TWI803315B - Semiconductor device and manufacturing method thereof - Google Patents

Abstract

The present invention provides a semiconductor device having excellent adhesion between an interlayer insulating film in a rewiring layer and a sealing material, and a method for manufacturing the same. A semiconductor device (1) includes: a semiconductor chip (2), a sealing material (3) covering the semiconductor chip, and a redistribution layer (4) having an area larger than that of the semiconductor chip in plan view. The absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the rewiring layer at a wavelength of 1310 nm is 0.0150 or more. The interlayer insulating film contains at least one selected from polyimide, polybenzoxazole, and a polymer having a phenolic hydroxyl group.

Description

Semiconductor device and manufacturing method thereof

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

Various methods exist in semiconductor packaging methods in semiconductor devices. As a semiconductor packaging method, for example, there is a packaging method in which a semiconductor chip is covered with a sealing material (molding resin) to form an element sealing material, and further, a rewiring layer electrically connected to the semiconductor chip is formed. Among the semiconductor packaging methods, in recent years, the fan-out (Fan-Out) semiconductor packaging method is becoming the mainstream.

In the fan-out type semiconductor package, a chip sealing body larger than the chip size of the semiconductor chip is formed by covering the semiconductor chip with a sealing material. Furthermore, a rewiring layer reaching a region of the semiconductor chip and the sealing material is formed. The redistribution layer is formed with a relatively thin film thickness. Also, 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, the following patent document 1 is known as a fan-out type semiconductor device. [Prior Art Literature] [Patent Document]

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

[Problem to be solved by the invention]

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

This invention was made in view of this point, and it aims at providing the semiconductor device which is excellent in the adhesiveness of the interlayer insulating film in a rewiring layer, and a sealing material, and its manufacturing method. [Technical means to solve the problem]

One aspect of the semiconductor device of the present invention is characterized by comprising: a semiconductor chip, a sealing material covering the above-mentioned semiconductor chip, and a redistribution layer having an area larger than the above-mentioned semiconductor chip in plan view; The absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index at 1310 nm is 0.0150 or more.

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

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

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

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

(通式(1)中，X ¹為四價有機基，Y ¹為二價有機基，m為1以上之整數) [chemical 1]

(In general formula (1), ^X1 is a tetravalent organic group, ^Y1 is a divalent organic group, m is an integer of 1 or more)

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

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

[Chem 2]

[Chem 3]

(通式(4)中，R ₉為氧原子、硫原子、或二價有機基) [chemical 4]

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

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

[chemical 5]

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

(R ₁₀、R ₁₁、R ₁₂及R ₁₃為氫原子、碳數為1～5之一價脂肪族基或羥基，可相同亦可不同) [chemical 6]

(R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are a hydrogen atom, a valent aliphatic group with 1 to 5 carbons or a hydroxyl group, which may be the same or different)

(R ₁₄～R ₂₁為氫原子、鹵素原子、碳數為1～5之一價有機基或羥基，可相互不同亦可相同) [chemical 7]

(R ₁₄ to R ₂₁ are a hydrogen atom, a halogen atom, a valent organic group with a carbon number of 1 to 5, or a hydroxyl group, which may be different from each other or the same)

(R ₂₂為二價基，R ₂₃～R ₃₀為氫原子、鹵素原子、碳數為1～5之一價脂肪族基或羥基，可相同亦可不同) [chemical 8]

(R ₂₂ is a divalent group, R ₂₃ to R ₃₀ are a hydrogen atom, a halogen atom, a valent aliphatic group with 1 to 5 carbons or a hydroxyl group, which may be the same or different)

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

[chemical 9]

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

(通式(10)中，U與V為二價有機基) [chemical 10]

(In general formula (10), U and V are divalent organic groups)

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

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

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

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

(R ₁₀、R ₁₁、R ₁₂及R ₁₃為氫原子、碳數為1～5之一價脂肪族基，可相同亦可不同) [chemical 11]

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

(R ₁₄～R ₂₁為氫原子、鹵素原子、碳數為1～5之一價有機基，可相互不同亦可相同) [chemical 12]

(R ₁₄ to R ₂₁ are a hydrogen atom, a halogen atom, or a valent organic group with 1 to 5 carbon atoms, which may be different or the same)

(R ₂₂為二價基，R ₂₃～R ₃₀為氫原子、鹵素原子、碳數為1～5之一價脂肪族基，可相同亦可不同) [chemical 13]

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

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

[chemical 14]

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

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

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

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

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

In one aspect of the semiconductor device of the present invention, it is preferable that the first interlayer insulating film is in contact with the sealing material, and the absolute difference between the in-plane refractive index and the out-of-plane refractive index of the first interlayer insulating film is The value is 0.0150 or more.

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

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

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

In one aspect of the semiconductor device of the present invention, the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the rewiring layer is preferably 0.0155 or more.

In one aspect of the semiconductor device of the present invention, it is preferable that the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the rewiring layer is 0.0160 or more.

In one aspect of the semiconductor device of the present invention, it is preferable that the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the rewiring layer is 0.0165 or more.

In one aspect of the semiconductor device of the present invention, it is preferable that the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the rewiring layer is 0.0170 or more.

In one aspect of the semiconductor device of the present invention, it is preferable that the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the rewiring layer is 0.0200 or more.

In one aspect of the semiconductor device of the present invention, the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the rewiring layer is preferably 0.50 or less.

In one aspect of the semiconductor device of the present invention, the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the rewiring layer is preferably 0.40 or less.

In one aspect of the semiconductor device of the present invention, the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the rewiring layer is preferably 0.30 or less.

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

In one aspect of the manufacturing method of the semiconductor device of the present invention, it is preferable to include the step of forming an interlayer insulating film: using at least one of polymers capable of forming polyimide, polybenzoxazole, and phenolic hydroxyl groups. The photosensitive resin composition of the compound forms the above-mentioned interlayer insulating film.

In one aspect of the method for manufacturing a semiconductor device of the present invention, preferably, the step of forming the interlayer insulating film includes the step of setting the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film to 0.0150 In the above method, the above-mentioned interlayer insulating film is formed by using the above-mentioned photosensitive resin composition adjusted with additives.

One aspect of the semiconductor device of the present invention is characterized by comprising: a semiconductor wafer, a sealing material covering the semiconductor wafer, and a rewiring layer having an area larger than the semiconductor wafer in plan view; The etch rate during plasma treatment is above 0.05 μm/min.

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

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

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

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

(通式(1)中，X ¹為四價有機基，Y ¹為二價有機基，m為1以上之整數) [chemical 15]

(In general formula (1), ^X1 is a tetravalent organic group, ^Y1 is a divalent organic group, m is an integer of 1 or more)

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

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

[chemical 16]

[chemical 17]

(通式(4)中，R ₉為氧原子、硫原子、或二價有機基) [chemical 18]

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

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

[chemical 19]

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

(R ₁₀、R ₁₁、R ₁₂及R ₁₃為氫原子、碳數為1～5之一價脂肪族基或羥基，可相同亦可不同) [chemical 20]

(R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are a hydrogen atom, a valent aliphatic group with 1 to 5 carbons or a hydroxyl group, which may be the same or different)

(R ₁₄～R ₂₁為氫原子、鹵素原子、碳數為1～5之一價有機基或羥基，可相互不同亦可相同) [chem 21]

(R ₁₄ to R ₂₁ are a hydrogen atom, a halogen atom, a valent organic group with a carbon number of 1 to 5, or a hydroxyl group, which may be different from each other or the same)

(R ₂₂為二價基，R ₂₃～R ₃₀為氫原子、鹵素原子、碳數為1～5之一價脂肪族基或羥基，可相同亦可不同) [chem 22]

(R ₂₂ is a divalent group, R ₂₃ to R ₃₀ are a hydrogen atom, a halogen atom, a valent aliphatic group with 1 to 5 carbons or a hydroxyl group, which may be the same or different)

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

[chem 23]

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

(通式(10)中，U與V為二價有機基) [chem 24]

(In general formula (10), U and V are divalent organic groups)

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

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

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

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

(R ₁₀、R ₁₁、R ₁₂及R ₁₃為氫原子、碳數為1～5之一價脂肪族基，可相同亦可不同) [chem 25]

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

(R ₁₄～R ₂₁為氫原子、鹵素原子、碳數為1～5之一價有機基，可相互不同亦可相同) [chem 26]

(R ₁₄ to R ₂₁ are a hydrogen atom, a halogen atom, or a valent organic group with 1 to 5 carbon atoms, which may be different or the same)

(R ₂₂為二價基，R ₂₃～R ₃₀為氫原子、鹵素原子、碳數為1～5之一價脂肪族基，可相同亦可不同) [chem 27]

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

In the present invention, V in the general formula (10) includes a structure represented by the following general formula (9).

[chem 28]

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

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

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

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

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

In one aspect of the semiconductor device of the present invention, preferably, the first interlayer insulating film is in contact with the sealing material, and the etching rate of the first interlayer insulating film during oxygen plasma treatment is 0.05 μm/min. above.

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

In one aspect of the semiconductor device of the present invention, it is preferable that the etching rate of the oxygen plasma treatment of the second interlayer insulating film layer is different from the etching rate of the oxygen plasma treatment of the first interlayer insulating film layer.

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

In one aspect of the semiconductor device of the present invention, it is preferable that the etching rate of the interlayer insulating film of the rewiring layer is 0.08 μm/minute or more during the oxygen plasma treatment.

In one aspect of the semiconductor device of the present invention, it is preferable that the etching rate of the interlayer insulating film of the rewiring layer is 0.10 μm/minute or more during the oxygen plasma treatment.

