JP2022123007A - Semiconductor device, manufacturing method thereof, and interlayer insulating film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a semiconductor device having excellent adhesion between a sealing material and an interlayer insulating film in a rewiring layer, and a manufacturing method of the same.

SOLUTION: A semiconductor device (1) includes a semiconductor chip (2), a sealing material (3) covering the semiconductor chip, and a rewiring layer (4) having a larger area than the semiconductor chip in plan view. The absolute value of a difference between the in-plane refractive index and the out-of-plane refractive index at a wavelength of 1310 nm of the interlayer insulating film (6) of the rewiring layer is less than 0.0150. The interlayer insulating film contains at least one selected from polyimide, polybenzoxazole, and a polymer having a phenolic hydroxyl group.

SELECTED DRAWING: Figure 1

COPYRIGHT: (C)2022,JPO&INPIT

Description

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

There are various methods for semiconductor package methods in semiconductor devices. As a semiconductor package method, for example, there is a packaging method in which a semiconductor chip is covered with a sealing material (mold resin) to form an element sealing material, and a rewiring layer is formed to electrically connect with the semiconductor chip. be. Among semiconductor package methods, a semiconductor package method called Fan-Out has become mainstream in recent years.

In a 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 is formed that extends to the semiconductor chip and encapsulant region. The rewiring layer is formed with a thin film thickness. Further, 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, Patent Document 1 below is known as a fan-out type semiconductor device.

JP 2011-129767 A

A fan-out type semiconductor device requires high adhesion between an interlayer insulating film in a rewiring layer and a sealing material. However, conventional fan-out semiconductor devices do not have sufficient adhesion between the interlayer insulating film in the rewiring layer and the encapsulant.

SUMMARY OF THE INVENTION It is an object of the present invention to provide a semiconductor device having excellent adhesion between an interlayer insulating film in a rewiring layer and a sealing material, and a method of manufacturing the same.

One aspect of the semiconductor device of the present invention includes a semiconductor chip, a sealing material covering the semiconductor chip, and a rewiring layer having an area larger than that of the semiconductor chip in a plan view, wherein the rewiring layer is provided with interlayer insulation. The absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the film at a wavelength of 1310 nm is less than 0.0150.

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

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

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

（一般式（１）中、Ｘ^１は４価の有機基であり、Ｙ^１は２価の有機基であり、ｍは１以上の整数である。）

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

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

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

（一般式（４）中、Ｒ₉は酸素原子、硫黄原子、または２価の有機基である。）

(In general formula ( ₄ ), R9 is an oxygen atom, a sulfur atom, or a divalent organic group.)

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

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

（Ｒ_１０、Ｒ_１１、Ｒ_１２及びＲ_１３は、水素原子、炭素数が１～５の１価の脂肪族基又は水酸基であり、同一であっても異なっていてもよい。）

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

（Ｒ_１４～Ｒ_２１は、水素原子、ハロゲン原子、炭素数が１～５の１価の有機基又は水酸基であり、互いに異なっていても、同一であってもよい。）

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

（Ｒ_２２は２価の基であり、Ｒ_２３～Ｒ_３０は、水素原子、ハロゲン原子、炭素数が１～５の１価の脂肪族基又は水酸基であり、同一であっても異なっていてもよい。）

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

In one aspect of the semiconductor device of the present invention, Y1 in General Formula ( ¹ ) preferably includes a structure represented by General Formula (9) below.

In one aspect of the semiconductor device of the present invention, the polybenzoxazole preferably contains polybenzoxazole having a structure represented by the following general formula (10).

（一般式（１０）中、ＵとＶは、２価の有機基である。）

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

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

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

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

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

（Ｒ_１０、Ｒ_１１、Ｒ_１２及びＲ_１３は、水素原子、炭素数が１～５の１価の脂肪族基であり、同一であっても異なっていてもよい。）

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

（Ｒ_１４～Ｒ_２１は、水素原子、ハロゲン原子、炭素数が１～５の１価の有機基であり、互いに異なっていても、同一であってもよい。）

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

（Ｒ_２２は２価の基であり、Ｒ_２３～Ｒ_３０は、水素原子、ハロゲン原子、炭素数が１～５の１価の脂肪族基であり、同一であっても異なっていてもよい。）

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

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

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 contains 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 phenolic resin having no unsaturated hydrocarbon group and a modified phenolic resin having an unsaturated hydrocarbon group.

In one aspect of the semiconductor device of the present invention, when the rewiring layer is viewed in cross section, the rewiring layer includes a first interlayer insulating film layer, a second interlayer insulating film layer, and a first interlayer insulating film layer. It is preferable to include an intermediate layer provided between the first interlayer insulating film layer and the second interlayer insulating film layer in a layer different from the insulating film layer and the second interlayer insulating film layer.

In one aspect of the semiconductor device of the present invention, the first interlayer insulating film layer is in contact with the sealing material, and the difference between the in-plane refractive index and the out-of-plane refractive index of the first interlayer insulating film layer is Preferably the absolute value is less than 0.0150.

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

In one aspect of the semiconductor device of the present invention, the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the second interlayer insulating film layer is equal to the in-plane refractive index of the first interlayer insulating film layer. It is preferably different from the absolute value of the outer refractive index difference.

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

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 0.0145 or less.

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

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

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

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

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

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

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

One aspect of the method for manufacturing a semiconductor device of the present invention includes a step of covering a semiconductor chip with a sealing material, and a step of forming a rewiring layer having an area larger than that of the semiconductor chip in plan view and including an interlayer insulating film. 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 is less than 0.0150.

In one aspect of the method for manufacturing a semiconductor device of the present invention, the interlayer insulating film is formed of a photosensitive resin composition capable of forming at least one compound of polyimide, polybenzoxazole, and a polymer having a phenolic hydroxyl group. It is preferable to include a film forming step.

In one aspect of the method for manufacturing a semiconductor device of the present invention, in the step of forming an interlayer insulating film, addition is performed so that the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film is less than 0.0150. It is preferable to include the step of forming the interlayer insulating film with the photosensitive resin composition adjusted with an agent.

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

It is a cross-sectional schematic diagram of the semiconductor device of this embodiment. 1 is a schematic plan view of a semiconductor device according to an embodiment; FIG. It is an example of the manufacturing process of the semiconductor device of this embodiment. FIG. 2 is a comparison diagram between a flip-chip BGA and a fan-out type WLCSP;

DESCRIPTION OF THE PREFERRED EMBODIMENTS An embodiment (hereinafter abbreviated as "embodiment") of a semiconductor device of the present invention will be described in detail below with reference to the drawings. It should be noted that the present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present invention.

(semiconductor device)
FIG. 1 is a schematic cross-sectional view of the semiconductor device of this embodiment. As shown in FIG. 1 , a semiconductor device (semiconductor IC) 1 includes a semiconductor chip 2 , a sealing material (molding resin) 3 covering the semiconductor chip 2 , and a rewiring layer that adheres to the semiconductor chip 2 and the sealing material 3 . 4 and .

