JP2024037691A - Semiconductor device and manufacturing method of them - Google Patents

Abstract

To provide a semiconductor device that includes an insulation layer with an excellent developing property, and has an excellent adhesion property in the insulation layer and an intermediate layer after a green laser irradiation.SOLUTION: A semiconductor device 1 comprises: a semiconductor chip 2; a sealing material 3 contacted to the semiconductor chip 2; and a re-wiring layer 4 that is wired to at least one surface side of the semiconductor chip 2 and the sealing material 3, and of which an area is larger than that of the semiconductor chip 2 in a thickness direction flat surface. The re-wiring layer 4 contains: an intermediate layer electrically connected to the semiconductor chip 2, and an insulation layer 6 contacted to the intermediate layer. The insulation layer 6 has a single layer structure or a multi-layer structure. In at least one layer constructing their layer structure, a region 6a that a transmission coefficient in 532nm when the layer is converted into a 10 μm in a thickness is 0.5 to 50% is contained.SELECTED DRAWING: Figure 1

Description

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

There are various methods for packaging semiconductors in semiconductor devices. One example is a method in which a semiconductor chip is covered with a sealing material, and a rewiring layer electrically connected to the semiconductor chip is formed over the semiconductor chip and the sealing material. Among these, in recent years, a semiconductor packaging method called Fan-Out has become mainstream.

In the fan-out type semiconductor packaging method, a chip sealing body having a semiconductor chip and a sealing material in contact with the semiconductor chip is formed, and a rewiring layer is formed over the chip sealing body. Since the rewiring layer is formed over the sealing material, the area of the rewiring layer can be secured, and therefore, when forming external connection terminals on the rewiring layer, it is easy to form a large number of external connection terminals. As a fan-out type semiconductor device, the content described in Patent Document 1 is known.

Japanese Patent Application Publication No. 2011-129767

The rewiring layer includes an intermediate layer that is electrically connected to the semiconductor chip and an insulating layer that is in contact with the intermediate layer, and the insulating layer is patterned using a lithography technique. Therefore, the insulating layer is required to have a certain level of developability.

Further, electronic components (DRAM, external connection terminals, etc.) may be provided in the rewiring layer. Therefore, the rewiring layer is irradiated with a laser having a predetermined wavelength, and as a result, alignment marks for positioning electronic components may be printed on the rewiring layer. The wavelength of the laser for printing the alignment mark may be 355 nm or 532 nm. In recent years, there has been a demand for printing alignment marks using a 532 nm wavelength laser (green laser) with low output energy.

However, when printing alignment marks on the redistribution layer using a green laser, there is a problem in that the intermediate layer and the insulating layer may peel off depending on the irradiation conditions of the green laser. Regarding printing of alignment marks, there may be a trade-off in that if an attempt is made to suppress peeling of the intermediate layer and the insulating layer, suitable printing performance on the redistribution layer using a green laser cannot be achieved.

Therefore, the present invention aims to provide a semiconductor device having an insulating layer with excellent developability and good adhesion between the insulating layer and the intermediate layer after green laser irradiation, and a method for manufacturing the same. purpose.

（式（４）中、Ｒ₉は、酸素原子、硫黄原子、又は２価の有機基である。）
で表される少なくとも１つの構造を含む、項目１３又は１４に記載の半導体装置。
［１６］
前記式（１）のＸ¹は、下記一般式（５）：

で表される構造を含む、項目１５に記載の半導体装置。
［１７］
前記式（１）のＹ¹は、下記一般式（６）～（８）：
（式中、Ｒ₁₀～Ｒ₁₃は、それぞれ独立に、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る。）
（式中、Ｒ₁₄～Ｒ₂₁は、それぞれ独立に、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る。）
（式中、Ｒ₂₂は、２価の基又は酸素原子であり、Ｒ₂₃～Ｒ₃₀は、それぞれ独立に、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る。）
で表される少なくとも１つの構造を含む、項目１３～１６のいずれか１項に記載の半導体装置。
［１８］
前記式（１）のＹ¹は、下記一般式（９）：
で表される構造を含む、項目１３～１７のいずれか１項に記載の半導体装置。
［１９］
前記絶縁層は、以下の一般式（１０）：