In one aspect of the semiconductor device of the present invention, it is preferable that the etching rate of the interlayer insulating film of the rewiring layer is 0.15 μm/minute or more during the oxygen plasma treatment.

In one aspect of the semiconductor device of the present invention, it is preferable that the etching rate of the interlayer insulating film of the rewiring layer is 0.20 μm/minute or more during the oxygen plasma treatment.

In one aspect of the semiconductor device of the present invention, it is preferable that the etching rate of the interlayer insulating film of the rewiring layer is 0.30 μm/minute or more during the oxygen plasma treatment.

In one aspect of the semiconductor device of the present invention, it is preferable that the etching rate of the interlayer insulating film of the rewiring layer is 3.0 μm/min or less during the oxygen plasma treatment.

In one aspect of the semiconductor device of the present invention, it is preferable that the etching rate during the oxygen plasma treatment of the interlayer insulating film of the rewiring layer is 2.0 μm/min or less.

In one aspect of the semiconductor device of the present invention, it is preferable that the etching rate during the oxygen plasma treatment of the interlayer insulating film of the rewiring layer is 1.0 μm/minute or less.

An aspect of the manufacturing method of the semiconductor device of the present invention is characterized in that it includes: a step of covering the semiconductor wafer with a sealing material; and a step of forming a rewiring layer having an area larger than the semiconductor wafer in plan view and including an interlayer insulating film; and The etching rate of the above-mentioned interlayer insulating film during the oxygen plasma treatment is 0.05 μm/minute or more.

In one aspect of the manufacturing method of the semiconductor device of the present invention, it is preferable to include the step of forming an interlayer insulating film: using at least one of polymers capable of forming polyimide, polybenzoxazole, and phenolic hydroxyl groups. The photosensitive resin composition of the compound forms the above-mentioned interlayer insulating film.

In one aspect of the method for manufacturing a semiconductor device according to the present invention, it is preferable that the step of forming the interlayer insulating film includes the step of: making the etching rate of the interlayer insulating film 0.05 μm/min or higher during the oxygen plasma treatment The above-mentioned interlayer insulating film is formed by using the above-mentioned photosensitive resin composition adjusted with additives. [Effect of Invention]

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

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

(semiconductor device) FIG. 1 is a schematic cross-sectional view of a semiconductor device according to this embodiment. As shown in FIG. 1, a semiconductor device (semiconductor IC (Integrated Circuit, integrated circuit)) 1 is composed of a semiconductor chip 2, a sealing material (molding resin) 3 covering the semiconductor chip 2, and a semiconductor chip 2 and the redistribution layer 4 in close contact with the sealing material 3 .

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

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

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

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

Here, the "rewiring layer 4" in this embodiment is a thin film layer having the wiring 5 and the interlayer insulating film 6 as described above, and does not contain an interposer or a printed wiring board. Figure 4 is a comparison diagram between flip-chip BGA and fan-out (Fan-Out) WLCSP. The semiconductor device (semiconductor IC) 1 (refer to FIG. 1 ) uses the rewiring layer 4, so 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. In addition, 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 from above (observed in the direction of arrow A), it is as shown in FIG. 2 below. FIG. 2 is a schematic top view of the semiconductor device of the present embodiment. In addition, the sealing material 3 is omitted.

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

Also, the semiconductor chip 2 and the rewiring layer 4 may have the same or different shapes. In FIG. 2 , the shapes of the semiconductor chip 2 and the redistribution layer 4 may both be rectangular or other shapes.

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

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

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

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

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

(interlayer insulating film) The first aspect of this embodiment is characterized in that the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film 6 is 0.0150 or more. Here, the so-called in-plane refractive index is the average value of the refractive index in the x-direction and y-direction of the interlayer insulating film 6 with thickness z, width x, and length y at a wavelength of 1310 nm. The so-called out-of-plane refractive index is the refractive index in the z direction at a wavelength of 1310 nm. Hereinafter, the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index at a wavelength of 1310 nm is referred to as a refractive index difference.

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

When the refractive index difference is 0.0150 or more, the adhesion between the interlayer insulating film 6 and the sealing material 3 after chemical treatment is excellent. Although the reason is not certain, the inventors of the present invention presume as follows.

In the manufacturing process of the fan-out semiconductor device 1 (see FIG. 1 ), in order to form the rewiring layer 4 , a photosensitive resin composition is applied to the wafer sealing body composed of the semiconductor wafer 2 and the sealing material 3 . Next, the photosensitive resin composition is exposed to light containing i rays. Thereafter, the photosensitive resin composition is developed and cured to selectively form a portion where the cured product of the photosensitive resin composition exists and a portion without the cured product of the photosensitive resin composition. The cured product of the photosensitive resin composition becomes the interlayer insulating film 6 . Moreover, the wiring 5 is formed in the part which does not have the hardened|cured material of the photosensitive resin composition. Usually, the rewiring layer 4 is multilayered in many cases. That is, the photosensitive resin composition is further coated on the interlayer insulating film 6 and the wiring 5, exposed, developed, and cured, and the wiring is formed. Various chemical solutions are used in the step of forming the interlayer insulating film 6 or the step of forming the wiring 5 .

In the interlayer insulating film 6 with a small refractive index difference, the polymer molecular chains are not aligned in the in-plane direction, and the intermolecular force is weak. Therefore, the gap between the polymer molecular chains of the interlayer insulating film 6 with a small refractive index difference is large, and the liquid medicine is easy to penetrate. The sealing material 3 is degraded by the chemical solution penetrating into the interlayer insulating film 6 , and cracks are generated, and peeling occurs between the interlayer insulating film 6 and the sealing material 3 , thereby reducing the adhesion. In particular, epoxy resins are easily deteriorated by chemical solutions. Therefore, it is considered that when epoxy resin is used for the sealing material 3, the decrease in the adhesiveness between the interlayer insulating film 6 and the sealing material 3 after chemical treatment is accelerated.

In the first aspect of this embodiment, the difference in refractive index of the interlayer insulating film 6 is as large as 0.0150 or more. Therefore, in this embodiment, it is presumed that the chemical solution is less likely to permeate into the interlayer insulating film 6, and the deterioration of the sealing material 3 is less likely to occur, so that the adhesion between the interlayer insulating film 6 and the sealing material 3 can be improved.

In addition, by making the interlayer insulating film 6 thick, seeping of the chemical solution into the sealing material 3 can be suppressed. However, there arises a disadvantage that the semiconductor device 1 becomes thicker as a whole. The semiconductor device 1 of this embodiment does not make the whole semiconductor device 1 thicker, and the interlayer insulating film 6 in the rewiring layer 4 and the sealing material 3 have excellent adhesion.

The difference in refractive index of the interlayer insulating film 6 is preferably at least 0.0150, more preferably at least 0.0155, more preferably at least 0.0160, and more preferably from the viewpoint of the adhesion between the interlayer insulating film 6 and the sealing material 3 after chemical treatment. Preferably 0.0165 or more, preferably 0.0170 or more, preferably 0.0175 or more, preferably 0.0180 or more, preferably 0.0185 or more, preferably 0.0190 or more, preferably 0.0195 or more, preferably 0.0200 or more, preferably 0.0200 or more 0.0210 or more, preferably 0.0220 or more, preferably 0.0230 or more, preferably 0.0240 or more, preferably 0.0250 or more, preferably 0.0260 or more, preferably 0.0270 or more, preferably 0.0280 or more, preferably 0.0290 or more , preferably more than 0.0300, preferably more than 0.0320, preferably more than 0.0340, preferably more than 0.0360, preferably more than 0.0380, preferably more than 0.040, preferably more than 0.042, preferably more than 0.044, more preferably Preferably at least 0.046, preferably at least 0.048, preferably at least 0.050, preferably at least 0.055, preferably at least 0.060, preferably at least 0.070, preferably at least 0.080, preferably at least 0.090, preferably at least 0.090. Above 0.10.

Also, the upper limit of the difference in refractive index of the interlayer insulating film 6 is not particularly limited, and may be 0.50 or less, 0.40 or less, 0.30 or less, 0.20 or less, 0.10 or less, 0.08 or less, or 0.08 or less. It is 0.06 or less, and may be 0.04 or less.

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

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

In the case where the interlayer insulating film 6 is multi-layered, among the layers of multiple layers, at least one layer needs to have a refractive index difference of 0.0150 or more, preferably the interlayer insulating film layer in contact with the sealing material 3 (first interlayer insulating film layer). The refractive index difference of the insulating film layer) is more than 0.0150. If the refractive index difference between the interlayer insulating film layers in contact with the sealing material 3 is 0.0150 or more, the deterioration of the sealing material can be effectively prevented when forming the interlayer insulating film layers not in contact with the sealing material 3 . The preferred range of the refractive index difference of each interlayer insulating film layer is the same as the preferred range of the refractive index difference of the interlayer insulating film 6 .

The second aspect of this embodiment is characterized in that the etching rate of the interlayer insulating film 6 during the oxygen plasma treatment is 0.05 μm/minute or more. Hereinafter, the etching rate during the oxygen plasma treatment is simply described as "etching rate".