As shown in FIG. 1, the encapsulant 3 covers the surface of the semiconductor chip 2 and has an area larger than the area of the semiconductor chip 2 in plan view (as viewed by arrow A).

The rewiring layer 4 includes a plurality of wirings 5 electrically connected to a plurality of terminals 2 a provided on the semiconductor chip 2 and an interlayer insulating film 6 filling the spaces between the wirings 5 . A plurality of terminals 2a provided on the semiconductor chip 2 and wirings 5 in the rewiring layer 4 are electrically connected. 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 entirely covered with an interlayer insulating film 6. As shown in FIG.

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

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

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

In this embodiment, the film thickness of the rewiring layer 4 can be set to approximately 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. Also, 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 (as viewed from arrow A), it is as shown in FIG. 2 below. FIG. 2 is a schematic plan view of the semiconductor device of this embodiment. Note that the sealing material 3 is omitted.

The semiconductor device 1 shown in FIG. 2 (see FIG. 1) is configured such that the area S1 of the rewiring layer 4 is larger than the area S2 of the semiconductor chip 2 . The area S1 of the rewiring layer 4 is not particularly limited, but from the viewpoint of increasing the number of external connection terminals, the area S1 of the rewiring layer 4 should be at least 1.05 times the area S2 of the semiconductor chip 2. is preferably 1.1 times or more, more preferably 1.2 times or more, and particularly preferably 1.3 times or more. Although there is no particular upper limit, the area S1 of the rewiring layer 4 may be 50 times or less, 25 times or less, or 10 times or less the area S2 of the semiconductor chip 2. It may be 5 times or less. In FIG. 2 , the area of the rewiring layer 4 covered with the semiconductor chip 2 is also included in the area S1 of the rewiring layer 4 .

Also, the outer shapes of the semiconductor chip 2 and the rewiring layer 4 may be the same or different. In FIG. 2, the external shapes of the semiconductor chip 2 and the rewiring layer 4 are similar rectangular shapes, but the shapes may be other than rectangular.

The rewiring layer 4 may be one layer, or may be multiple layers of two or more layers. The rewiring layer 4 includes wirings 5 and interlayer insulating films 6 filling spaces between the wirings 5 . may be included.

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

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

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

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

(Interlayer insulating film)
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 less than 0.0150. Here, the in-plane refractive index is the average value of the refractive indices at a wavelength of 1310 nm in the x and y directions of the interlayer insulating film 6 having a thickness z, a width x and a length y. The out-of-plane refractive index is the refractive index at a wavelength of 1310 nm in the z direction. Hereinafter, the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index at a wavelength of 1310 nm is defined as a refractive index difference.

The width x direction of the interlayer insulating film 6 is the planar direction of the interlayer insulating film 6 in FIG. 2, and the length y direction is the planar direction of the interlayer insulating film 6 in FIG. 2 and is perpendicular to the width x direction. and the thickness z direction is a direction perpendicular to the width x direction and the length y direction.

When the refractive index difference is less than 0.0150, the adhesion between the interlayer insulating film 6 and the sealing material 3 is excellent during high temperature treatment. The reason for this is not clear, but the inventors presume as follows.

In order to form the rewiring layer 4 in the manufacturing process of the fan-out type semiconductor device 1 (see FIG. 1), a photosensitive resin composition is applied onto the chip sealing body composed of the semiconductor chip 2 and the sealing material 3. apply. Subsequently, the photosensitive resin composition is exposed to light containing i-line. Thereafter, the photosensitive resin composition is developed and cured to selectively form a portion with and without a cured product of the photosensitive resin composition. A cured product of the photosensitive resin composition becomes the interlayer insulating film 6 . Wiring 5 is formed in a portion where there is no cured product of the photosensitive resin composition. Usually, the rewiring layer 4 is often multi-layered. That is, the photosensitive resin composition is further coated, exposed, developed, and cured on the interlayer insulating film 6 and the wiring 5 .

By the way, the process of forming the interlayer insulating film 6 and the wiring 5 may include a reflow process depending on the manufacturing method. In the reflow process, if the sealing material is heated for a long time, gas may be generated from the sealing material. When the interlayer insulating film 6 has molecular chains arranged neatly in the in-plane direction and is packed, that is, when the refractive index difference is large, the gas generated from the sealing material cannot pass through the interlayer insulating film 6, hard to escape. As a result, gas accumulates at the interface between the sealing material 3 and the interlayer insulating film 6, and the sealing material 3 and the interlayer insulating film 6 are likely to separate. In particular, epoxy resins tend to generate gas due to high-temperature heat history. Therefore, it is considered that the adhesion between the interlayer insulating film 6 and the sealing material 3 is lowered when the epoxy resin is used as the sealing material 3 .

The interlayer insulating film 6 of this embodiment has a small refractive index difference of less than 0.0150, and the molecular chains of the interlayer insulating film 6 are highly random. Therefore, in the present embodiment, even under conditions in which gas easily escapes from the interlayer insulating film 6 and gas is likely to be generated from the sealing material 3, peeling between the interlayer insulating film 6 and the sealing material 3 is minimized, and adhesion is achieved. presumed to be highly likely.

From the viewpoint of adhesion between the interlayer insulating film 6 and the sealing material 3 after high temperature treatment, the refractive index difference of the interlayer insulating film 6 is preferably less than 0.0150, preferably 0.0145 or less, and 0 0.0140 or less, preferably 0.0135 or less, preferably 0.0130 or less, preferably 0.0125 or less, preferably 0.0120 or less, and 0 0.0115 or less, preferably 0.0110 or less, preferably 0.0095 or less, preferably 0.0090 or less, preferably 0.0085 or less, 0 It is preferably 0.0080 or less, preferably 0.0075 or less, preferably 0.0070 or less, preferably 0.0065 or less, preferably 0.0060 or less, and 0 It is preferably 0.0055 or less, preferably 0.0050 or less, preferably 0.0045 or less, preferably 0.0040 or less, preferably 0.0035 or less, and 0 It is preferably 0.0030 or less, preferably 0.0025 or less, preferably 0.0020 or less, preferably 0.0010 or less.

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

Also, the interlayer insulating film 6 in the rewiring layer 4 may be multi-layered. That is, when the rewiring layer 4 is viewed in cross section, the rewiring layer 4 includes the first interlayer insulating film layer, the second interlayer insulating film layer, and the first interlayer insulating film layer and the second interlayer insulating film layer. An intermediate layer provided between the first interlayer insulating film layer and the second interlayer insulating film layer may be included in a layer different from the insulating film layer. The intermediate layer is the wiring 5, for example.

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

When the interlayer insulating film 6 is multi-layered, at least one layer of the interlayer insulating film 6 among the plurality of layers should have a refractive index difference of less than 0.0150. It is preferable that the interlayer insulating film 6 of the interlayer insulating film layer in contact with the sealing material 3 has a refractive index difference of less than 0.0150 because it is easily peeled off by gas. When the refractive index difference of the interlayer insulating film 6 of the interlayer insulating film layer in contact with the sealing material 3 is less than 0.0150, the gas generated in the sealing material 3 can be removed efficiently.