（式中、ＵとＶは、２価の有機基である。）
の構造を含む前記ポリベンゾオキサゾールを含む、項目１２に記載の半導体装置。
［２０］
前記式（１０）のＵは、炭素数１～３０の２価の有機基である、項目１９に記載の半導体装置。
［２１］
前記式（１０）のＵは、炭素数１～８、かつ、水素原子の一部又は全部がフッ素原子で置換された鎖状アルキレン基である、項目１９又は２０に記載の半導体装置。
［２２］
前記式（１０）のＶは、芳香族基を含む２価の有機基である、項目１９～２１のいずれか１項に記載の半導体装置。
［２３］
前記式（１０）のＶは、下記一般式（６）～（８）：
（式中、Ｒ₁₀～Ｒ₁₃は、それぞれ独立に、水素原子、炭素数が１～５の１価の脂肪族基である。）
（式中、Ｒ₁₄～Ｒ₂₁は、それぞれ独立に、水素原子、ハロゲン原子、炭素数が１～５の１価の有機基である。）
（式中、Ｒ₂₂は、２価の基又は酸素原子であり、Ｒ₂₃～Ｒ₃₀は、それぞれ独立に、水素原子、ハロゲン原子、炭素数が１～５の１価の脂肪族基である。）
で表される少なくとも１つの構造を含む、項目１９～２２のいずれか１項に記載の半導体装置。
［２４］
前記式（１０）のＶは、下記一般式（９）：
で表される構造を含む、項目１９～２３のいずれか１項に記載の半導体装置。
［２５］
前記式（１０）のＶは、炭素数１～４０の２価の有機基である、項目１９～２４のいずれか１項に記載の半導体装置。
［２６］
前記式（１０）のＶは、炭素数１～２０の２価の鎖状脂肪族基である、項目１９～２５のいずれか１項に記載の半導体装置。
［２７］
前記フェノール性水酸基を有するポリマーは、ノボラック型フェノール樹脂を含む、項目１２に記載の半導体装置。
［２８］
前記フェノール性水酸基を有するポリマーは、不飽和炭化水素基を有しないフェノール樹脂と、不飽和炭化水素基を有する変性フェノール樹脂と、を含む、項目１２に記載の半導体装置。
［２９］
前記半導体装置は、ファンアウト型のウェハレベルチップサイズパッケージ型の半導体装置である、項目１～２８のいずれか１項に記載の半導体装置。
［３０］
半導体チップを用意する第１工程と、
厚さ方向平面視で前記半導体チップよりも面積が大きい第１再配線層であって、かつ、前記半導体チップに電気的に接続される中間層、及び該中間層に接する絶縁層を含む該第１再配線層を、前記半導体チップの一方面側に配する第２工程と、
用意した半導体チップを、該半導体チップの他方面側が露出するように封止材で覆う第３工程と、
厚さ方向平面視で前記半導体チップよりも面積が大きい第２再配線層であって、かつ、前記半導体チップに電気的に接続される中間層、及び該中間層に接する絶縁層を含む該第２再配線層を、前記半導体チップの他方面側に配する第４工程と、を含み、
前記第１再配線層における絶縁層、及び前記第２再配線層における絶縁層の少なくとも一方は、１層構造又は多層構造であり、かつ、前記層構造を構成する少なくとも１つの層は、該層を厚さ１０μｍに換算した時の、５３２ｎｍ波長における透過率が、０．５～５０％である領域を有する、半導体装置の製造方法。
［３１］
前記第２工程では、前記領域を有する前記再配線層を配する、項目３０に記載の半導体装置の製造方法。
［３２］
前記絶縁層を、ポリイミドと、ポリベンゾオキサゾールと、フェノール性水酸基を有するポリマーと、の少なくとも１つの化合物を形成可能な感光性樹脂組成物で形成する絶縁層形成工程を含む、項目３０又は３１に記載の半導体装置の製造方法。
［３３］
半導体チップと、
前記半導体チップに接する封止材と、
を備える半導体装置における、前記半導体チップ及び前記封止材の少なくとも一方面側に配される再配線層であって、
前記再配線層は、前記半導体チップに電気的に接続される中間層、及び該中間層に接する絶縁層を含み、
前記絶縁層は、１層構造又は多層構造であり、かつ、前記層構造を構成する少なくとも１つの層は、該層を厚さ１０μｍに換算したときの、５３２ｎｍ波長における透過率が、０．５～５０％である領域を含む、再配線層。 Embodiments of the present invention are as follows.
[1]
semiconductor chip,
a sealing material in contact with the semiconductor chip;
a rewiring layer disposed on at least one side of the semiconductor chip and the sealing material and having a larger area than the semiconductor chip in a plan view in the thickness direction;
The rewiring layer includes an intermediate layer electrically connected to the semiconductor chip, and an insulating layer in contact with the intermediate layer,
The insulating layer has a single layer structure or a multilayer structure, and at least one layer constituting the layer structure has a transmittance of 0.5 at a wavelength of 532 nm when the thickness of the layer is 10 μm. A semiconductor device comprising an area of ˜50%.
[2]
The rewiring layer includes a first surface facing the semiconductor chip and a second surface opposite to the first surface, and the region is disposed on the second surface side. The semiconductor device according to item 1.
[3]
3. The semiconductor device according to item 1 or 2, wherein the region is arranged in the outermost layer of the rewiring layer.
[4]
The semiconductor device according to any one of items 1 to 3, wherein the region is arranged on an extension in the thickness direction of a portion where the intermediate layer and the insulating layer are in contact with each other.
[5]
When the rewiring layer is a first rewiring layer,
a second redistribution layer disposed on the other side of the semiconductor chip and the sealing material;
The semiconductor device according to any one of items 1 to 4, wherein the region is arranged in a second rewiring layer.
[6]
A RAM (Random Access Memory) can be arranged on the second surface of the second redistribution layer so as to be electrically connected to the intermediate layer exposed on the second surface,
6. The semiconductor device according to item 5, wherein the second surface of the first redistribution layer is capable of arranging an external connection terminal so as to be electrically connected to the intermediate layer exposed on the second surface.
[7]
The insulating layer has another layer in addition to the layer containing the region,
According to any one of items 1 to 6, the other layer includes another region having a transmittance of more than 50% to 95% at a wavelength of 532 nm when the thickness of the other layer is converted to 10 μm. semiconductor devices.
[8]
8. The semiconductor device according to any one of items 1 to 7, wherein the rewiring layer has three or more layers.
[9]
The semiconductor device according to any one of items 1 to 8, wherein a plurality of the semiconductor chips are arranged in parallel.
[10]
The semiconductor device according to any one of items 1 to 9, wherein the sealing material is in contact with the insulating layer.
[11]
The semiconductor device according to any one of items 1 to 10, wherein the sealing material contains an epoxy resin.
[12]
The semiconductor device according to any one of items 1 to 11, wherein the insulating layer contains at least one member selected from the group consisting of polyimide, polybenzoxazole, and a polymer having a phenolic hydroxyl group.
[13]
The insulating layer has the following general formula (1):
(In the formula, X ¹ is a tetravalent organic group derived from tetracarboxylic dianhydride, Y ¹ is a divalent organic group derived from diamine, and m is an integer of 1 or more. be.)
The semiconductor device according to any one of items 1 to 12, comprising a polyimide having a structure represented by:
[14]
Item 13, wherein X ¹ in the formula (1) is a tetravalent organic group containing an aromatic ring, and Y ¹ in the formula (1) is a divalent organic group containing an aromatic ring. semiconductor devices.
[15]
X ¹ in the formula (1) is represented by the following general formulas (2) to (4):