When the etching rate is 0.05 μm/min or more, the adhesion between the interlayer insulating film 6 and the sealing material 3 during high-temperature treatment is excellent. Although the reason is not certain, the inventors of the present invention presume 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 which consists of the semiconductor chip 2 and the sealing material 3. Next, the photosensitive resin composition is exposed to light containing i rays. Thereafter, the photosensitive resin composition is developed and cured to selectively form a portion where the cured product of the photosensitive resin composition exists and a portion without the cured product of the photosensitive resin composition. The cured product of the photosensitive resin composition becomes the interlayer insulating film 6 . Moreover, the wiring 5 is formed in the part which does not have the hardened|cured material of the photosensitive resin composition. Usually, the rewiring layer 4 is multilayered in many cases. That is, a photosensitive resin composition is further applied on the interlayer insulating film 6 and the wiring 5, 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 may be cases including a reflow step, and if heat is applied to the sealing material 3 for a long time, gas may be generated from the sealing material 3 . When the density of the interlayer insulating film 6 is high, that is, when the etching rate of the interlayer insulating film 6 is low, the gas generated from the sealing material 3 is less likely to escape to the outside. That is, the gas generated from the sealing material 3 cannot pass through the insulating film, so it is difficult to escape outward. Therefore, the gas is stored at the interface between the sealing material 3 and the interlayer insulating film 6, and the sealing material 3 and the interlayer insulating film 6 are easily peeled off. In particular, epoxy resins tend to generate gas due to high temperature heat history. Therefore, it is considered that when an epoxy resin is used for the sealing material 3 , the decrease in the adhesion between the interlayer insulating film 6 and the sealing material 3 is accelerated.

The etching rate of the interlayer insulating film 6 in the second aspect of this embodiment is relatively large, being above 0.05 μm/min. Therefore, it is presumed that in this embodiment, even under the condition that the gas is easily discharged from the interlayer insulating film 6 and the gas is easily generated from the sealing material 3, the peeling between the interlayer insulating film 6 and the sealing material 3 is less, and the adhesion is higher. .

The etching rate of the interlayer insulating film 6 is preferably at least 0.05 μm/min, preferably at least 0.06 μm/min, and more preferably at least 0.06 μm/min from the viewpoint of the adhesion between the interlayer insulating film and the sealing material 3 after high-temperature treatment. More than 0.07 microns/min, preferably more than 0.08 microns/min, preferably more than 0.09 microns/min, preferably more than 0.10 microns/min, preferably more than 0.15 microns/min, preferably more than 0.20 microns/min , preferably above 0.25 μm/min, preferably above 0.30 μm/min.

Also, the upper limit of the etching rate of the interlayer insulating film 6 is not particularly limited, and may be 3.0 μm/min or less, 2.0 μm/min or less, 1.0 μm/min or less, or 0.8 μm/min or less. It can also be 0.6 μm/min or less.

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

The first interlayer insulating film layer and the second interlayer insulating film layer may have the same composition or different compositions. The first interlayer insulating film layer and the second interlayer insulating film layer may have the same etching rate or different etching rates. The first interlayer insulating film layer and the second interlayer insulating film layer may have the same film thickness or different film thicknesses. If the first interlayer insulating film layer and the second interlayer insulating film layer have different compositions or different etching rates or different film thicknesses, it is preferable that the respective interlayer insulating film layers have different properties.

In the case where the interlayer insulating film 6 is multi-layered, among the layers of multiple layers, at least one layer of the interlayer insulating film 6 has an etching rate of 0.05 μm/min or more. The interlayer insulating film 6 of the interlayer insulating film layer in contact with the sealing material 3 is preferably etched at a rate of 0.05 μm/min or more because the gas is easily peeled off. If the etching rate of the interlayer insulating film 6 of the interlayer insulating film layer in contact with the sealing material 3 is 0.05 μm/minute or more, the gas generated in the sealing material 3 can be efficiently discharged. The preferred refractive index difference of each interlayer insulating film layer is the same as the preferred etching rate of the interlayer insulating film 6 .

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

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

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

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

R ¹及R ²分別獨立地為氫原子、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為四價有機基，Y ¹為二價有機基，m為1以上之整數。m較佳為2以上，更佳為5以上。 [chem 29]

R ¹ and R ² are independently a hydrogen atom, a saturated aliphatic group with 1 to 30 carbons, an aromatic group, a valent organic group with a carbon-carbon unsaturated double bond, or one of carbon-carbon unsaturated double bonds Valence ions. X ¹ is a tetravalent organic group, Y ¹ is a divalent organic group, and m is an integer of 1 or more. m is preferably 2 or more, more preferably 5 or more.

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

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

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

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

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

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

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

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

[chem 32]

[chem 33]

(通式(4)中，R ₉為氧原子、硫原子、二價有機基中之任一種) [chem 34]

(In the general formula (4), R 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 a hydroxyl group.

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

[chem 35]

Y ¹ is not particularly limited, and Y ¹ is a divalent organic group including an aromatic group from the viewpoint of the adhesion between the interlayer insulating film 6 and the sealing material 3 . Specifically, ^Y1 is a divalent organic group including at least one structure represented by the following general formulas (6) to (8).

(R ₁₀、R ₁₁、R ₁₂及R ₁₃為氫原子、碳數為1～5之一價脂肪族基，可相同亦可不同) [chem 36]

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

(R ₁₄～R ₂₁為氫原子、鹵素原子、碳數為1～5之一價有機基，可相互不同亦可相同) [chem 37]

(R ₁₄ to R ₂₁ are a hydrogen atom, a halogen atom, or a valent organic group with 1 to 5 carbon atoms, which may be different or the same)

(R ₂₂為二價基，R ₂₃～R ₃₀為氫原子、鹵素原子、碳數為1～5之一價脂肪族基，可相同亦可不同) [chem 38]

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

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

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

[chem 39]

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

Examples of tetracarboxylic dianhydrides used as raw materials include pyromellitic dianhydride, diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride, benzophenone-3,3 ',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic dianhydride, diphenyl-3,3',4,4'-tetracarboxylic acid Dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride)propane, 2,2-bis(3,4 -phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane and the like, but are not limited thereto. Moreover, these etc. can 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' -Diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4 '-Diaminodiphenylphenyl, 3,4'-diaminodiphenyl, 3,3'-diaminodiphenyl, 4,4'-diaminobiphenyl, 3,4 '-Diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'- Diaminobenzophenone, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 1,4-bis( 4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, bis[4-(4-amine phenylphenoxy)phenyl]pyridine, bis[4-(3-aminophenoxy)phenyl]pyridine, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis (3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1, 4-bis(4-aminophenyl)benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4 -aminophenyl)propane, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2 -Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, o-toluidine, 9,9 - bis(4-aminophenyl) terpene and the like. In addition, some of the hydrogen atoms on these benzene rings may be substituted. Moreover, these etc. can be used individually or in mixture of 2 or more types.

In the synthesis of polyamic acid ester (A), the method of carrying out the condensation reaction of the tetracarboxylic-acid diester obtained by carrying out the esterification reaction of the following tetracarboxylic-acid dianhydride directly with diamine is normally used preferably.

The alcohols used in the esterification reaction of the said tetracarboxylic dianhydride are alcohols which have an olefinic double bond. Specifically, examples thereof include 2-hydroxyethyl methacrylate, 2-methacryloxyethanol, glycerin diacrylate, glycerin dimethacrylate, and the like, but are not limited thereto. These alcohols can be used individually or in mixture of 2 or more types.

Regarding the specific synthesis method of the polyamide ester (A) used in this embodiment, a previously known method can be used. Regarding the synthesis method, for example, the method described in the specification of International Publication No. 00/43439 can be cited. That is, the method of converting the tetracarboxylic acid diester into the tetracarboxylic acid diester dichloride at one time, carrying out the condensation reaction of the tetracarboxylic acid diester dichloride and the diamine in the presence of a basic compound, and Polyamide ester (A) is produced. Moreover, the method which manufactures polyamic acid ester (A) by the method of making tetracarboxylic-acid diester and diamine condensation-react in presence of an organic dehydrating agent is mentioned.

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

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

、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苄基-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。其等之中，就光感度之方面而言，較佳為上述肟類。 (B1) Photoinitiator When the resin composition used for the formation of the interlayer insulating film 6 is a negative photosensitive resin, a photoinitiator is added. As the photoinitiator, for example, dibenzophenone, methyl o-benzoyl benzoate, 4-benzoyl-4'-methyl diphenyl ketone, dibenzyl ketone, and ketone and other diphenyl ketones can be used. Benzophenone derivatives; 2,2'-diethoxyacetophenone, and 2-hydroxy-2-methylpropiophenone and other acetophenone derivatives; 1-hydroxycyclohexyl phenyl ketone, 9-oxosulfur 𠮿

, 2-Methyl-9-oxosulfur 𠮿

, 2-isopropyl-9-oxothio𠮿

, and diethyl-9-oxosulfur

9-oxosulfur

Derivatives; benzoyl derivatives such as benzoyl, benzoyl dimethyl ketal and benzyl-β-methoxyethyl acetal; benzoin derivatives such as benzoin methyl ether; 2,6-bis(4 Azides such as '-diazidobenzylidene)-4-methylcyclohexanone and 2,6'-bis(4'-diazidobenzylidene)cyclohexanone; 1-phenyl -1,2-Butanedione-2-(O-methoxycarbonyl)oxime, 1-phenylpropanedione-2-(O-methoxycarbonyl)oxime, 1-phenylpropanedione-2 -(O-ethoxycarbonyl)oxime, 1-phenylpropanedione-2-(O-benzoyl)oxime, 1,3-diphenylpropanetrione-2-(O-ethoxy Carbonyl) oxime, 1-phenyl-3-ethoxyglycerone-2-(O-benzoyl) oxime and other oximes; N-aryl glycines such as N-phenylglycine; Peroxides such as benzoyl oxide; aromatic biimidazoles; and titanocenes, etc. Among them, the above-mentioned oximes are preferable in terms of photosensitivity.