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

(Composition of interlayer insulating film)
Although the composition of the interlayer insulating film 6 is not particularly limited, it is preferably a film containing at least one compound selected from polyimide, polybenzoxazole, and polymers having phenolic hydroxyl groups, for example.

(Resin composition for forming interlayer insulating film)
The resin composition used for forming the interlayer insulating film 6 is not particularly limited as long as it is a photosensitive resin composition, and is selected from polyimide precursors, polybenzoxazole precursors, or polymers having phenolic hydroxyl groups. A photosensitive resin composition containing at least one compound is preferred. The resin composition used for forming the interlayer insulating film 6 may be liquid or film. 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 the present embodiment, the pattern obtained by exposing and developing the photosensitive resin composition is referred to as a relief pattern, and the relief pattern heat-cured is referred to as a cured relief pattern. This cured 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 polyamides and polyamic acid esters. For example, a polyamic acid ester containing a repeating unit represented by the following general formula (11) can be used as the polyamic acid ester.

Ｒ^１及びＲ^２は、それぞれ独立に、水素原子、炭素数１～３０の飽和脂肪族基、芳香族基、炭素炭素不飽和二重結合を有する一価の有機基、又は、炭素炭素不飽和二重結合を有する一価のイオンである。Ｘ^１は４価の有機基であり、Ｙ^１は２価の有機基であり、ｍは１以上の整数である。ｍは２以上が好ましく、５以上がより好ましい。

R ¹ and R ² are each independently a hydrogen atom, a saturated aliphatic group having 1 to 30 carbon atoms, an aromatic group, a monovalent organic group having a carbon-carbon unsaturated double bond, or a carbon-carbon unsaturated It is a singly charged ion with a double bond. 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 in the general formula (11) are present as monovalent cations, O is negatively charged (exists as —O 2 ^— ). Moreover, X ¹ and Y ¹ may contain a hydroxyl group.

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

（一般式（１２）中、Ｒ₃、Ｒ₄及びＲ₅は、それぞれ独立に、水素原子又は炭素数１～５の有機基であり、そしてｍ₁は、１～２０の整数である。）

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

（一般式（１３）中、Ｒ₆、Ｒ₇及びＲ₈は、それぞれ独立に、水素原子又は炭素数１～５の有機基であり、そしてｍ₂は、１～２０の整数である。）

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

A plurality of polyamic acid esters represented by the general formula (11) may be mixed. Polyamic acid esters obtained by copolymerizing polyamic acid esters represented by general formula (11) may also be used.

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

（一般式（４）中、Ｒ₉は酸素原子、硫黄原子、２価の有機基のいずれかである。）

(In general formula ( ₄ ), R9 is an oxygen atom, a sulfur atom, or a divalent organic group.)

R ₉ in 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 adhesion between the interlayer insulating film 6 and the sealing material 3, X1 is particularly preferably ^a tetravalent organic group having a structure represented by the following general formula (5).

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

（Ｒ_１０、Ｒ_１１、Ｒ_１２及びＲ_１３は、水素原子、炭素数が１～５の１価の脂肪族基であり、同一であっても異なっていてもよい。）

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

（Ｒ_１４～Ｒ_２１は、水素原子、ハロゲン原子、炭素数が１～５の１価の有機基であり、互いに異なっていても、同一であってもよい。）

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

（Ｒ_２２は２価の基であり、Ｒ_２３～Ｒ_３０は、水素原子、ハロゲン原子、炭素数が１～５の１価の脂肪族基であり、同一であっても異なっていてもよい。）

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

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

From the viewpoint of adhesion between the interlayer insulating film 6 and the sealing material 3, Y1 is particularly preferably ^a divalent organic group having a structure represented by the following general formula (9).

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

Examples of tetracarboxylic dianhydrides used as raw materials include pyromellitic anhydride, diphenyl ether-3,3′,4,4′-tetracarboxylic dianhydride, benzophenone-3,3′,4,4′- tetracarboxylic dianhydride, biphenyl-3,3′,4,4′-tetracarboxylic dianhydride, diphenylsulfone-3,3′,4,4′-tetracarboxylic dianhydride, diphenylmethane-3, 3′,4,4′-tetracarboxylic dianhydride, 2,2-bis(3,4-phthalic anhydride) propane, 2,2-bis(3,4-phthalic anhydride)-1,1, Examples include, but are not limited to, 1,3,3,3-hexafluoropropane. Moreover, these may be used alone or in combination of two or more.

Diamines used as raw materials include, for example, p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 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-aminophenoxy)phenyl]sulfone, bis[4-(3-aminophenoxy)phenyl]sulfone, 4,4-bis(4-aminophenoxy)biphenyl, 4 , 4-bis(3-aminophenoxy)biphenyl, bis[4-(4-aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl ) benzene, 1,3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4- aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl)propane, 2,2-bis[4-(4-aminophenoxy)phenyl)hexafluoropropane, 1,4-bis (3-aminopropyldimethylsilyl)benzene, ortho-tolysine sulfone, 9,9-bis(4-aminophenyl)fluorene and the like. Also, some of the hydrogen atoms on these benzene rings may be substituted. Moreover, these may be used alone or in combination of two or more.

In the synthesis of the polyamic acid ester (A), a method in which a tetracarboxylic acid diester obtained by performing an esterification reaction of a tetracarboxylic acid dianhydride, which will be described later, is usually subjected to a condensation reaction with a diamine can be preferably used. .

Alcohols used in the esterification reaction of the tetracarboxylic dianhydride are alcohols having an olefinic double bond. Specific examples include 2-hydroxyethyl methacrylate, 2-methacryloyloxyethyl alcohol, glycerin diacrylate, glycerin dimethacrylate and the like, but are not limited to these. These alcohols can be used singly or in combination of two or more.

A conventionally known method can be adopted as a specific method for synthesizing the polyamic acid ester (A) used in the present embodiment. Synthetic methods include, for example, the method disclosed in International Publication No. 00/43439 pamphlet. That is, a tetracarboxylic acid diester is once converted to a tetracarboxylic acid diester diacid chloride, the tetracarboxylic acid diester diacid chloride and a diamine are subjected to a condensation reaction in the presence of a basic compound, and polyamic acid ester (A) is obtained. can be exemplified. Moreover, the method of manufacturing polyamic-acid ester (A) by the method of subjecting a tetracarboxylic-acid diester and diamine to a condensation reaction in presence of an organic dehydrating agent can be mentioned.