(In formula (4), R ₉ is an oxygen atom, a sulfur atom, or a divalent organic group.)
The semiconductor device according to item 13 or 14, including at least one structure represented by:
[16]
X ¹ in the formula (1) is represented by the following general formula (5):

The semiconductor device according to item 15, including the structure represented by.
[17]
Y ¹ in the above formula (1) is represented by the following general formulas (6) to (8):
(In the formula, R ₁₀ to R ₁₃ are each independently a hydrogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group.)
(In the formula, R ₁₄ to R ₂₁ are each independently a hydrogen atom, a halogen atom, a monovalent organic group having 1 to 5 carbon atoms, or a hydroxyl group.)
(In the formula, R ₂₂ is a divalent group or an oxygen atom, and R ₂₃ to R ₃₀ are each independently a hydrogen atom, a halogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group. )
The semiconductor device according to any one of items 13 to 16, including at least one structure represented by:
[18]
Y ¹ in the formula (1) is represented by the following general formula (9):
The semiconductor device according to any one of items 13 to 17, including a structure represented by:
[19]
The insulating layer has the following general formula (10):

(In the formula, U and V are divalent organic groups.)
The semiconductor device according to item 12, comprising the polybenzoxazole having the structure.
[20]
19. The semiconductor device according to item 19, wherein U in the formula (10) is a divalent organic group having 1 to 30 carbon atoms.
[21]
21. The semiconductor device according to item 19 or 20, wherein U in the formula (10) is a chain alkylene group having 1 to 8 carbon atoms and in which some or all of the hydrogen atoms are substituted with fluorine atoms.
[22]
22. The semiconductor device according to any one of items 19 to 21, wherein V in the formula (10) is a divalent organic group containing an aromatic group.
[23]
V in the formula (10) is represented by the following general formulas (6) to (8):
(In the formula, R ₁₀ to R ₁₃ are each independently a hydrogen atom or a monovalent aliphatic group having 1 to 5 carbon atoms.)
(In the formula, R ₁₄ to R ₂₁ are each independently a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 5 carbon atoms.)
(In the formula, R ₂₂ is a divalent group or an oxygen atom, and R ₂₃ to R ₃₀ are each independently a hydrogen atom, a halogen atom, or a monovalent aliphatic group having 1 to 5 carbon atoms. .)
The semiconductor device according to any one of items 19 to 22, including at least one structure represented by:
[24]
V in the formula (10) is represented by the following general formula (9):
The semiconductor device according to any one of items 19 to 23, including a structure represented by:
[25]
25. The semiconductor device according to any one of items 19 to 24, wherein V in the formula (10) is a divalent organic group having 1 to 40 carbon atoms.
[26]
The semiconductor device according to any one of items 19 to 25, wherein V in the formula (10) is a divalent chain aliphatic group having 1 to 20 carbon atoms.
[27]
13. The semiconductor device according to item 12, wherein the polymer having a phenolic hydroxyl group includes a novolac type phenolic resin.
[28]
13. The semiconductor device according to item 12, wherein the polymer having a phenolic hydroxyl group includes a phenol resin having no unsaturated hydrocarbon group and a modified phenol resin having an unsaturated hydrocarbon group.
[29]
29. The semiconductor device according to any one of items 1 to 28, wherein the semiconductor device is a fan-out type wafer level chip size package type semiconductor device.
[30]
A first step of preparing a semiconductor chip;
The first redistribution layer has a larger area than the semiconductor chip in a plan view in the thickness direction, and includes an intermediate layer electrically connected to the semiconductor chip, and an insulating layer in contact with the intermediate layer. a second step of disposing one rewiring layer on one side of the semiconductor chip;
a third step of covering the prepared semiconductor chip with a sealing material so that the other side of the semiconductor chip is exposed;
A second redistribution layer having a larger area than the semiconductor chip in a plan view in the thickness direction, the second redistribution layer including an intermediate layer electrically connected to the semiconductor chip, and an insulating layer in contact with the intermediate layer. a fourth step of disposing a second rewiring layer on the other side of the semiconductor chip;
At least one of the insulating layer in the first redistribution layer and the insulating layer in the second redistribution layer has a single layer structure or a multilayer structure, and at least one layer constituting the layer structure is A method for manufacturing a semiconductor device having a region having a transmittance of 0.5 to 50% at a wavelength of 532 nm when converted to a thickness of 10 μm.
[31]
31. The method for manufacturing a semiconductor device according to item 30, wherein in the second step, the rewiring layer having the region is provided.
[32]
Item 30 or 31 includes an insulating layer forming step of forming the insulating layer with a photosensitive resin composition capable of forming at least one compound of polyimide, polybenzoxazole, and a polymer having a phenolic hydroxyl group. A method of manufacturing the semiconductor device described above.
[33]
semiconductor chip,
a sealing material in contact with the semiconductor chip;
A rewiring layer disposed on at least one side of the semiconductor chip and the sealing material in a semiconductor device comprising:
The rewiring layer includes an intermediate layer electrically connected to the semiconductor chip, and an insulating layer in contact with the intermediate layer,
The insulating layer has a single layer structure or a multilayer structure, and at least one layer constituting the layer structure has a transmittance of 0.5 at a wavelength of 532 nm when the thickness of the layer is 10 μm. A redistribution layer containing an area of ~50%.