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

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

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

(C) Additives The difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film 6 according to the first aspect of this embodiment can be adjusted by the type or amount of additives. If an additive that interacts with polymer molecular chains and has a relatively high planar structure is used, the molecular chains are easily aligned in the in-plane direction, and the difference between the in-plane refractive index and the out-of-plane refractive index can be increased. As an additive for increasing the refractive index difference, for example, N-(4-bromophenyl)phthalimide, N-(4-chlorophenyl)phthalimide, biphenyl, and the like can be used. The amount of the additive may be appropriately adjusted according to the intended difference between the in-plane refractive index and the out-of-plane refractive index.

＜How to adjust the etching rate＞ The method for adjusting the etching rate in the second aspect of this implementation is described. There is a tendency that the etching rate decreases when the imidization rate increases, and the etching rate tends to increase when the imidization rate decreases. In order to reduce the imidization rate, it is only necessary to reduce the amount of imidization accelerator, or lower the temperature during thermal hardening.

Usually, an amine compound can be suitably used as an imidization accelerator. Examples thereof include primary amines such as aniline, secondary amines such as methylaniline, and tertiary amines such as pyridine. Among them, secondary amines and tertiary amines are preferred from the viewpoint of storage stability of the varnish. Furthermore, among them, heterocyclic amines are preferable, and piperidine, pyrrolidine, purine, pyrimidine, pyridine and derivatives thereof are more preferable.

(D) solvent It will not specifically limit if it is a solvent which can dissolve or disperse each component. For example, N-methyl-2-pyrrolidone, (gamma)-butyrolactone, acetone, methyl ethyl ketone, dimethyl sulfoxide, etc. are mentioned. These solvents can be used in the range of 30-1500 mass parts with respect to 100 mass parts of (A) photosensitive resins according to coating film thickness and viscosity.

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

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

(development) After exposing the polyimide precursor composition, unnecessary parts are washed with a developing solution. The developer used is not particularly limited, and in the case of a polyimide precursor composition for development using a solvent, N,N-dimethylformamide, dimethylsulfide, N , N-dimethylacetamide, N-methyl-2-pyrrolidone, cyclopentanone, γ-butyrolactone, acetates and other good solvents; these good solvents are mixed with lower alcohols, water, aromatic Mixed solvents of poor solvents such as hydrocarbons, etc. Rinse and wash with a poor solvent etc. as needed after developing.

In the case of a polyimide precursor composition that is developed using an alkaline aqueous solution, it is preferably an aqueous solution of tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, Sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate Aqueous solutions of basic compounds such as esters, cyclohexylamine, ethylenediamine, and hexamethylenediamine.

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

The heating temperature used for thermal curing of the polyimide precursor composition is not particularly limited, and generally, the higher the thermal curing temperature, the larger the refractive index difference tends to be. The heating temperature is preferably 160°C or higher, more preferably 180°C or higher, and most preferably 200°C or higher from the viewpoint of expressing a refractive index difference of 0.0150 or higher in the present embodiment. From the viewpoint of the influence on other components, it is preferably 400°C or lower.

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

[chemical 40]

X ¹ , Y 1 , m in general formula ( ¹ ) are the same as X ¹ , Y ¹ , m in general formula (11), X ¹ is a tetravalent organic group, Y ¹ is a divalent organic group, and m is An integer of 1 or more. The 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 an 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 in the polybenzoxazole precursor composition, poly(o-hydroxyamide) containing a repeating unit represented by the following general formula (14) can be used.

(通式(14)中，U與V為二價有機基) [chem 41]

(In general formula (14), U and V are divalent organic groups)

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

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

(R ₁₀、R ₁₁、R ₁₂及R ₁₃為氫原子、碳數為1～5之一價脂肪族基，可相同亦可不同) [chem 42]

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

(R ₁₄～R ₂₁為氫原子、鹵素原子、碳數為1～5之一價有機基，可相互不同亦可相同) [chem 43]

(R ₁₄ to R ₂₁ are a hydrogen atom, a halogen atom, or a valent organic group with 1 to 5 carbon atoms, which may be different or the same)

(R ₂₂為二價基，R ₂₃～R ₃₀為氫原子、鹵素原子、碳數為1～5之一價脂肪族基，可相同亦可不同) [chem 44]

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

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

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

[chem 45]

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

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

Dichloride derivatives can be synthesized by allowing a halogenating agent to act on a dicarboxylic acid derivative. As the halogenating agent, thionyl chloride, phosphoryl chloride, phosphorus oxychloride, phosphorus pentachloride, etc. which are generally used in the chlorination reaction of acyl chlorides of 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, or a method of distilling off the excess after reacting in an excess of a halogenating agent, etc. can be used for synthesis.

Examples of dicarboxylic acids used in dicarboxylic acid derivatives include: isophthalic acid, terephthalic acid, 2,2-bis(4-carboxyphenyl)-1,1,1,3,3 ,3-hexafluoropropane, 4,4'-dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxytetraphenylsilane, bis(4-carboxyphenyl)sulfone, 2,2-bis(p-carboxyphenyl)propane, 5-tert-butylisophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2, 6-naphthalenedicarboxylic acid, malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinate 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, dodecafluorosuberic 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, hexadecanedioic acid, docosanedioic acid, tricosanedioic acid, tetradecanedioic acid, Hexacanedioic acid, hexacanedioic acid, heptacanedioic acid, octadecanedioic acid, hexacanedioic acid, triacanedioic acid, triacanedioic acid, thirty Dioxanedioic acid, diglycolic acid, etc. These can be mixed and used.

Examples of hydroxyl-containing diamines include 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, bis (3-amino-4-hydroxyphenyl)propane, bis(4-amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)propane, bis(4-amino -3-hydroxyphenyl) phenyl, 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4 -Amino-3-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane and the like. These can be mixed and used.

(B2) Photoacid generator The photoacid generator has the function of increasing the solubility of the alkaline aqueous solution of the light-irradiated part. Examples of photoacid generators include diazonaphthoquinone compounds, aryldiazonium salts, diaryliodonium salts, triarylconium salts, and the like. Among them, diazonaphthoquinone compounds are more preferable because of their higher sensitivity.

＜How to adjust the etching rate＞ The method for adjusting the etching rate in the second aspect of this implementation is described. When the cyclization rate of polybenzoxazole increases, the etching rate decreases, and when the cyclization rate decreases, the etching rate tends to increase.

In order to reduce the cyclization rate, just reduce the amount of cyclization accelerator, or lower the temperature during thermal hardening.

As a cyclization accelerator, a sulfonic acid, phosphoric anhydride, etc. are mentioned, for example. Among them, p-toluenesulfonic acid is preferred from the viewpoint of storage stability of the varnish.

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

(D) solvent It will not specifically limit as long as 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 adhesive agent, a thermal acid generator, and the like.

(development) After exposing the polybenzoxazole precursor composition, unnecessary parts are washed with a developing solution. The developer used is not particularly limited, for example, sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, tetramethyl hydroxide An alkaline aqueous solution such as ammonium ammonium is preferred.

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

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

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

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

[chem 46]

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

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

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

Phenolic resin is a polycondensation product of phenol or its derivatives and aldehydes. Polycondensation is carried out in the presence of catalysts such as acid or alkali. In particular, the phenol resin obtained when an acid catalyst is used is called a novolak-type phenol resin.

Examples of phenol derivatives include phenol, cresol, ethylphenol, propylphenol, butylphenol, amylphenol, benzylphenol, adamantanephenol, benzyloxyphenol, xylenol, phthalate Phenol, Resorcinol, Ethyl Resorcinol, Hexyl Resorcinol, Hydroquinone, Pyrogallol, Phloroglucinol, 1,2,4-Trihydroxybenzene, Rosebic Acid, Bi 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) fluorene, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2,2-bis(2-hydroxy- 5-biphenyl)propane, dihydroxybenzoic acid, etc.

Examples of the aldehyde compound include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, pivalaldehyde, butyraldehyde, valeraldehyde, hexanal, trioxane, glyoxal, cyclohexanal, diphenylacetaldehyde, Ethylbutyraldehyde, benzaldehyde, glyoxylic acid, 5-norcamphene-2-carboxyaldehyde, malondialdehyde, succinaldehyde, glutaraldehyde, salicaldehyde, naphthaldehyde, 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. The above-mentioned (b) component is more preferably one further modified by the reaction of a phenolic hydroxyl group and a polybasic acid anhydride.

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

(b) Modified phenolic resins with unsaturated hydrocarbon groups are usually phenol or its derivatives and compounds with unsaturated hydrocarbon groups (preferably those with 4 to 100 carbon atoms) (hereinafter referred to as "unsaturated hydrocarbon group-containing resins" as appropriate) Compounds") (hereinafter referred to as "unsaturated hydrocarbon group-modified phenol derivatives"), polycondensation products with aldehydes, or reaction products of phenol resins and unsaturated hydrocarbon group-containing compounds.

Regarding the phenol derivative here, the same thing as the above-mentioned phenol derivative can be used as a raw material of the phenol resin of the (A) component.

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

Examples of unsaturated hydrocarbon group-containing compounds 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 fats esters. Examples of suitable unsaturated fatty acids include crotonic acid, myristic acid, palmitoleic acid, oleic acid, elaidic acid, vacantoleic acid, codoleic acid, erucic acid, tetradecenoic acid, and linoleic acid. , α-linolenic acid, linoleic acid, stearidonic acid, eicosadonic acid, eicosapentaenoic acid, herring acid and docosahexaenoic acid. Among them, esters of unsaturated fatty acids with 8 to 30 carbons and monohydric to trihydric alcohols with 1 to 10 carbons are more preferred, especially unsaturated fatty acids with 8 to 30 carbons and trihydric alcohols. esters of glycerol.