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

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

(B1) Photoinitiator When the resin composition used for forming the interlayer insulating film 6 is a negative photosensitive resin, a photoinitiator is added. Photoinitiators include, for example, benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4′-methyldiphenyl ketone, dibenzyl ketone, and benzophenone derivatives such as fluorenone, 2,2′-diethoxyacetophenone, and 2 - acetophenone derivatives such as hydroxy-2-methylpropiophenone, thioxanthone derivatives such as 1-hydroxycyclohexylphenyl ketone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone and diethylthioxanthone, benzyl, benzyl dimethyl ketal and benzyl- benzyl derivatives such as β-methoxyethyl acetal; benzoin derivatives such as benzoin methyl ether; azides, 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-ethoxycarbonyl)oxime, 1-phenyl-3-ethoxypropanetrione-2 Oximes such as -(O-benzoyl)oxime, N-arylglycines such as N-phenylglycine, peroxides such as benzoyl peroxide, aromatic biimidazoles, and titanocenes are used. Among these, the above oximes are preferable from the viewpoint of photosensitivity.

The amount of these photoinitiators added is preferably 1 to 40 parts by mass, more preferably 2 to 20 parts by mass, per 100 parts by mass of the polyamic acid ester (A). By adding 1 part by mass or more of the photoinitiator to 100 parts by mass of the polyamic acid ester (A), the photosensitivity is excellent. Further, by adding 40 parts by mass or less, the 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 including a photoacid generator, an acid is generated in the ultraviolet-exposed area, and the solubility of the exposed area in an alkaline aqueous solution is increased. Thereby, it can be used as a positive photosensitive resin composition.

Examples of photoacid generators include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, iodonium salts and the like. Among these, the quinonediazide compound is preferably used because it exhibits an excellent dissolution inhibiting effect and enables a highly sensitive positive photosensitive resin composition to be obtained. Moreover, you may contain 2 or more types of photo-acid generators.

(C) Additives The difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film 6 can be adjusted by the type and amount of additive. When an additive having a bulky structure is used, the additive enters between the polymer molecular chains, disturbing the arrangement of the polymer molecular chains. Disordered alignment of polymer molecular chains reduces the intermolecular force between polymer molecular chains, making it easier for the molecular chains to be randomly aligned in the in-plane and out-of-plane directions, resulting in a difference in the in-plane and out-of-plane refractive indices. can reduce the difference. Additives having a bulky structure include, for example, additives having a bicyclo structure. Examples of additives that reduce the refractive index difference include bicyclooctane and adamantane. Moreover, the amount of the additive may be appropriately adjusted according to the target difference between the in-plane refractive index and the out-of-plane refractive index. In addition, the difference between the in-plane refractive index and the out-of-plane refractive index can be reduced by lowering the temperature at which the relief pattern is thermally cured.

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

(E) Others The polyimide precursor composition may contain a cross-linking agent. As the cross-linking agent, a cross-linking agent capable of cross-linking the photosensitive resin (A) or capable of forming a cross-linked network by itself is used when the polyimide precursor composition is exposed and developed and then heat-cured. be able to. By using a cross-linking agent, the heat resistance and chemical resistance of the cured film (interlayer insulating film) can be further enhanced.

In addition, it may contain a sensitizer for improving photosensitivity, an adhesion aid for improving adhesion to the substrate, and the like.

(developing)
After exposing the polyimide precursor composition, unnecessary portions are washed away with a developer. The developer to be used is not particularly limited, but in the case of a polyimide precursor composition that is developed with a solvent, N,N-dimethylformamide, dimethylsulfoxide, N,N-dimethylacetamide, N-methyl-2 Good solvents such as -pyrrolidone, cyclopentanone, γ-butyrolactone and acetic esters, mixed solvents of these good solvents with poor solvents such as lower alcohols, water and aromatic hydrocarbons are used. After development, rinsing with a poor solvent or the like is performed as necessary.

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

(thermosetting)
By heating the polyimide precursor composition after exposure after development, a polyimide precursor is ring-closed and a polyimide is formed. This polyimide becomes the cured relief pattern, that is, the interlayer insulating film 6 .

The heating temperature for thermosetting the polyimide precursor composition is not particularly limited, but generally, the lower the heat-hardening temperature, the smaller the refractive index difference tends to be. From the viewpoint of manifesting a refractive index difference of less than 0.0150 in the present embodiment, the heating temperature is preferably 200° C. or lower, preferably 180° C. or lower, and preferably 160° C. or lower.

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

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

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

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

（一般式（１４）中、ＵとＶは２価の有機基である。）

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

From the viewpoint of adhesion between the interlayer insulating film 6 and the sealing material 3, U is preferably a divalent organic group having 1 to 30 carbon atoms, and a chain alkylene group having 1 to 15 carbon atoms (provided that Hydrogen atoms of the chain alkylene may be substituted with halogen atoms) is more preferred, and a chain alkylene group having 1 to 8 carbon atoms and having some or all of the hydrogen atoms substituted with fluorine atoms is particularly preferred.

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

（Ｒ_１０、Ｒ_１１、Ｒ_１２及びＲ_１３は、水素原子、炭素数が１～５の１価の脂肪族基であり、同一であっても異なっていてもよい。）

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

（Ｒ_１４～Ｒ_２１は、水素原子、ハロゲン原子、炭素数が１～５の１価の有機基であり、互いに異なっていても、同一であってもよい。）

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

（Ｒ_２２は２価の基であり、Ｒ_２３～Ｒ_３０は、水素原子、ハロゲン原子、炭素数が１～５の１価の脂肪族基であり、同一であっても異なっていてもよい。）

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

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

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

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

A polybenzoxazole precursor can generally be synthesized from a dicarboxylic acid derivative and a hydroxy group-containing diamine. Specifically, it can be synthesized by converting a dicarboxylic acid derivative into a dihalide derivative and then reacting it with a diamine. A dichloride derivative is preferable as the dihalide derivative.

A dichloride derivative can be synthesized by reacting a dicarboxylic acid derivative with a halogenating agent. As the halogenating agent, thionyl chloride, phosphoryl chloride, phosphorus oxychloride, phosphorus pentachloride, and the like, which are used for the acid chloride reaction of a carboxylic acid, can be used.

As a method for synthesizing the dichloride derivative, a method of reacting a dicarboxylic acid derivative and the halogenating agent in a solvent, a method of reacting in an excess of the halogenating agent and then distilling off the excess can be used.

Examples of dicarboxylic acids used for 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, methylsuccinic 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, sebacic acid, hexadecafluorosebacic acid, 1,9-nonanedioic acid , dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, heneicosanedioic acid, docosanedioic acid, tricosanedioic acid, tetracosane diacid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, diglycolic acid, and the like. A mixture of these may be used.

Examples of hydroxy group-containing diamines include 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, and bis(3-amino-4-hydroxyphenyl). Propane, bis(4-amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, 2,2-bis(3-amino -4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-amino-3-hydroxyphenyl)-1,1,1,3,3,3 - hexafluoropropane and the like. A mixture of these may be used.

(B2) Photo-acid generator The photo-acid generator has the function of increasing the solubility of the light-irradiated portion in an alkaline aqueous solution. Examples of photoacid generators include diazonaphthoquinone compounds, aryldiazonium salts, diaryliodonium salts, triarylsulfonium salts and the like. Among these, diazonaphthoquinone compounds are preferred because of their high sensitivity.