According to the present invention, it is possible to provide a semiconductor device that has an insulating layer with excellent developability and has good adhesion between the insulating layer and an intermediate layer after green laser irradiation, and a method for manufacturing the same. .

FIG. 1 is a schematic cross-sectional view showing one aspect of a semiconductor device according to the present embodiment. FIG. 1 is a schematic plan view showing one aspect of a semiconductor device according to the present embodiment. It is an example of the manufacturing process of the semiconductor device based on this embodiment. FIG. 7 is a schematic cross-sectional view showing another aspect of the semiconductor device according to the present embodiment.

Embodiments of the present invention (hereinafter referred to as "embodiments") will be described below with reference to the drawings. In this specification, the upper limit or lower limit of a numerical range described in stages may be replaced with the upper or lower limit of another numerical range described in stages, and the values shown in the examples May be replaced. In this specification, an aspect expressed as "surface side" with respect to a predetermined surface includes an aspect in which an arbitrary member is interposed between the surface and the surface, in addition to an aspect in which the surface is in contact with the surface. The structures of moieties represented by the same symbol in the general formula may be the same or different from each other when a plurality of moieties exist in the molecule. The scale, shape, length, etc. shown in the drawings may be exaggerated for further clarity.

In this specification, a pattern obtained by exposing and developing a photosensitive resin composition is referred to as a "relief pattern", and a relief pattern obtained by heating and curing is referred to as a "cured relief pattern".

[Embodiment 1]
<Semiconductor device>
[Summary of configuration]
1(a) is a schematic cross-sectional view of the semiconductor device of this embodiment, FIG. 1(b) is an enlarged schematic diagram of the field of view a in FIG. 1, and FIG. 2 is a schematic cross-sectional view of the semiconductor device of this embodiment. FIG. As illustrated, the semiconductor device (semiconductor IC) 1 includes:
semiconductor chip 2;
a sealing material 3 in contact with the semiconductor chip 2;
A rewiring layer 4 disposed on at least one side of the semiconductor chip 2 and the sealing material 3 and having a larger area than the semiconductor 2 chip in a plan view in the thickness direction,
The rewiring layer 4 includes an intermediate layer (for example, a wiring 5) electrically connected to the semiconductor chip 2, and an insulating layer 6 in contact with the intermediate layer,
The insulating layer 6 has a single layer structure or a multilayer structure, and at least one layer constituting the layer structure has a transmittance of 0.5 at a wavelength of 532 nm when the thickness of the layer is converted to 10 μm. 50%. According to the semiconductor device 1, the insulating layer 6 has excellent developability, and the adhesion between the insulating layer 6 and the intermediate layer after green laser irradiation is good.

(semiconductor chip)
The semiconductor chip 2 is made of a semiconductor such as silicon, and has a circuit formed therein. When the semiconductor device 1 includes a plurality of semiconductor chips 2, the semiconductor chips 2 may be arranged in parallel. In FIG. 1A, two semiconductor chips 2 are arranged in parallel along the plane direction (direction perpendicular to direction A). Each configuration of the plurality of semiconductor chips 2 and each configuration associated therewith may be the same or different. The number of parallel semiconductor chips 2 may be three or more.

In FIG. 1, the semiconductor chip 2 is illustrated in a cubic shape having one side 2a, another side 2b opposite to the one side 2a, and four side surfaces 2c between the one side 2a and the other side 2b. ing. One surface 2a of the semiconductor chip 2 is in contact with the rewiring layer 4, the other surface 2b is in contact with the terminals 9 and the protective layer 8, and the four side surfaces 2c are in contact with the sealing material 3. In terms of the relationship with the encapsulant 3, one surface 2a and the other surface 2b of the semiconductor chip 2 are not in contact with the encapsulant 3, that is, the one surface 2a and the other surface 2b are exposed from the encapsulant 3. ing.