The esters of unsaturated fatty acids with 8-30 carbon atoms and glycerol can be commercially obtained in the form of vegetable oil. Vegetable oils include non-drying oils with an iodine value of 100 or less, semi-drying oils with an iodine value of more than 100 and less than 130, or drying oils with an iodine value of 130 or more. Examples of non-drying oils include olive oil, morning glory seed oil, Polygonum multiflorum seed oil, camellia oleifera oil, camellia oil, castor oil, and peanut oil. As a semi-dry oil, corn oil, cottonseed oil, and sesame oil are mentioned, for example. 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 also be used.

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

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

When preparing the component (b), first, the above-mentioned phenol derivative is reacted with the above-mentioned unsaturated hydrocarbon group-containing compound to produce an unsaturated hydrocarbon group-modified phenol derivative. The above reaction is preferably carried out at 50-130°C. Regarding the reaction ratio between the phenol derivative 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 to 100 parts by mass of the phenol derivative. 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 if necessary.

By polycondensing the unsaturated hydrocarbon group-modified phenol derivative produced by the above reaction with aldehydes, a phenol resin modified with an unsaturated hydrocarbon group-containing compound is produced. Regarding aldehydes, the same ones as those described above can be used as aldehydes for obtaining the phenol resin.

The reaction of the above-mentioned aldehydes with the above-mentioned unsaturated hydrocarbon group-modified phenol derivatives is a polycondensation reaction, and the previously known synthesis conditions of phenol resins can be used. The reaction is preferably carried out in the presence of a catalyst such as an acid or a base, more preferably using an acid catalyst. As a catalytic acid, hydrochloric acid, sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid, and oxalic acid are mentioned, for example. These acid catalysts can be used individually by 1 type or in combination of 2 or more types.

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

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

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

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

The reaction between the phenolic resin and the unsaturated hydrocarbon group-containing compound is usually preferably carried out at 50-130°C. Also, regarding the reaction ratio between 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 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. If the unsaturated hydrocarbon group-containing compound is less than 1 part by mass, the flexibility of the cured film tends to decrease, and if it exceeds 100 parts by mass, the possibility of gelation during the reaction tends to increase, and the cured film tends to be Tendency to decrease heat resistance. At this time, p-toluenesulfonic acid, trifluoromethanesulfonic acid, or the like can be used as a catalyst if necessary. In addition, solvents such as toluene, xylene, methanol, and tetrahydrofuran can be used in the reaction.

Furthermore, the polybasic acid anhydride is made to react with the phenolic hydroxyl group remaining in the phenol resin modified with the unsaturated hydrocarbon group containing compound produced by the above-mentioned method. Thereby, an 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 will not be specifically limited if it has the acid anhydride group formed by the dehydration condensation of the carboxyl group of the polybasic acid which has several carboxyl groups. Examples of polybasic acid anhydrides include phthalic anhydride, succinic anhydride, octenylsuccinic anhydride, penta(dodecenyl)succinic anhydride, maleic anhydride, itaconic anhydride, and tetrahydrophthalic anhydride. , Hexahydrophthalic Anhydride, Methyltetrahydrophthalic Anhydride, Methylhexahydrophthalic Anhydride, Resilicate Anhydride, 3,6-endomethylenetetrahydrophthalic Anhydride, Methane Dibasic acid anhydrides such as methylene tetrahydrophthalic anhydride, tetrabromophthalic anhydride and trimellitic anhydride; biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, diphenyl ether tetracarboxylic Aromatic tetrabasic acid dianhydrides such as acid dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic dianhydride, and benzophenone tetracarboxylic dianhydride. These may be used individually by 1 type or in combination of 2 or more types. Among them, the polybasic acid anhydride is preferably a dibasic acid anhydride, more preferably at least one selected from the group consisting of tetrahydrophthalic anhydride, succinic anhydride, and hexahydrophthalic anhydride. In this case, there is an advantage that a resist pattern having a better shape can be formed.

Moreover, (A) the alkali-soluble resin which has a phenolic hydroxyl group can contain the phenol resin which made polybasic acid anhydride react and acid-modified further. When (A) component contains the phenol resin which acid-modified with polybasic acid anhydride, the solubility with respect to alkaline aqueous solution (developing solution) of (A) component improves further.

Examples of the polybasic acid anhydride include: phthalic anhydride, succinic anhydride, octenyl succinic anhydride, penta(dodecenyl) succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride Anhydride, Hexahydrophthalic Anhydride, Methyltetrahydrophthalic Anhydride, Methylhexahydrophthalic Anhydride, Resilicate Anhydride, 3,6-endomethylenetetrahydrophthalic Anhydride, Methyl endomethylene tetrahydrophthalic anhydride, tetrabromophthalic anhydride, trimellitic anhydride and other dibasic acid anhydrides; biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, diphenyl ether tetra Aliphatic and aromatic tetracarboxylic dianhydrides such as carboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, etc. . These may be used individually by 1 type or in combination of 2 or more types. Among them, 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 Examples of photoacid generators include diazonaphthoquinone compounds, aryldiazonium salts, diaryliodonium salts, triarylconium salts, and the like. Among them, diazonaphthoquinone compounds are more preferable because of their higher sensitivity.

＜How to adjust the etching rate＞ The method for adjusting the etching rate in the second aspect of this implementation is described. If the thermal crosslinking rate of phenol increases, the etching rate decreases, and if the thermal crosslinking rate decreases, the etching rate increases.

In order to reduce the thermal crosslinking rate, just reduce the amount of thermal crosslinking accelerator, or lower the temperature during thermal hardening.

As thermal crosslinking accelerators, for example, epoxy compounds, oxetane compounds, oxazoline compounds, aldehydes, modified aldehydes, isocyanate compounds, unsaturated bond-containing compounds, polyol compounds, polyhydric alcohol compounds, Amine compounds, melamine compounds, metal chelating agents, C-methylol-based compounds, N-methylol-based compounds, etc.

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

(D) solvent It will not specifically limit as long as it is a solvent which can dissolve or disperse each component.

(E) Other It may contain thermal crosslinking agent, sensitizer, adhesive agent, dye, surfactant, dissolution accelerator, crosslinking accelerator, etc. However, when the photosensitive resin film after pattern formation is heated and hardened by containing a thermal crosslinking agent, a thermal crosslinking agent component and (A) component react and form a bridge structure. Thereby, hardening at a low temperature can be performed, and brittleness of the film and melting of the film can be prevented. As the thermal crosslinking agent component, specifically, a compound having a phenolic hydroxyl group, a compound having a methylolamine group, and a compound having an epoxy group are preferably used.

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

(thermohardening) After the development, the polymers having phenolic hydroxyl groups are heated to thermally crosslink the polymers having phenolic hydroxyl groups. The crosslinked polymer becomes the cured relief pattern, that is, the interlayer insulating film 6 .

The heating temperature for thermal curing of the polymer having a phenolic hydroxyl group is not particularly limited, and the heating temperature is preferably a relatively low temperature from the viewpoint of influence on other members. The heating temperature is preferably lower than 250°C, more preferably lower than 230°C, more preferably lower than 200°C, especially preferably lower than 180°C.

(Manufacturing method of semiconductor device) A method of manufacturing a semiconductor device in this embodiment will be described with reference to FIG. 3 . FIG. 3 is an example of manufacturing steps of the semiconductor device of this embodiment. In FIG. 3A, a wafer 10 having completed the previous steps is prepared. Then, in FIG. 3B , the wafer 10 that has completed the previous steps is diced to form a plurality of semiconductor chips 2 . The semiconductor wafer 2 can be purchased. As shown in FIG. 3C, the semiconductor wafer 2 prepared in the above-mentioned manner is attached to the support 11 at a certain interval.

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

Furthermore, in this embodiment, the above-mentioned 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 chip 2 .

The interlayer insulating film in the rewiring layer may be multilayered. Therefore, the rewiring layer forming step may include a plurality of emboss 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 each semiconductor wafer 2 are formed (bump formation), and each semiconductor wafer 2 is diced. 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 the first aspect of this embodiment, the difference in refractive index of the cured relief pattern (interlayer insulating film) formed through the above steps can be set to be 0.0150 or more. Here, the refractive index difference of the interlayer insulating film can be adjusted by the amount of additives.

In the second aspect of this embodiment, the etching rate of the hardened relief pattern (interlayer insulating film) formed through the above steps can be set to 0.05 μm/minute or more.

In this embodiment, in the step of forming the interlayer insulating film, it is preferable to use a combination of photosensitive resins capable of forming at least one compound among polyimide, polybenzoxazole, and polymers having phenolic hydroxyl groups. form an interlayer insulating film. [Example]

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

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

Next, under cooling in an ice bath, a solution obtained by dissolving dicyclohexylcarbodiimide (DCC) in γ-butyrolactone was added to the mixture for 40 minutes while stirring. Then, what suspends 4,4'- diamino diphenyl ether (DADPE) which is a diamine in γ-butyrolactone was added over 60 minutes, stirring. Furthermore, after stirring at room temperature for 2 hours, ethanol was added and stirred for 1 hour, and then, γ-butyrolactone was added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction 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 after the obtained precipitate was separated by filtration, vacuum drying was carried out to obtain a powdered polymer (polyimide precursor (polymer A -1)). The mass of the compound used for component A-1 is shown in Table 1 below.