(C) Additives Preferable types and amounts of additives are the same as those described in the polyimide precursor composition section.

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

(E) Others The polybenzoxazole precursor composition can contain a cross-linking agent, a sensitizer, an adhesion aid, a thermal acid generator, and the like.

(developing)
After exposing the polybenzoxazole precursor composition, unwanted portions are washed away with a developer. The developer to be used is not particularly limited, but alkaline aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine and tetramethylammonium hydroxide are preferred. It is mentioned as.

Although the positive-type polybenzoxazole precursor composition has been mainly described above, it may be a negative-type polybenzoxazole precursor composition.

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

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

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

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

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

Among these, phenolic resins are preferred, and novolak-type phenolic resins are particularly preferred, because of their low cost and small volume shrinkage during curing.

Phenolic resins are polycondensation products of phenol or its derivatives and aldehydes. Polycondensation is carried out in the presence of a catalyst such as an acid or base. A phenolic resin obtained when an acid catalyst is used is particularly called a novolak-type phenolic resin.

Phenol derivatives include, for example, phenol, cresol, ethylphenol, propylphenol, butylphenol, amylphenol, benzylphenol, adamantanephenol, benzyloxyphenol, xylenol, catechol, resorcinol, ethylresorcinol, hexylresorcinol, hydroquinone, pyrogallol, phlorolog Rucinol, 1,2,4-trihydroxybenzene, pararosolic acid, biphenol, bisphenol A, bisphenol AF, bisphenol B, bisphenol F, bisphenol S, dihydroxydiphenylmethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1, 4-bis(3-hydroxyphenoxybenzene), 2,2-bis(4-hydroxy-3-methylphenyl)propane, α,α'-bis(4-hydroxyphenyl)-1,4-diisopropylbenzene, 9, 9-bis(4-hydroxy-3-methylphenyl)fluorene, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2,2-bis(2-hydroxy-5-biphenylyl)propane, dihydroxy benzoic acid and the like.

Aldehyde compounds include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, pivalaldehyde, butyraldehyde, pentanal, hexanal, trioxane, glyoxal, cyclohexylaldehyde, diphenylacetaldehyde, ethylbutyraldehyde, benzaldehyde, glyoxylic acid, 5-norbornene-2. - carboxaldehyde, malondialdehyde, succindialdehyde, glutaraldehyde, salicylaldehyde, naphthaldehyde, terephthalaldehyde and the like.

The component (A) preferably contains (a) a phenolic resin having no unsaturated hydrocarbon group and (b) a modified phenolic resin having an unsaturated hydrocarbon group. It is more preferable that the component (b) is further modified by a reaction between a phenolic hydroxyl group and a polybasic acid anhydride.

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

(b) Modified phenolic resin having an unsaturated hydrocarbon group is generally a compound having phenol or a derivative thereof and an unsaturated hydrocarbon group (preferably those having 4 to 100 carbon atoms) (hereinafter sometimes simply referred to as "unsaturated (hereinafter referred to as "unsaturated hydrocarbon group-modified phenol derivative") and condensation polymerization products of aldehydes, or phenolic resin and unsaturated hydrocarbon It is a reaction product with a group-containing compound.

The phenol derivative referred to herein can be the same as the phenol derivative described above as a raw material for the phenol resin as the component (A).

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

Examples of unsaturated hydrocarbon group-containing compounds include unsaturated hydrocarbons having 4 to 100 carbon atoms, polybutadiene having a carboxyl group, epoxidized polybutadiene, linolyl alcohol, oleyl alcohol, unsaturated fatty acids, and unsaturated fatty acid esters. . Suitable unsaturated fatty acids include crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, erucic acid, nervonic acid, linoleic acid, α-linolenic acid, eleostearic acid, stearidone. acids, arachidonic acid, eicosapentaenoic acid, sardine acid and docosahexaenoic acid. Among these, esters of unsaturated fatty acids having 8 to 30 carbon atoms and monohydric to trihydric alcohols having 1 to 10 carbon atoms are particularly preferable, and unsaturated fatty acids having 8 to 30 carbon atoms and trihydric alcohols are more preferable. Esters with glycerin are particularly preferred.

Esters of unsaturated fatty acids having 8 to 30 carbon atoms and glycerin are commercially available as vegetable oils. Vegetable oils include non-drying oils with an iodine value of 100 or less, semi-drying oils with an iodine value of more than 100 and less than 130, and drying oils with an iodine value of 130 or more. Non-drying oils include, for example, olive oil, morning glory seed oil, cashew seed oil, turmeric oil, camellia oil, castor oil and peanut oil. Semi-drying oils include, for example, corn oil, cottonseed oil and sesame oil. Drying oils include, for example, tung oil, linseed oil, soybean oil, walnut oil, safflower oil, sunflower oil, perilla oil and mustard oil. Moreover, you may use the processed vegetable oil obtained by processing these vegetable oils.

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

These unsaturated hydrocarbon group-containing compounds are used singly or in combination of two or more.

In preparing the component (b), first, the phenol derivative and the unsaturated hydrocarbon group-containing compound are reacted to produce an unsaturated hydrocarbon group-modified phenol derivative. The reaction is preferably carried out at 50-130°C. From the viewpoint of improving the flexibility of the cured film (resist pattern), the reaction ratio between the phenol derivative and the unsaturated hydrocarbon group-containing compound is 1 to 100 parts by mass of the unsaturated hydrocarbon group-containing compound per 100 parts by mass of the phenol derivative. It is preferably parts by mass, more preferably 5 to 50 parts by mass. If the unsaturated hydrocarbon group-containing compound is less than 1 part by mass, the cured film tends to be less flexible, and if it exceeds 100 parts by mass, the cured film tends to be less heat resistant. In the above reaction, p-toluenesulfonic acid, trifluoromethanesulfonic acid or the like may be used as a catalyst, if necessary.

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

The reaction between the aldehyde and the unsaturated hydrocarbon group-modified phenol derivative is a polycondensation reaction, and conventionally known synthesis conditions for phenol resins can be used. The reaction is preferably carried out in the presence of a catalyst such as acid or base, more preferably using an acid catalyst. Acid catalysts include, for example, hydrochloric acid, sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid and oxalic acid. These acid catalysts can be used singly or in combination of two or more.

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

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

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

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

The reaction between the phenol resin and the unsaturated hydrocarbon group-containing compound is usually preferably carried out at 50 to 130°C. In addition, from the viewpoint of improving the flexibility of the cured film (resist pattern), the reaction ratio between the phenolic resin and the unsaturated hydrocarbon group-containing compound is 1 part of the unsaturated hydrocarbon group-containing compound per 100 parts by mass of the phenolic resin. It is preferably up to 100 parts by mass, more preferably 2 to 70 parts by mass, even more preferably 5 to 50 parts by mass. If the unsaturated hydrocarbon group-containing compound is less than 1 part by mass, the flexibility of the cured film tends to decrease, and if it exceeds 100 parts by mass, the possibility of gelation during the reaction tends to increase and curing The heat resistance of the film tends to decrease. At this time, if necessary, p-toluenesulfonic acid, trifluoromethanesulfonic acid, or the like may be used as a catalyst. Solvents such as toluene, xylene, methanol, and tetrahydrofuran can be used for the reaction.