(protective layer)
The protective layer 8 is composed of a hardened relief pattern, and can protect the semiconductor chip 2 from physical impact. From the viewpoint of protecting the semiconductor chip 2, the Young's modulus of the protective layer 8 may be adjusted as appropriate. Terminals 9 for ensuring conduction between the semiconductor chip 2 side and the wiring 5 side are arranged on the other surface 2b side of the semiconductor chip 2, and the protective layer 8 is arranged so as to fill in the spaces between the terminals 9. , are arranged on the other surface 2b side. Assuming that the semiconductor chip 2 is viewed in a plan view in the thickness direction from the one surface 2a side (as viewed from arrow A in FIG. 1), the protective layer 8 is in the shadow of the semiconductor chip 2 and cannot be observed.

The protective layer 8 is in contact with both the semiconductor chip 2 (the other surface 2b of the semiconductor chip 2) and the insulating layer 6. According to this, it becomes easy to protect the semiconductor chip 2 suitably. However, the protective layer 8 can be omitted, and a member different from the protective layer 8 may be interposed between the semiconductor chip 2 and the insulating layer 6 within the scope of the present invention.

It is preferable that the protective layer 8 contains at least one compound selected from the group consisting of, for example, polyimide, polybenzoxazole, and a polymer having a phenolic hydroxyl group. The resin composition used to form the protective layer 8 may be a photosensitive resin composition, and includes at least one selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and a polymer having a phenolic hydroxyl group. A photosensitive resin composition containing two compounds may be used. The resin composition used to form the protective layer 8 may be in liquid or film form, and may be in negative or positive type.

(Encapsulant)
The sealing material 3 is in contact with the semiconductor chip 2, and here, is in contact with the four side surfaces 2c of the semiconductor chip 2. As shown in the figure, it is preferable that the sealing material 3 is in direct contact with the semiconductor chip 2 and the rewiring layer 4. According to this, the sealing performance from the surface of the semiconductor chip 2 to the surface of the rewiring layer 4 can be effectively improved. Moreover, it is preferable that the sealing material 3 is in contact with the insulating layer 6. According to this, the sealing performance up to the surface of the insulating layer 6 can be effectively improved. The sealing material 3 may be in contact with the protective layer 8 in addition to the semiconductor chip 2 and the rewiring layer 4 . A wiring 5 penetrates through the sealing material 3 in the thickness direction, and the wiring 5 is electrically connected to the wiring 5 in the redistribution layer 4 .

The sealing material 3 may be, for example, an epoxy resin from the viewpoint of heat resistance and adhesion to the insulating layer. The sealing material 3 may be a single layer or a multilayer. When the sealing material 3 is multilayered, the configuration of each layer may be the same or different.

[Rewiring layer]
The rewiring layer 4 is arranged on at least one side of the semiconductor chip 2 and the sealing material 3, and has a larger area than the semiconductor 2 chip in a plan view in the thickness direction (arrow A in FIG. 1(a)). . FIG. 2 shows the relationship: area S1 of rewiring layer 4>area S2 of semiconductor chip 2. In FIG. 2, a portion of the rewiring layer 4 overlapping the semiconductor chip 2 is also included in the area S1 of the rewiring layer 4. Note that the rewiring layer in this embodiment does not include a printed wiring board.

The external shapes of the semiconductor chip 2 and the rewiring layer 4 may be the same or different. In FIG. 2, the semiconductor chip 2 and the rewiring layer 4 both have similar rectangular outer shapes, but each may have a shape other than a rectangle and may not have a similar shape.

The thickness of the rewiring layer 4 is approximately 3 to 30 μm. The film thickness may be 1 μm or more, 5 μm or more, or 10 μm or more. Further, the film thickness may be 40 μm or less, 30 μm or less, or 20 μm or less.

The rewiring layer 4 includes an intermediate layer (for example, a wiring 5) electrically connected to the semiconductor chip 2, and an insulating layer 6 in contact with the intermediate layer. Among these, the wiring 5 is preferably made of a highly conductive material, and copper is generally used. The redistribution layer 4 can be configured as a laminate of interconnects 5 and insulating layers 6. The number of layers of the rewiring layer 4 corresponds to the number of insulating layer forming steps described below.

It is preferable that the rewiring layer 4 has three or more layers. When the rewiring layer 4 includes three or more layers, it becomes easier to smooth out the steps in the rewiring layer 4. The number of rewiring layers may be nine or less. From the same viewpoint, it is preferable that the insulating layer 6 includes two or more layers. In FIG. 1(b), from the side of the semiconductor chip 2 and the sealing material 3, there are three layers including a first insulating layer 6-1, a second insulating layer, and a third insulating layer 6-3. A redistribution layer 4 of the structure is shown. The third insulating layer 6-3 corresponds to the outermost layer, and the outermost layer is configured as the region 6a. Further, the first insulating layer 6-1 and the second insulating layer 6-2 are configured as another region 6b.

(First redistribution layer and second redistribution layer)
When the rewiring layer 4 disposed on one side of the semiconductor chip 2 and the encapsulant 3 is the first redistribution layer 4A, the semiconductor device 1 is arranged on the other side of the semiconductor chip 2 and the encapsulant 3. A second redistribution layer 4B may be provided. In this case, a configuration can be realized in which the first rewiring layer 4A and the second rewiring layer 4B face each other with the semiconductor chip 2 interposed therebetween. The first rewiring layer 4A and the second rewiring layer 4B each include a first surface 4a on the semiconductor chip 2 side and a second surface 4b opposite to the first surface 4a. Various electronic components can be arranged on each second surface 4b of the first rewiring layer 4A and the second rewiring layer 4B.