(Synthesis of polymers A-2 to A-4) Change the tetracarboxylic dianhydride and diamine to the following Table 1, except that, react in the same manner as the method described in the above-mentioned polymer A-1, and obtain the polyimide precursor (polymer A-2～A-4).

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

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

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

[Examples 1-9, Comparative Examples 1-2] It prepared like Table 2 shown below, and obtained the solution of the photosensitive resin composition. In addition, the unit of Table 2 is a mass part.

Using the compound described in Table 2, each photosensitive resin composition of Examples 1-9 and Comparative Examples 1-2 was produced by the compounding quantity described in Table 3 and Table 4.

(1) Refractive index difference measurement test, (2) Crack resistance test after chemical treatment, (3) Adhesion test with sealing material after chemical treatment was performed on the photosensitive resin composition produced. The results of each test are shown in Tables 3 and 4 below.

(1) Refractive index difference measurement test A fan-out wafer-level chip size packaging type semiconductor device was produced using the photosensitive resin composition produced in the examples and comparative examples. An interlayer insulating film with a thickness of 10 μm was taken out as neatly as possible from the manufactured semiconductor device. The difference between the in-plane refractive index and the out-of-plane refractive index at a measurement wavelength of 1310 nm was measured for the taken-out interlayer insulating film using a Metricon Co., Ltd. manufactured coupling device (PC-2010).

(2) Crack resistance test after chemical treatment R4000 series manufactured by Nagase Chemtex Co., Ltd. was prepared as an epoxy-based sealing material. Next, the sealing material was spin-coated so that the thickness may become about 150 micrometers on the aluminum sputtered polysiloxane wafer, and it heat-cured at 130 degreeC, and the epoxy-type sealing material was hardened. The photosensitive resin composition produced in the Example and the comparative example was apply|coated on the said epoxy-type cured film so that the final film thickness might become 10 micrometers. For the coated photosensitive resin composition, under the exposure conditions of 1200 mJ/cm ² in Examples 1-4, 8, and 2500 mJ/cm ² in Examples 5-7, 9, and Comparative Examples After surface exposure, it was thermally cured at 200°C for 2 hours to form a cured film of the first layer with a thickness of 10 μm.

A chemical solution (DMSO (dimethylsulfoxide, dimethylsulfoxide): 93% by weight, 2-aminoethanol: 5% by weight, TMAH: 2% by weight) preheated to 50°C was added dropwise to the above test piece from the cured film side , washed with water and dried after 5 minutes.

After cutting the cross-section with a test piece FIB (Focused Ion Beam) device (manufactured by JEOL Corporation, JIB-4000), check the presence or absence of cracks in the epoxy part to evaluate the degree of deterioration. The case where a crack was not seen was evaluated as ◯, and the case where a crack was seen even in one piece was evaluated as x.

(3) Adhesion test with sealing material after drug treatment The pin was erected on the photosensitive resin cured film of the sample produced in the test of (2), and the adhesion test was performed using a coil tester (manufactured by Quad Group, Sebastian 5 type). Evaluation: Adhesive strength over 70 MPa Adhesive force◎ More than 50 MPa - less than 70 MPa Adhesion force○ More than 30 MPa - less than 50 MPa Adhesion force△ Less than 30 MPa Adhesive force×

光酸產生劑 D-2

交聯劑 E-1

折射率差調整劑 F-1 N-(4-溴苯基)鄰苯二甲醯亞胺 F-2 聯苯 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

crosslinking agent E-1

Refractive Index Difference Adjuster F-1 N-(4-Bromophenyl)phthalimide F-2 biphenyl solvent G-1 γ-butyrolactone G-2 DMSO G-3 Propylene Glycol Monomethyl Ether Acetate G-4 ethyl lactate

[table 3] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 polymer A-1 100 A-2 100 A-3 100 A-4 100 B-1 100 B-2 100 B-3 100 Photoinitiator D-1 2 2 2 2 photoacid generator D-2 10 10 10 crosslinking agent E-1 Refractive Index Difference Adjuster F-1 10 10 10 10 8 8 8 F-2 solvent G-1 160 160 160 160 225 225 225 G-2 40 40 40 40 G-3 25 25 25 G-4 Refractive index difference 0.0166 0.0163 0.0161 0.0152 0.0155 0.0155 0.0151 Crack resistance test ○ ○ ○ ○ ○ ○ ○ Adhesion test with sealing material ◎ ○ ○ △ ○ ○ △

[Table 4] Example 8 Example 9 Comparative example 1 Comparative example 2 polymer A-1 100 A-2 A-3 A-4 100 B-1 100 B-2 B-3 100 Photoinitiator D-1 2 2 photoacid generator D-2 10 10 crosslinking agent E-1 Refractive Index Difference Adjuster F-1 F-2 10 8 solvent G-1 160 225 160 225 G-2 40 40 G-3 25 25 G-4 Refractive index difference 0.0165 0.0153 0.0147 0.0148 Crack resistance test ○ ○ x x Adhesion test with sealing material ◎ ○ x x

As can be clearly seen from Tables 3 and 4, according to the results of the tests (1) to (3) performed on the photosensitive resin compositions of Examples 1 to 9, it was confirmed that when the difference in refractive index is 0.0150 or more, in the case of pharmaceuticals In the crack resistance test after treatment, no cracks were seen in the epoxy part, and in the adhesion test with the sealing material after chemical treatment, the evaluation of the adhesion force was any one of ◎, ○, and △.

On the other hand, as can be clearly seen from Tables 3 and 4, according to the results of the tests (1) to (3) performed on the photosensitive resin compositions of Comparative Examples 1 and 2, it was confirmed that the refractive index difference did not reach 0.0150. In some cases, cracks were observed in the epoxy portion in the crack resistance test after chemical treatment, and the evaluation of the adhesion force in the adhesive test with the sealing material after chemical treatment was ×.

Also, using the photosensitive resin compositions of Examples 1 to 9, a fan-out wafer-level chip size package type semiconductor device in which epoxy resin was included in the molding resin was produced, and as a result, it operated without any problem.

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

Next, under cooling in an ice bath, a solution obtained by dissolving dicyclohexylcarbodiimide (DCC) in γ-butyrolactone was added to the mixture for 40 minutes while stirring. Then, what suspends 4,4'- diamino diphenyl ether (DADPE) which is a diamine in γ-butyrolactone was added over 60 minutes, stirring. Furthermore, after stirring at room temperature for 2 hours, ethanol was added and stirred for 1 hour, and then, γ-butyrolactone was added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction 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 after the obtained precipitate was separated by filtration, vacuum drying was carried out to obtain a powdered polymer (polyimide precursor (polymer H -1)). The mass of the compound used for component H-1 is shown in Table 5 shown below.

(Synthesis of Polymers H-2～H-3) Change the tetracarboxylic dianhydride and diamine to the following Table 5, except that, react in the same manner as the method described in the above-mentioned polymer H-1, and obtain the polyimide precursor (polymer H-2～H-3).

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

(Synthesis of Polymer I-2) Except that the dicarboxylic acid and diaminophenol were changed to Table 1 shown below, the polybenzoxazole precursor was obtained by reacting in the same manner as described in the above polymer I-1. material (polymer I-2).

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

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

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

[table 5] polymer Tetracarboxylic dianhydride (A) A mass (g) Diamine (B) Mass of B (g) Polyimide Precursor Polymer H-1 4,4'-Oxydiphthalic dianhydride (ODPA) 147.11 4,4'-Diaminodiphenyl ether (DADPE) 92.9 Polymer H-2 4,4'-Oxydiphthalic dianhydride (ODPA) 147.11 2,2'-Bisdimethyl-4,4'-diaminobiphenyl (m-TB) 98.5 Polymer H-3 4,4'-Oxydiphthalic dianhydride (ODPA) 147.11 p-phenylenediamine (PPD) 50.18 polymer Dicarboxylic acid (C) Mass of C (g) Diaminophenol (D) D mass (g) Polybenzoxazole Precursor Polymer I-1 4,4'-Diphenyl ether dicarboxylic acid 15.48 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane 18.3 Polymer I-2 sebacic acid 12.13 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane 18.3 polymer Cresol Novolak Resin (E) Mass of E (g) Modified phenolic resin (F) Mass of F (g) Phenolic resin Polymer J-1 C1 resin 85 C2 resin 15 Polymer J-2 C1 resin 100 C2 resin 0

[Examples 10-16, Comparative Examples 3-4] It prepared like Table 6 shown below, and obtained the solution of the photosensitive resin composition. In addition, the unit of Table 6 is a mass part.

Using the compound described in Table 6, each photosensitive resin composition of Examples 10-16 and Comparative Examples 3-4 was produced by the compounding quantity described in Table 7 and Table 8.

(1) Etching rate measurement test during oxygen plasma treatment, (2) Reflow resistance test of sealing material, (3) Adhesion test with sealing material was performed on the prepared photosensitive resin composition. The results of each test are shown in Table 7 below.

(1) Etching rate measurement test during oxygen plasma treatment A fan-out wafer-level chip size packaging type semiconductor device was produced using the photosensitive resin composition produced in the examples and comparative examples. An interlayer insulating film with a thickness of 10 μm was taken out as neatly as possible from the manufactured semiconductor device. The taken-out interlayer insulating film was treated with an EXAM device manufactured by Shinko Electric Co., Ltd. under the conditions of 133 W and 50 Pa for 3 minutes, and the film thickness before and after the treatment was measured to measure the etching rate during oxygen plasma treatment.

