20 carbon atoms. The semiconductor device according to claim 5, wherein the polymer having a phenolic hydroxyl group contains a novolac-type phenol resin. The semiconductor device according to claim 5, wherein the polymer having a phenolic hydroxyl group contains a phenol resin not having an unsaturated hydrocarbon group and a modified phenol resin having an unsaturated hydrocarbon group. The semiconductor device according to any one of claims 1 to 21, wherein the rewiring layer includes a first interlayer insulating film layer, a second interlayer insulating film layer, a The first interlayer insulating film layer and the second interlayer insulating film layer are different, and are provided in an intermediate layer between the first interlayer insulating film layer and the second interlayer insulating film layer. The semiconductor device of claim 22, wherein the first interlayer insulating film layer is in contact with the sealing material, and the volatile gas per 1 cm ² of the first interlayer insulating film layer when kept at 100° C. for 60 minutes is 0.4× 10 ^-6 to 1.8×10 ^-6 Pa. The semiconductor device according to claim 22 or 23, wherein the second interlayer insulating film layer has a different composition from that of the first interlayer insulating film layer. The semiconductor device according to any one of claims 22 to 24, wherein the volatile gas when the second interlayer insulating film is kept at 100°C for 60 minutes and the volatile gas when the first interlayer insulating film is kept at 100°C for 60 minutes Volatile gases are different. The semiconductor device according to any one of claims 1 to 25, wherein the semiconductor device is a fan-out type wafer-level chip-scale package type semiconductor device. The semiconductor device according to any one of claims 1 to 26, wherein the volatile gas per 1 cm ² of the interlayer insulating film between the rewiring layers is 0.6×10 ⁻⁶ to 1.8×10 when kept at 100° C. for 60 minutes. ^-6 Pa. The semiconductor device of claim 27, wherein the volatile gas per 1 cm ² of the interlayer insulating film between the rewiring layers is 0.6×10 ^-6 to 1.6×10 ^-6 Pa per 100° C. for 60 minutes. The semiconductor device of claim 27, wherein the volatile gas per 1 cm ² of the interlayer insulating film between the rewiring layers is 0.6×10 ^-6 to 1.4×10 ^-6 Pa when kept at 100° C. for 60 minutes. The semiconductor device according to any one of claims 1 to 29, wherein the above-mentioned interlayer insulating film contains a thermal crosslinking agent. The semiconductor device according to any one of claims 1 to 29, wherein the interlayer insulating film contains a volatilization modifier. The semiconductor device according to any one of claims 1 to 29, wherein the interlayer insulating film contains a thermal crosslinking agent and a volatilization modifier. The semiconductor device according to any one of claims 1 to 32, wherein the rewiring layer includes an inorganic film in contact with the interlayer insulating film. The semiconductor device of claim 33, wherein the inorganic film has a reaction layer in which a volatile gas contained in the interlayer insulating film reacts with a component of the inorganic film. A method of manufacturing a semiconductor device, comprising: a step of covering a semiconductor wafer with a sealing material, and a step of forming a rewiring layer having an area larger than the semiconductor wafer in plan view and containing an interlayer insulating film, and the interlayer insulating film is heated at 100° C. The volatilized gas in 1 cm ² is 0.4×10 ^-6 to 1.8×10 ^-6 Pa when it is kept at low temperature for 60 minutes. The method for manufacturing a semiconductor device according to claim 35, comprising the step of forming an interlayer insulating film: using a photosensitive resin that can form at least one compound of polyimide, polybenzoxazole, and a polymer having a phenolic hydroxyl group The composition forms the above-mentioned interlayer insulating film. The method for manufacturing a semiconductor device according to claim 36, wherein the interlayer insulating film forming step comprises the step of: using the volatile gas when the interlayer insulating film is kept at 100° C. for 60 minutes to become 0.4×10 ⁻⁶ to 1.8×10 ⁻ The above-mentioned photosensitive resin composition adjusted by the method of ⁶ Pa forms the above-mentioned interlayer insulating film. The method for manufacturing a semiconductor device according to claim 37, wherein the step of forming the interlayer insulating film comprises the step of: using the volatile gas when the interlayer insulating film is kept at 100° C. for 60 minutes to become 0.4×10 ⁻⁶ to 1.8×10 ⁻ The above-mentioned photosensitive resin composition adjusted by a thermal crosslinking agent and/or a volatilization modifier in the form of ⁶ Pa forms the above-mentioned interlayer insulating film.

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