A RAM (including DRAM, indicated by the symbol D in FIG. 1) may be provided on the second surface 4b of the first redistribution layer 4A; 4b may be provided with an external connection terminal 7. Since a predetermined area is secured on the second surface 4b, it is easy to suitably arrange various DRAMs in the first redistribution layer 4A, and a large number of external connection terminals 7 in the second redistribution layer 4B. It is easy to arrange them appropriately. Furthermore, connection with electronic components (DRAM, external connection terminals, etc.) can be easily secured through the wiring 5 exposed on the second surface 4b.

When the semiconductor chip 2 and the redistribution layer 4 are viewed from above in the thickness direction, the area S1 of the redistribution layer 4 is set to ensure a suitable area for arranging various DRAMs and for providing a large number of external connection terminals 7. In view of this, the area S2 of the semiconductor chip 2 is preferably 1.05 times or more, more preferably 1.1 times or more, even more preferably 1.2 times or more, and particularly preferably 1.3 times or more. The area S1 may be 50 times or less, 25 times or less, 10 times or less, or 5 times or less as large as the area S2.

The size, shape, and thickness of the second rewiring layer 4B are as described for the rewiring layer 4 above, and may be the same or different from the size, shape, and thickness of the first rewiring layer 4A. However, the thickness of the first redistribution layer 4A is preferably smaller than that of the second redistribution layer 4B. According to this, the overall package thickness of the semiconductor device 2 can be easily reduced.

A sealing material 3 is disposed between the first redistribution layer 4A and the second redistribution layer 4B, and the wiring 5 passing through the sealing material 3 is connected to the wiring 5 in the first rewiring layer 4A, It is electrically connected to both the wiring 5 in the second rewiring layer 4B. In this specification, a configuration that can be adopted for both the first rewiring layer 4A and the second rewiring layer 4B is also simply referred to as a "rewiring layer", but will be described simply as a "rewiring layer". Even if the configuration applies only to the first redistribution layer 4A, only to the second redistribution layer 4B, or to both the first redistribution layer 4A and the second redistribution layer 4B, good. The configurations of the first redistribution layer 4A and the second redistribution layer 4B may be different from each other.

In FIG. 1, although the protective layer 8 is interposed between the second rewiring layer 4B and the semiconductor chip 2, the first rewiring layer 4A is in direct contact with one surface 2a of the semiconductor chip 2. However, a protective layer may be disposed between the first redistribution layer 4A and the semiconductor chip 2 from the viewpoint of protecting against physical impact from the one surface 2a side of the semiconductor chip 2.

(insulating layer)
The insulating layer 6 can be composed of a cured relief pattern, and the insulating layer 6 can prevent unintended conduction between the wirings 5. The insulating layer 6 is in contact not only with the semiconductor chip 2 but also with the sealing material 3, thereby forming a fan-out type wafer level chip size package (WLCSP) type semiconductor device 1. There is. The insulating layer 6 and the intermediate layer (here, the wiring 5) are required to have high adhesion.

Preferably, the insulating layer 6 contains at least one selected from the group consisting of C, H, N, O, Si, and Ti. Among these, an insulating layer in which the amount of a compound into which a functional group with a large free volume, such as a halogen atom, is introduced is reduced (or does not contain the compound) is easy to prevent a decrease in chemical resistance.

(region)
Here, the insulating layer 6 has a single layer structure or a multilayer structure, and at least one layer constituting the layer structure has a transmittance at a wavelength of 532 nm (hereinafter simply " It includes a region 6a in which the transmittance (also referred to as "transmittance") is 0.5 to 50%. If the transmittance is 0.5% or more, it is possible to ensure sufficient sensitivity to the i-line or ghi-line, which is a general exposure wavelength, in the exposure process for forming the insulating layer. It is possible to form a pattern shape (circular hole shape, etc.) suitable for providing electronic components and also suitable for forming wiring 5 in conjunction therewith. If the transmittance is 50% or less, the adhesion between the insulating layer 6 and the intermediate layer after irradiation with the green laser is good.

In one embodiment, the insulating layer 6 in the first redistribution layer 4A includes the region 6a. In this case, it is easy to form a pattern shape suitable for providing a DRAM or the like in the first redistribution layer 4A, and also suitable for forming the wiring 5 in association therewith.

In one embodiment, the insulating layer 6 in the second redistribution layer 4B includes the region 6a. In this case, it is easy to form a pattern shape that is suitable for providing the external connection terminals 7 and the like on the second rewiring layer 4B, and also suitable for forming the wiring 5 in conjunction therewith.

However, the external connection terminals 7 may be arranged in the insulating layer 6 of the first redistribution layer 4A, and the DRAM may be arranged in the insulating layer 6 of the second redistribution layer 4B. If the transmittance is 0.5% or more, the insulating layer 6 can be suitably formed using i-line or ghi-line, which is a general exposure wavelength, depending on the aspect of the electronic component provided on the insulating layer 6. Can be done.

The present inventors believe that the reason why the above effects can be obtained when the transmittance is 0.5% to 50% is as follows. In other words, when irradiating a laser with a wavelength of 532 nm to form an alignment mark on an insulating layer, by setting the transmittance at that wavelength to 50% or less, the amount of laser that reaches the inside of the redistribution layer (semiconductor chip side) can be reduced. This makes it possible to suppress heat generation in the intermediate layer. Therefore, it is possible to suppress volatile gases caused by thermal decomposition of the insulating layer around the intermediate layer, thereby achieving good adhesion. In addition, by setting the transmittance at 532 nm to 0.5% or more, sufficient transmittance of the i-line or ghi-line, which is a common wavelength, can be ensured in the exposure process required when forming an insulating layer. , the developability becomes good.