The phenolic hydroxyl groups remaining in the phenol resin modified by the unsaturated hydrocarbon group-containing compound produced by the above method are further reacted with a polybasic acid anhydride. As a result, an acid-modified phenolic resin can be used as the component (b). Acid modification with a polybasic acid anhydride introduces a carboxy group, further improving the solubility of component (b) in an alkaline aqueous solution (developer).

The polybasic acid anhydride is not particularly limited as long as it has an acid anhydride group formed by dehydration condensation of the carboxy groups of a polybasic acid having a plurality of carboxy groups. Examples of polybasic acid anhydrides include phthalic anhydride, succinic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride. Acids, dibasic acid anhydrides such as methylhexahydrophthalic anhydride, nadic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride and trimellitic anhydride, biphenyl Tetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, pyromellitic anhydride and benzophenonetetracarboxylic dianhydride Aromatic tetrabasic acid dianhydrides such as anhydrides can be mentioned. You may use these individually by 1 type or in combination of 2 or more types. Among these, the polybasic acid anhydride is preferably a dibasic acid anhydride, and more preferably one or more selected from the group consisting of tetrahydrophthalic anhydride, succinic anhydride and hexahydrophthalic anhydride. . In this case, there is an advantage that a resist pattern having a better shape can be formed.

In addition, (A) the alkali-soluble resin having a phenolic hydroxyl group can further contain a phenolic resin that has been acid-modified by reacting with a polybasic acid anhydride. Since the component (A) contains a phenolic resin modified with a polybasic acid anhydride, the solubility of the component (A) in an alkaline aqueous solution (developer) is further improved.

Examples of the polybasic acid anhydride include phthalic anhydride, succinic anhydride, octenyl succinic anhydride, pentadodecenyl succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methyltetrahydroanhydride. dibasic acid anhydrides such as phthalic acid, methylhexahydrophthalic anhydride, nadic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride, and trimellitic anhydride; Biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid Aliphatic such as dianhydride, aromatic tetrabasic acid dianhydride, and the like. You may use these individually by 1 type or in combination of 2 or more types. Among these, the polybasic acid anhydride is preferably a dibasic acid anhydride, for example, one or more selected from the group consisting of tetrahydrophthalic anhydride, succinic anhydride and hexahydrophthalic anhydride. more preferred.

(B2) Photoacid Generator Examples of photoacid generators include diazonaphthoquinone compounds, aryldiazonium salts, diaryliodonium salts, and triarylsulfonium salts. Among these, diazonaphthoquinone compounds are preferred because of their high sensitivity.

(C) Additives Preferable types and amounts of additives are the same as those described in the polyimide precursor composition section.

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

(E) Others Thermal cross-linking agents, sensitizers, adhesion aids, dyes, surfactants, dissolution accelerators, cross-linking accelerators and the like can be included. Among these, by containing a thermal cross-linking agent, when the photosensitive resin film after pattern formation is heated and cured, the thermal cross-linking agent component reacts with the component (A) to form a crosslinked structure. This makes it possible to cure at a low temperature, and prevents fragility of the film and melting of the film. Specifically, a compound having a phenolic hydroxyl group, a compound having a hydroxymethylamino group, and a compound having an epoxy group can be preferably used as the thermal cross-linking agent component.

(developing)
After exposing the polymer having phenolic hydroxyl groups, unwanted portions are washed away with a developer. The developer to be used is not particularly limited, but examples thereof include alkaline aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide (TMAH). is preferably used.

(thermosetting)
After development, the polymers having phenolic hydroxyl groups are thermally crosslinked by heating 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 thermosetting the polymer having a phenolic hydroxyl group is not particularly limited, but from the viewpoint of the influence on other members, the heating temperature is preferably low. The heating temperature is preferably 250° C. or lower, more preferably 230° C. or lower, more preferably 200° C. or lower, and particularly preferably 180° C. or lower.

(Method for manufacturing semiconductor device)
A method for manufacturing a semiconductor device according to this embodiment will be described with reference to FIG. FIG. 3 shows an example of the manufacturing process of the semiconductor device of this embodiment. In FIG. 3A, a pre-processed wafer 10 is prepared. Then, in FIG. 3B, the pre-processed wafer 10 is diced to form a plurality of semiconductor chips 2 . The semiconductor chip 2 may be a purchased item. The semiconductor chips 2 prepared in this manner are attached on a support 11 at predetermined intervals, as shown in FIG. 3C.

Subsequently, a mold resin 12 is applied from the semiconductor chip 2 to the support 11, and the semiconductor chip 2 and the support 11 are molded and sealed as shown in FIG. 3D. Subsequently, the support 11 is peeled off, and the mold resin 12 is turned over (see FIG. 3E). As shown in FIG. 3E, the semiconductor chip 2 and the mold resin 12 appear on substantially the same plane. Subsequently, in the step shown in FIG. 3F, a photosensitive resin composition 13 is applied onto the semiconductor chip 2 and the mold resin 12 . Then, the applied photosensitive resin composition 13 is exposed and developed to form a relief pattern (relief pattern forming step). Incidentally, the photosensitive resin composition 13 may be either positive type or negative type. Furthermore, the relief pattern is heated to form a cured relief pattern (interlayer insulating film forming step). Further, wiring is formed at locations where no cured relief pattern is to be formed (wiring forming step).

In this embodiment, the relief pattern forming process, the interlayer insulating film forming process, and the wiring forming process are combined into a rewiring layer forming process for forming a rewiring layer connected to the semiconductor chip 2 .

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

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

In this embodiment, the refractive index difference of the cured relief pattern (interlayer insulating film) formed through the above steps can be less than 0.0150. Here, the i-line transmittance of the interlayer insulating film can be adjusted by the amount of additive.

In the present embodiment, in the step of forming an interlayer insulating film, the interlayer insulating film may be formed from a photosensitive resin composition capable of forming at least one compound of polyimide, polybenzoxazole, and a polymer having a phenolic hydroxyl group. preferable.

EXAMPLES Examples carried out to clarify the effects of the present invention will be described below. In the examples, the following materials and measurement methods were used.

EXAMPLES Examples carried out to clarify the effects of the present invention will be described below.

(Polymer A-1: Synthesis of polyimide precursor)
4,4′-Oxydiphthalic dianhydride (ODPA) was placed in a 2-liter separable flask as a tetracarboxylic dianhydride. Further, 2-hydroxyethyl methacrylate (HEMA) and γ-butyrolactone were added and stirred at room temperature, and pyridine was added while stirring to obtain a reaction mixture. After the end of heat generation due to the reaction, the mixture was allowed to cool to room temperature and allowed to stand for 16 hours.