(2) Reflow resistance test of sealing material R4000 series manufactured by Nagase Chemtex Co., Ltd. was prepared as an epoxy-based sealing material. Next, the sealing material was spin-coated so that the thickness may become about 150 micrometers on the aluminum sputtered polysiloxane wafer, and it heat-cured at 130 degreeC, and the epoxy-type sealing material was hardened. The photosensitive resin composition produced in the Example and the comparative example was applied on the said epoxy-type cured film so that the final film thickness might become 10 micrometers. The entire surface of the coated photosensitive resin composition was exposed to 200 mJ/cm 2 in Examples 1 to 3, 200 mJ/cm ² in Comparative Example 1, 500 mJ/cm 2 in Examples 4, 5, and 500 mJ/cm ² in Comparative Example 2. After exposure, it was thermally cured at 150° C. for 4 hours to form a cured film of the first layer with a thickness of 10 μm.

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

The test piece after the hardened film of the second layer is formed is under the simulated reflow condition of using mesh belt type continuous baking furnace (manufactured by Koyo Thermo Systems, model name 6841-20AMC-36), under nitrogen atmosphere, heated to The peak temperature is 260°C. The so-called simulated reflow conditions are based on the IPC (Institute of Printed Circuits)/JEDEC (Joint Electronic Device Engineering Council, United Electronics) as a standard specification of the American semiconductor industry group related to the evaluation method of semiconductor devices. Equipment Engineering Committee) J-STD-020A item 7.6 of the reflow conditions recorded in the form, the solder melting point is assumed to be a high temperature of 220 ℃, and standardized.

After the cured film processed under the above-mentioned simulated reflow conditions was cut with a FIB device (JIB-4000 manufactured by JEOL Ltd.), the degree of deterioration was evaluated by checking the presence or absence of pores in the epoxy part. The case where no void was seen was evaluated as ◯, and the case where even one void was observed was evaluated as x.

(3) Adhesion test with sealing material The pin was erected on the photosensitive resin cured film of the sample produced in the test of (2), and the adhesion test was performed using a coil tester (manufactured by Quad Group, Sebastian 5 type). Evaluation: Adhesive strength over 70 MPa Adhesive force◎ More than 50 MPa - less than 70 MPa Adhesion force○ More than 30 MPa - less than 50 MPa Adhesion force△ Less than 30 MPa Adhesive force×

光酸產生劑 K-2

交聯劑 L-1

硬化促進劑 M-1 2,6-二甲基哌啶 M-2 對甲苯磺酸 溶劑 N-1 γ-丁內酯 N-2 二甲基亞碸 N-3 丙二醇單甲醚乙酸酯 N-4 乳酸乙酯 [Table 6] Photoinitiator K-1

photoacid generator K-2

crosslinking agent L-1

hardening accelerator M-1 2,6-Dimethylpiperidine M-2 p-Toluenesulfonic acid solvent N-1 γ-butyrolactone N-2 DMSO N-3 Propylene Glycol Monomethyl Ether Acetate N-4 ethyl lactate

[Table 7] Example 10 Example 11 Example 12 Example 13 Example 14 Example 15 Example 16 polymer H-1 100 H-2 100 H-3 100 I-1 100 I-2 100 J-1 100 J-2 100 Photoinitiator K-1 2 2 2 photoacid generator K-2 10 10 15 15 crosslinking agent L-1 15 15 solvent N-1 160 160 160 225 225 N-2 40 40 40 N-3 25 25 N-4 120 120 hardening temperature 150°C 150°C 150°C 150°C 150°C 150°C 150°C etch rate 0.15 0.13 0.14 0.12 0.12 0.1 0.08 Reflow resistance test ○ ○ ○ ○ ○ ○ ○ Adhesion test with sealing material ◎ ○ ○ ○ ○ ○ △

[Table 8] Comparative example 3 Comparative example 4 polymer H-1 100 H-2 H-3 I-1 100 I-2 J-1 J-2 Photoinitiator K-1 2 photoacid generator K-2 10 crosslinking agent L-1 hardening accelerator M-1 5 M-2 5 solvent N-1 160 225 N-2 40 N-3 25 N-4 hardening temperature 150°C 150°C etch rate 0.03 0.02 Reflow resistance test x x Adhesion test with sealing material x x

Using the photosensitive resin composition described in Examples 10 to 16, a fan-out wafer-level chip size package type semiconductor device in which epoxy resin is included in the molding resin was produced, and it operated without any problem. .

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

This application is based on Japanese Patent Application No. 2017-149057 filed on August 1, 2017, and Japanese Patent Application No. 2017-149059 filed on August 1, 2017. The content is included in this article.

1: Semiconductor device 2: Semiconductor wafer 2a: terminal 3: Sealing material 4: Redistribution layer 5: Wiring 6: Interlayer insulating film 7: External connection terminal 10:Wafer 11: Support body 12: Molding resin 13: Photosensitive resin composition A: arrow S1: area S2: area

FIG. 1 is a schematic cross-sectional view of a semiconductor device according to this embodiment. FIG. 2 is a schematic top view of the semiconductor device of the present embodiment. FIG. 3 is an example of manufacturing steps of the semiconductor device of this embodiment. FIG. 4 is a comparison diagram between a flip-chip BGA (Ball Grid Array) and a fan-out (Fan-Out) WLCSP (Wafer Level Chip Scale Package).

Claims (70)

A semiconductor device, characterized by comprising: a semiconductor wafer, a sealing material, and a redistribution layer having an area larger than that of the semiconductor wafer in plan view; and the sealing material has a portion in direct contact with the interlayer insulating film of the redistribution layer, When the thickness of the interlayer insulating film of the wiring layer is 10 μm, the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index at a wavelength of 1310 nm is 0.0150 or more. The semiconductor device according to claim 1, wherein the sealing material contains epoxy resin. The semiconductor device according to claim 1 or 2, wherein the above-mentioned interlayer insulating film contains polyimide, polybenzo

At least one of an azole and a polymer having a phenolic hydroxyl group. The semiconductor device according to claim 3, wherein the interlayer insulating film contains 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). Such as the semiconductor device of claim 4, wherein X in the above general formula ( ¹ ) is a tetravalent organic group comprising an aromatic ring, and Y in the above general formula ( ¹ ) is a divalent organic group comprising an aromatic ring . Such as the semiconductor device of claim 4, wherein ^X in the above general formula (1) includes at least one structure represented by the following general formula (2) to general formula (4),

(In the general formula (4), R ₉ is an oxygen atom, a sulfur atom, or a divalent organic group). Such as the semiconductor device of claim 6, wherein ^X in the above-mentioned general formula (1) comprises a structure represented by the following general formula (5),

Such as the semiconductor device of claim 4, wherein ^Y in the above-mentioned general formula (1) includes at least one structure represented by the following general formula (6) to general formula (8),

(R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are a hydrogen atom, a valent aliphatic group or a hydroxyl group with a carbon number of 1 to 5, which may be the same or different)

(R ₁₄ ~R ₂₁ are hydrogen atom, halogen atom, valent organic group with 1~5 carbon number or hydroxyl group, they can be different or the same)[Chemical 8]

(R ₂₂ is a divalent group, and R ₂₃ to R ₃₀ are hydrogen atoms, halogen atoms, aliphatic groups with 1 to 5 carbon atoms or hydroxyl groups, which may be the same or different). Such as the semiconductor device of claim 8, wherein ^Y in the above general formula (1) comprises a structure represented by the following general formula (9),

The semiconductor device according to claim 3, wherein the interlayer insulating film contains polybenzone having a structure of the following general formula (10)

azole,

(In general formula (10), U and V are divalent organic groups). The semiconductor device according to claim 10, wherein U in the above general formula (10) is a divalent organic group with 1 to 30 carbon atoms. The semiconductor device according to claim 11, wherein U in the above general formula (10) is a chain alkylene group having 1 to 8 carbon atoms and part or all of the hydrogen atoms are substituted with fluorine atoms. The semiconductor device according to claim 10, wherein V in the above general formula (10) is a divalent organic group containing an aromatic group. The semiconductor device according to claim 13, wherein V of the above-mentioned general formula (10) includes at least one structure represented by the following general formula (6) to general formula (8),

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

(R ₁₄ ~R ₂₁ are hydrogen atom, halogen atom, or a valent organic group with carbon number 1~5, which may be different or the same)

(R ₂₂ is a divalent group, and R ₂₃ to R ₃₀ are hydrogen atoms, halogen atoms, or aliphatic groups with 1 to 5 carbon atoms, which may be the same or different). The semiconductor device according to claim 14, wherein V of the above-mentioned general formula (10) includes a structure represented by the following general formula (9),