From the viewpoint of adhesion between the insulating layer 6 and the wiring 5, the transmittance is preferably 40% or less, more preferably 30% or less. Further, the transmittance at a wavelength of 532 nm is preferably 1% or more, more preferably 2% or more, from the viewpoint of developability.

Transmittance can be controlled by the composition of the insulating layer, and can also be controlled by adjusting the colorability of the insulating layer. The colorability of the insulating layer can be controlled by adjusting the type and/or amount of additives added to the resin composition for forming the insulating layer. Generally, the stronger the coloring property of the insulating layer, the lower the laser transmittance tends to be.

The insulating layer 6 may include an Nth insulating layer (N is an integer of 1 or more) from the semiconductor chip 2 side when the rewiring layer 4 is viewed in cross section. The composition, characteristics, film thickness, etc. of each insulating layer may be the same or different. An intermediate layer can be disposed between each insulating layer.

In the insulating layer 6, the layer including the region 6a may be one layer or multiple layers. For example, in FIG. 1(b), the third insulating layer 6-3, the outermost layer, is the layer including the region 6a. Illustrated. The region 6a is preferably arranged on the second surface 4b side of the rewiring layer 4 from the viewpoint of visibility of the alignment mark. From the same viewpoint, it is preferable that the region 6a be disposed in the outermost layer of the rewiring layer 4.

Transmittance is measured by the method described in Examples. For example, when the region 6a is arranged in the outermost layer, the transmittance at a wavelength of 532 nm is measured when the thickness of the outermost layer is converted to 10 μm. Further, when the region 6a is arranged on the Nth insulating layer (N is an integer of 1 or more), the transmittance at a wavelength of 532 nm when the thickness of the Nth insulating layer is converted to 10 μm is be measured. The transmittance value measured for a sample (a part that constitutes a part of a semiconductor device, for example, a rewiring layer) for measuring transmittance is measured for a semiconductor device having the same configuration as the sample. It may be regarded as a value of transmittance. If it is difficult to peel off the insulating layer from the package and measure it, a reflection method using an integrating sphere is used. If the film thickness is not 10 μm (assuming y μm), the measured transmittance is multiplied by {(transmittance/100) ^10/y }×100 to calculate the transmittance converted to 10 μm.

If the resin composition for forming the region 6a having the above-described transmittance is used as the resin composition for forming the outermost layer of the rewiring layer 4, the region 6a can be formed during the manufacturing process of the semiconductor device 1. easy. When the outermost layer of the redistribution layer 4 is viewed from above in the thickness direction, the area ratio of the region 6a (area of the region 6a/area of the insulating layer 6) is preferably 50% or more, based on the total area of the insulating layer 6. It is preferably 75% or more, preferably 90% or more, and may be 100%. The insulating layer that constitutes the second surface 4b of the rewiring layer 4, that is, the insulating layer that constitutes the outermost layer of the rewiring layer 4, may be configured as the region 6a.

The region 6a is preferably disposed on an extension in the thickness direction of a portion where the intermediate layer and the insulating layer 6 are in contact, from the viewpoint of better preventing peeling of the intermediate layer and the insulating layer. From the same point of view, it is preferable that the region 6a having the above-mentioned transmittance be disposed on an extension of the portion where the intermediate layer and the insulating layer 6 are in contact with each other in the green laser irradiation direction.

The region 6a is preferably arranged in at least the first rewiring layer 4A of the first rewiring layer 4A and the second rewiring layer 4B. This facilitates suitably stacking electronic components (such as DRAM) with high positioning requirements on the first redistribution layer 4A. However, the region 6a may be arranged in the second rewiring layer 4B, or may be arranged in both the first rewiring layer 4A and the second rewiring layer 4B.

The insulating layer 6 includes other layers in addition to the layer including the region 6a. The other layers correspond to, for example, the first insulating layer 6-1 and the second insulating layer 6-2 in FIG. 1(b). Preferably, such other layer includes another region 6b having a transmittance of more than 50% to 95% at a wavelength of 532 nm when the thickness of the other layer is converted to 10 μm. According to this, variations in the configuration of the rewiring layer can be easily increased. For example, assume that it is possible to form another region that is more advantageous in developability than the above region. In this case, the insulating layer (in one embodiment, the outermost insulating layer) where alignment mark visibility is particularly required is provided with the above-mentioned region that is advantageous for visibility, and the insulating layer where developability is particularly required. It is possible to realize an embodiment in which the layer (in one embodiment, the inner insulating layer) is provided with the above-mentioned other regions that are advantageous for the developability. From the viewpoint of increasing the adhesion between the plurality of insulating layers, the transmittance in the other region 6b is preferably 60% or more, and more preferably 70% or more. Further, the transmittance in the other region 6b is preferably 90% or less, more preferably 85% or less, from the viewpoint of reducing damage to the semiconductor chip. The other region 6b may be arranged in the outermost layer of the rewiring layer 4, or may be arranged in the layer of the rewiring layer 4. The region 6a and the other region 6b do not need to be layered.