Next, under ice-cooling, a solution of dicyclohexylcarbodiimide (DCC) dissolved in γ-butyrolactone was added to the reaction mixture over 40 minutes while stirring. Subsequently, a suspension of 4,4'-diaminodiphenyl ether (DADPE) as a diamine in γ-butyrolactone was added with stirring over 60 minutes. Further, after stirring at room temperature for 2 hours, ethyl alcohol was added and stirred for 1 hour, then γ-butyrolactone was added. A precipitate formed in the reaction mixture was removed by filtration to obtain a reaction liquid.

The resulting reaction solution was added to ethyl alcohol to form a precipitate consisting of a crude polymer. The resulting crude polymer was separated by filtration and dissolved in tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was added dropwise to water to precipitate the polymer, and the obtained precipitate was filtered off and dried in vacuum to obtain a powdery polymer (polyimide precursor (polymer A-1)). . The masses of the compounds used in Component A-1 are shown in Table 1 below.

(Synthesis of polymers A-2 to A-4)
Except for changing the tetracarboxylic dianhydride and diamine as shown in Table 1 below, the reaction was performed in the same manner as described for the polymer A-1 described above to obtain polyimide precursors (polymers A-2 to A-4). got

(Polymer B-1: Synthesis of polybenzoxazole precursor)
A 0.5-liter flask equipped with a stirrer and a thermometer was charged with 15.48 g of 4,4′-diphenyletherdicarboxylic acid as a dicarboxylic acid and N-methylpyrrolidone. After cooling the flask to 5° C., thionyl chloride was added dropwise and allowed to react for 30 minutes to obtain a solution of dicarboxylic acid chloride. Then, N-methylpyrrolidone was charged into 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 bisaminophenol and 2.18 g of m-aminophenol, pyridine was added. Then, while maintaining the temperature at 0 to 5° C., the dicarboxylic acid chloride solution was added dropwise over 30 minutes, and then stirring was continued for 30 minutes. The solution was poured into 3 liters of water, and the precipitate was collected, washed with pure water three times, and dried under reduced pressure to obtain a polymer (polybenzoxazole precursor (polymer B-1)). The masses of the compounds used in Polymer B-1 are shown in Table 1 below.

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

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

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

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

[Examples 1-11, Comparative Examples 1-2]
A solution of a photosensitive resin composition was obtained by blending as shown in Table 2 below. In addition, the unit of Table 2 is a mass part.

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

The prepared photosensitive resin composition was subjected to (1) a refractive index difference measurement test, (2) a reflow resistance test of the encapsulant, and (3) an adhesion test with the encapsulant. The results of each test are shown in Table 3 below.

(1) Refractive Index Difference Measurement Test Using the photosensitive resin compositions prepared in Examples and Comparative Examples, semiconductor devices of fan-out wafer level chip size package type were prepared. An interlayer insulating film having a thickness of 10 μm was taken out as cleanly as possible from the manufactured semiconductor device. Using a prism coupler (PC-2010) manufactured by METRICON, 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 interlayer insulating film thus taken out.

(2) Reflow Resistance Test of Encapsulating Material R4000 series manufactured by Nagase Chemtex Co., Ltd. was prepared as an epoxy-based encapsulating material. Next, the sealing material was spin-coated on the aluminum-sputtered silicone wafer to a thickness of about 150 μm, and thermally cured at 130° C. to cure the epoxy-based sealing material.

The photosensitive resin compositions prepared in Examples and Comparative Examples were coated on the epoxy-based cured film so that the final film thickness was 10 μm. The entire surface of the coated photosensitive resin composition was exposed under the exposure conditions of 200 mJ/cm ² for Examples 1 to 4 and 10 and Comparative Example 1, and 500 mJ/cm ² for Examples 5 to 7 and 11 and Comparative Example 2. After that, it was heat-cured at 150° C. for 4 hours to prepare a first cured film having a thickness of 10 μm.

The photosensitive resin composition used in forming the cured film of the first layer is applied onto the cured film of the first layer, and the entire surface is exposed to light under the same conditions as when forming the cured film of the first layer, followed by thermal curing. , to form a second cured film having a thickness of 10 μm.

Under simulated solder reflow conditions using a mesh belt type continuous firing furnace (manufactured by Koyo Thermo Systems Co., Ltd., model name 6841-20AMC-36), the test piece after the formation of the second layer of cured film was subjected to peak temperature in a nitrogen atmosphere. Heated to 260°C. The simulated reflow conditions refer to the solder reflow conditions set forth in Section 7.6 of IPC/JEDEC J-STD-020A, which is the standard of the US semiconductor industry group regarding evaluation methods for semiconductor devices, and the melting point of the solder is adjusted. Normalized assuming a high temperature of 220°C.

After cutting the cross section of the cured film after treatment under the simulated reflow conditions with an FIB device (manufactured by JEOL Ltd., JIB-4000), the degree of deterioration was evaluated by checking for the presence or absence of voids in the epoxy portion. . A sample with no voids was rated as ◯, and a sample with at least one void was rated as x.

(3) Adhesion test with sealing material A pin is placed on the photosensitive resin cured film of the sample prepared in the test of (2), and the adhesion is measured using a take-off tester (Sebastian 5, manufactured by Quad Group). did the test.
Evaluation: Adhesion strength of 70 MPa or more ・・・・・・・・ Adhesion ◎
50 MPa or more - less than 70 MPa ... Adhesion ○
30 MPa or more and less than -50 MPa ... Adhesion △
Less than 30 MPa ・・・・・・・Adhesion ×

As is clear from Tables 3 and 4, from the results of the tests (1) to (3) performed on the photosensitive resin compositions of Examples 1 to 11, when the refractive index difference is less than 0.0150, sealing In the reflow resistance test of the sealing material, no voids were found in the epoxy portion, and in the adhesion test with the sealing material, it was confirmed that the adhesion strength was evaluated as either ⊚, ◯, or Δ.

On the other hand, as is clear from Tables 3 and 4, from the results of the tests (1) to (3) performed on the photosensitive resin compositions of Comparative Examples 1 and 2, when the refractive index difference exceeds 0.0150, In the reflow resistance test of the encapsulant, voids were found in the epoxy portion, and in the adhesion test with the encapsulant, it was confirmed that the evaluation of the adhesion strength was x.

Further, using the photosensitive resin compositions of Examples 1 to 11, a fan-out type wafer level chip size package type semiconductor device containing an epoxy resin as a 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 rewiring layer connected to the semiconductor chip, particularly to a fan-out type wafer level chip size package type semiconductor device.