The semiconductor device according to claim 10, wherein V in the above general formula (10) is a divalent organic group with 1 to 40 carbon atoms. The semiconductor device according to claim 16, wherein V in the above general formula (10) is a divalent chain aliphatic group with 1 to 20 carbon atoms. The semiconductor device according to claim 3, wherein the polymer having a phenolic hydroxyl group comprises a novolak type phenolic resin. The semiconductor device according to claim 3, wherein the polymer having a phenolic hydroxyl group includes a phenol resin not having an unsaturated hydrocarbon group and a modified phenol resin having an unsaturated hydrocarbon group. The semiconductor device according to claim 1 or 2, wherein the redistribution layer includes: a first interlayer insulating film layer; a second interlayer insulating film layer; and an intermediate layer, which is the same as the above-mentioned A layer different from the first interlayer insulating film layer and the second interlayer insulating film layer is provided between the first interlayer insulating film layer and the second interlayer insulating film layer. The semiconductor device according to claim 20, wherein the first interlayer insulating film layer is in contact with the sealing material, and the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the first interlayer insulating film layer is 0.0150 or more. The semiconductor device according to claim 20, wherein the second interlayer insulating film layer has a composition different from that of the first interlayer insulating film layer. The semiconductor device according to claim 20, wherein the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the second interlayer insulating film layer is different from the in-plane refractive index and out-of-plane refractive index of the first interlayer insulating film layer The absolute value of the rate difference. The semiconductor device according to claim 1 or 2, wherein the semiconductor device is a fan-out wafer-level chip size package semiconductor device. The semiconductor device according to claim 1 or 2, wherein the surface of the interlayer insulating film of the redistribution layer The absolute value of the difference between the inner refractive index and the outer refractive index is 0.0155 or more. The semiconductor device according to claim 25, wherein the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the rewiring layer is 0.0160 or more. The semiconductor device according to claim 25, wherein the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the redistribution layer is 0.0165 or more. The semiconductor device according to claim 25, wherein the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the rewiring layer is 0.0170 or more. The semiconductor device according to claim 25, wherein the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the rewiring layer is 0.0200 or more. The semiconductor device according to claim 1 or 2, wherein the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the rewiring layer is 0.50 or less. The semiconductor device according to claim 30, wherein the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the rewiring layer is 0.40 or less. The semiconductor device according to claim 30, wherein the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the rewiring layer is 0.30 or less. A method of manufacturing a semiconductor device, characterized by comprising: a step of preparing a semiconductor wafer; a step of forming a rewiring layer having an area larger than the semiconductor wafer in plan view and including an interlayer insulating film; The step of coating the sealing material in direct contact with the film; and when the thickness of the above-mentioned interlayer insulating film is 10 μm, the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index is 0.0150 or more. The method for manufacturing a semiconductor device as claimed in item 33, which includes the step of forming an interlayer insulating film, which utilizes polyimide, polybenzo

A photosensitive resin composition comprising at least one compound of an azole or a polymer having a phenolic hydroxyl group forms the above-mentioned interlayer insulating film. The method of manufacturing a semiconductor device according to claim 34, wherein the step of forming the interlayer insulating film includes the step of using an additive such that the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film becomes 0.0150 or more. The adjusted photosensitive resin composition forms the interlayer insulating film. A semiconductor device, characterized by comprising: a semiconductor chip, a sealing material, and a rewiring layer having an area larger than the semiconductor chip in plan view; and the sealing material has a portion in direct contact with the interlayer insulating film of the rewiring layer, The etching rate of the interlayer insulating film of the rewiring layer is above 0.05 μm/min during the oxygen plasma treatment (treatment at 133W and 50Pa for 3 minutes). The semiconductor device according to claim 36, wherein the sealing material contains epoxy resin. The semiconductor device according to claim 36 or 37, wherein the above-mentioned interlayer insulating film contains polyimide, polybenzo

At least one of an azole and a polymer having a phenolic hydroxyl group. The semiconductor device according to claim 38, wherein the interlayer insulating film contains 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). Such as the semiconductor device of claim 39, wherein X in the above general formula (1) is a tetravalent organic group comprising an aromatic ring, and Y in ^the above general formula ( ¹ ) is a divalent organic group comprising an aromatic ring . Such as the semiconductor device of claim 39, wherein ^X in the above-mentioned general formula (1) includes at least one structure represented by the following general formula (2) to general formula (4),

(In the general formula (4), R ₉ is an oxygen atom, a sulfur atom, or a divalent organic group). Such as the semiconductor device of claim 41, wherein ^X in the above-mentioned general formula (1) comprises a structure represented by the following general formula (5),

Such as the semiconductor device of claim 39, wherein ^Y in the above-mentioned general formula (1) includes at least one structure represented by the following general formula (6) to general formula (8), [Chem. 20]

(R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are a hydrogen atom, a valent aliphatic group or a hydroxyl group with a carbon number of 1 to 5, which may be the same or different)

(R ₁₄ ~R ₂₁ are hydrogen atom, halogen atom, valent organic group with 1~5 carbon number or hydroxyl group, they can be different or the same)

(R ₂₂ is a divalent group, and R ₂₃ to R ₃₀ are hydrogen atoms, halogen atoms, aliphatic groups with 1 to 5 carbon atoms or hydroxyl groups, which may be the same or different). Such as the semiconductor device of claim 43, wherein ^Y in the above general formula (1) comprises a structure represented by the following general formula (9),

The semiconductor device as claimed in claim 38, wherein the above-mentioned polybenzo

Azole includes polybenzoic acid containing the structure of the following general formula (10):

azole,

(In general formula (10), U and V are divalent organic groups). The semiconductor device according to claim 45, wherein U in the above general formula (10) is a divalent organic group with 1 to 30 carbon atoms. The semiconductor device according to claim 46, wherein U in the above general formula (10) is a chain alkylene group having 1 to 8 carbon atoms and part or all of the hydrogen atoms are substituted with fluorine atoms. The semiconductor device according to claim 45, wherein V in the above general formula (10) is a divalent organic group containing an aromatic group. Such as the semiconductor device of claim 48, wherein V of the above-mentioned general formula (10) includes at least one structure represented by the following general formula (6) to general formula (8),

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

(R ₁₄ ~R ₂₁ are hydrogen atoms, halogen atoms, or valent organic groups with 1 to 5 carbon atoms, which may be different or the same)

(R ₂₂ is a divalent group, and R ₂₃ to R ₃₀ are hydrogen atoms, halogen atoms, or aliphatic groups with 1 to 5 carbon atoms, which may be the same or different). The semiconductor device according to claim 49, wherein V of the above-mentioned general formula (10) includes a structure represented by the following general formula (9),

The semiconductor device according to claim 45, wherein V in the above general formula (10) is a divalent organic group with 1 to 40 carbon atoms. The semiconductor device according to claim 51, wherein V in the above general formula (10) is a divalent chain aliphatic group with 1 to 20 carbon atoms. The semiconductor device according to claim 38, wherein the polymer having a phenolic hydroxyl group includes a novolac type phenolic resin. The semiconductor device according to claim 38, wherein the polymer having a phenolic hydroxyl group includes a phenol resin not having an unsaturated hydrocarbon group and a modified phenol resin having an unsaturated hydrocarbon group. The semiconductor device according to claim 36 or 37, wherein the above-mentioned redistribution layer includes: a first interlayer insulating film layer; a second interlayer insulating film layer; and an intermediate layer, which is the same as the above-mentioned A layer different from the first interlayer insulating film layer and the second interlayer insulating film layer is provided between the first interlayer insulating film layer and the second interlayer insulating film layer. The semiconductor device according to claim 55, wherein the first interlayer insulating film layer is in contact with the sealing material, and the etching rate of the first interlayer insulating film layer during oxygen plasma treatment is 0.05 μm/minute or more. The semiconductor device according to claim 55, wherein the second interlayer insulating film layer has a composition different from that of the first interlayer insulating film layer. The semiconductor device according to claim 55, wherein the etching rate of the oxygen plasma treatment of the second interlayer insulating film layer is different from the etching rate of the oxygen plasma treatment of the first interlayer insulating film layer. The semiconductor device according to claim 36 or 37, wherein the semiconductor device is a fan-out wafer-level chip size package semiconductor device. The semiconductor device according to claim 36 or 37, wherein the etching rate of the interlayer insulating film of the rewiring layer is 0.08 μm/minute or more during the oxygen plasma treatment. The semiconductor device according to claim 60, wherein the etching rate of the interlayer insulating film of the rewiring layer is 0.10 μm/minute or more during the oxygen plasma treatment. The semiconductor device according to claim 60, wherein the etching rate of the interlayer insulating film of the rewiring layer during the oxygen plasma treatment is 0.15 μm/minute or more. The semiconductor device according to claim 60, wherein the etching rate of the interlayer insulating film of the rewiring layer during the oxygen plasma treatment is 0.20 μm/minute or more. The semiconductor device according to claim 60, wherein the etching rate of the interlayer insulating film of the rewiring layer is 0.30 μm/minute or more during the oxygen plasma treatment. The semiconductor device according to claim 36 or 37, wherein the etching rate of the interlayer insulating film of the rewiring layer is 3.0 μm/minute or less during the oxygen plasma treatment. The semiconductor device according to claim 65, wherein the etching rate of the interlayer insulating film of the rewiring layer is 2.0 μm/minute or less during the oxygen plasma treatment. The semiconductor device according to claim 65, wherein the etching rate of the interlayer insulating film of the rewiring layer is 1.0 μm/minute or less during the oxygen plasma treatment. A method of manufacturing a semiconductor device, characterized by comprising: a step of preparing a semiconductor wafer; 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; The step of coating the sealing material in direct contact with the insulating film; and the etching rate of the above-mentioned interlayer insulating film during oxygen plasma treatment (treatment at 133W and 50Pa for 3 minutes) is above 0.05 μm/min. The method of manufacturing a semiconductor device as claimed in claim 68, which includes the step of forming an interlayer insulating film, which utilizes polyimide, polybenzo

A photosensitive resin composition comprising at least one compound of an azole or a polymer having a phenolic hydroxyl group forms the above-mentioned interlayer insulating film. The method for manufacturing a semiconductor device according to claim 69, wherein the step of forming the interlayer insulating film includes the step of using an additive-adjusted etching rate during the oxygen plasma treatment of the interlayer insulating film to be 0.05 μm/min or more. The said photosensitive resin composition forms the said interlayer insulating film.

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