1 semiconductor device 2 semiconductor chip 3 sealing material 4 rewiring layer 5 wiring 6 interlayer insulating film 7 external connection terminal 10 wafer 11 support 12 mold resin 13 photosensitive resin composition

One aspect of the semiconductor device of the present invention includes a semiconductor chip, a sealing material in contact with the semiconductor chip, and a rewiring layer having a larger area than the semiconductor chip in plan view, and the sealing material It has a portion in direct contact with the interlayer insulating film of the rewiring layer, and 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 of the interlayer insulating film of the rewiring layer is less than 0.0150. Characterized by

One aspect of the present invention is an interlayer insulating film in a semiconductor device comprising a semiconductor chip, a sealing material in contact with the semiconductor chip, and a rewiring layer having a larger area than the semiconductor chip in plan view, wherein the rewiring 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 of the interlayer insulating film of the rewiring layer, which is in direct contact with the encapsulating material and is used for forming a layer. Characterized by a value less than 0.0150.

Claims (36)

a semiconductor chip;
a sealing material covering the semiconductor chip;
a rewiring layer having a larger area than the semiconductor chip in plan view,
A semiconductor device, wherein 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 of the interlayer insulating film of the rewiring layer is less than 0.0150. 2. The semiconductor device according to claim 1, wherein said sealing material is in direct contact with said interlayer insulating film. 3. The semiconductor device according to claim 1, wherein the sealing material contains epoxy resin. 4. The semiconductor device according to claim 1, wherein said interlayer insulating film contains at least one selected from polyimide, polybenzoxazole, and a polymer having a phenolic hydroxyl group. 5. The semiconductor device according to claim 4, wherein the interlayer insulating film contains polyimide having a structure represented by the following general formula (1).

(In 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.) X ¹ in the general formula (1) is a tetravalent organic group containing an aromatic ring,
6. The semiconductor device according to claim 5, wherein Y1 in said general formula ( ¹ ) is a divalent organic group containing an aromatic ring. The semiconductor according to claim 5 or 6, wherein X ¹ in the general formula (1) includes at least one structure represented by the following general formulas (2) to (4): Device.

(In general formula ( ₄ ), R9 is an oxygen atom, a sulfur atom, or a divalent organic group.) 8. The semiconductor device according to claim 7, wherein X1 in the general formula ( ¹ ) includes a structure represented by the following general formula (5).

Any one of claims 5 to 8, wherein Y ¹ in the general formula (1) includes at least one structure represented by the following general formulas (6) to (8) The semiconductor device described.

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

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

(R ₂₂ is a divalent group, and R ₂₃ to R ₃₀ are a hydrogen atom, a halogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group, and may be the same or different. is also good.) 10. The semiconductor device according to claim 9, wherein Y1 in the general formula ( ¹ ) includes a structure represented by the following general formula (9).

5. The semiconductor device according to claim 4, wherein the polybenzoxazole contains polybenzoxazole having a structure represented by the following general formula (10).

(In general formula (10), U and V are divalent organic groups.) 12. The semiconductor device according to claim 11, wherein U in said general formula (10) is a divalent organic group having 1 to 30 carbon atoms. 13. The semiconductor device according to claim 12, wherein U in the general formula (10) is a chain alkylene group having 1 to 8 carbon atoms and having some or all of the hydrogen atoms substituted with fluorine atoms. . 14. The semiconductor device according to claim 11, wherein V in said general formula (10) is a divalent organic group containing an aromatic group. 15. The semiconductor device according to claim 14, wherein 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 and R ₁₃ are hydrogen atoms, monovalent aliphatic groups having 1 to 5 carbon atoms, and may be the same or different.)

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

(R ₂₂ is a divalent group, and R ₂₃ to R ₃₀ are a hydrogen atom, a halogen atom, or a monovalent aliphatic group having 1 to 5 carbon atoms, which may be the same or different. .) 16. The semiconductor device according to claim 15, wherein V in the general formula (10) includes a structure represented by the following general formula (9).

14. The semiconductor device according to claim 11, wherein V in the general formula (10) is a divalent organic group having 1 to 40 carbon atoms. 18. The semiconductor device according to claim 17, wherein V in said general formula (10) is a divalent chain aliphatic group having 1 to 20 carbon atoms. 5. The semiconductor device according to claim 4, wherein the polymer having a phenolic hydroxyl group contains a novolak type phenolic resin. 5. The semiconductor device according to claim 4, wherein said polymer having a phenolic hydroxyl group includes a phenolic resin having no unsaturated hydrocarbon group and a modified phenolic resin having an unsaturated hydrocarbon group. When the rewiring layer is viewed cross-sectionally, the rewiring layer includes a first interlayer insulating film layer, a second interlayer insulating film layer, and the first interlayer insulating film layer and the second interlayer insulating film layer. 21. The method according to any one of claims 1 to 20, further comprising an intermediate layer provided between the first interlayer insulating film layer and the second interlayer insulating film layer in a layer different from the film layer. 1. The semiconductor device according to claim 1. The first interlayer insulating film layer is in contact with the sealing material, and the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the first interlayer insulating film layer is less than 0.0150. 22. The semiconductor device according to claim 21, characterized by: 23. The semiconductor device according to claim 21, wherein said second interlayer insulating film layer has a composition different from that of said first interlayer insulating film layer. The absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the second interlayer insulating film layer is different from the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the first interlayer insulating film layer. 24. The semiconductor device according to claim 21, wherein: 25. The semiconductor device according to claim 1, wherein said semiconductor device is a fan-out type wafer level chip size package type semiconductor device. 26. The semiconductor device according to claim 1, wherein the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the rewiring layer is 0.0145 or less. . 27. The semiconductor device according to claim 26, 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 said rewiring layer is 0.0140 or less. 27. The semiconductor device according to claim 26, 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 said rewiring layer is 0.0135 or less. 27. The semiconductor device according to claim 26, 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 said rewiring layer is 0.0130 or less. 27. The semiconductor device according to claim 26, 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 said rewiring layer is 0.0120 or less. 31. The semiconductor device according to claim 1, wherein the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film of the rewiring layer is 0.0005 or more. . 32. The semiconductor device according to claim 31, 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 said rewiring layer is 0.0010 or more. 32. The semiconductor device according to claim 31, wherein an absolute value of a difference between an in-plane refractive index and an out-of-plane refractive index of said interlayer insulating film of said rewiring layer is 0.0015 or more. a step of covering the semiconductor chip with a sealing material;
forming a rewiring layer having an area larger than that of the semiconductor chip in plan view and including an interlayer insulating film;
A method of manufacturing a semiconductor device, 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 is less than 0.0150. 34. The step of forming the interlayer insulating film from a photosensitive resin composition capable of forming at least one compound of polyimide, polybenzoxazole, and a polymer having a phenolic hydroxyl group. A method for manufacturing the semiconductor device according to 1. In the interlayer insulating film forming step, the photosensitive resin composition is adjusted with an additive so that the absolute value of the difference between the in-plane refractive index and the out-of-plane refractive index of the interlayer insulating film is less than 0.0150. 36. The method of manufacturing a semiconductor device according to claim 35, further comprising the step of forming an interlayer insulating film.

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