The composition of the insulating layer 6 preferably includes at least one compound selected from the group consisting of polyimide, polybenzoxazole, and a polymer having a phenolic hydroxyl group. The resin composition used to form the insulating layer 6 may be a photosensitive resin composition, and includes at least one selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, and a polymer having a phenolic hydroxyl group. A photosensitive resin composition containing two compounds may be used. The resin composition used to form the insulating layer 6 may be in liquid form or film form. The resin composition used to form the insulating layer 6 may be negative type or positive type.

Ｒ¹及びＲ²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。Ｘ¹は、テトラカルボン酸二無水物に由来する４価の有機基であり、Ｙ¹は、ジアミンに由来する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。 <Polyimide precursor composition>
(A) Photosensitive resin Examples of the photosensitive resin used in the polyimide precursor composition include polyamide, polyamic acid ester, and the like. For example, as the polyamic acid ester, a polyamic acid ester containing a repeating unit represented by the following general formula (11) can be used.

R ¹ and R ² are each independently a hydrogen atom, a saturated aliphatic group having 1 to 30 carbon atoms, an aromatic group, a monovalent organic group having a carbon-carbon unsaturated double bond, or a carbon-carbon It is a monovalent ion with unsaturated double bonds. X ¹ is a tetravalent organic group derived from tetracarboxylic dianhydride, Y ¹ is a divalent organic group derived from diamine, 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 above general formula (11) exist as monovalent cations, O is negatively charged (exists as -O 2 ^- ). Moreover, X ¹ and Y ¹ may contain a hydroxyl group.

（式中、Ｒ₃～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。）

（式中、Ｒ₆～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。） R ¹ and R ² in the general formula (11) are each independently more preferably a monovalent organic group represented by the following general formula (12) or 1 represented by the following general formula (13). It has a structure with an ammonium ion at the end of a valent organic group.

(In the formula, R ₃ to R ₅ are each independently a hydrogen atom or an organic group having 1 to 5 carbon atoms, and m1 is an integer of 1 to 20.)

(In the formula, R ₆ to 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. Alternatively, a polyamic acid ester obtained by copolymerizing polyamic acid esters represented by the general formula (11) may be used.

From the viewpoint of Young's modulus and/or chemical resistance, X ¹ is preferably a tetravalent organic group containing an aromatic group. Specifically, X ¹ is preferably a tetravalent organic group containing at least one structure represented by the following general formulas (2) to (4).

（式中、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 the formula, R ₉ is an oxygen atom, a sulfur atom, or a divalent organic group.)

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

From the viewpoint of developability, X ¹ is particularly preferably a tetravalent organic group containing a structure represented by the following general formula (5).

（式中、Ｒ₁₀～Ｒ₁₃は、それぞれ独立に、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。）

（式中、Ｒ₁₄～Ｒ₂₁は、それぞれ独立に、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。）

（式中、Ｒ₂₂は、２価の基又は酸素原子であり、Ｒ₂₃～Ｒ₃₀は、それぞれ独立に、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。） From the viewpoint of Young's modulus and chemical resistance ^{, Y 1 is} preferably a divalent organic group containing an aromatic group. Specifically, Y ¹ is preferably a divalent organic group containing at least one structure represented by the following general formulas (6) to (8).

(In the formula, R ₁₀ to R ₁₃ are each independently a hydrogen atom or a monovalent aliphatic group having 1 to 5 carbon atoms, and may be the same or different.)

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

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

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

From the viewpoint of developability, Y ¹ is particularly preferably a divalent organic group containing a structure represented by the following general formula (9).

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

Examples of the tetracarboxylic dianhydride used as a raw material include pyromellitic anhydride (PMDA), diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride (4,4'-oxydiphthalic dianhydride), compound: ODPA), 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, Examples include 2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane. These may be used alone or in combination of two or more.

Examples of diamines used as raw materials include p-phenylenediamine (PPD), m-phenylenediamine, 4,4'-diaminodiphenyl ether (DADPE), 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, , 4'-diamino-2,2'-dimethylbiphenyl (m-TB) 4,4'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 3,3'-diaminodiphenylsulfide, 4,4'- Diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, 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-amino phenyl)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-toridine sulfone, 9,9-bis(4-aminophenyl) ) Fluorene, etc. Further, some of the hydrogen atoms on these benzene rings may be substituted. Further, these may be used alone or in combination of two or more.

In the synthesis of polyamic acid ester (A), it is usually preferable to use a method in which a tetracarboxylic acid diester obtained by carrying out an esterification reaction of a tetracarboxylic dianhydride, which will be described later, is directly subjected to a condensation reaction with a diamine. .

The alcohol used in the above-mentioned esterification reaction of the tetracarboxylic dianhydride is an alcohol having an olefinic double bond. Specific examples include 2-hydroxyethyl methacrylate, 2-methacryloyloxyethyl alcohol, glycerin diacrylate, and glycerin dimethacrylate. These alcohols can be used alone or in combination of two or more.

As for the specific method for synthesizing the polyamic acid ester (A) used in this embodiment, conventionally known methods can be employed. As for the synthesis method, for example, the method shown in International Publication No. 00/43439 pamphlet can be mentioned. That is, the tetracarboxylic acid diester is once converted into the tetracarboxylic acid diester diacyl chloride, and the tetracarboxylic acid diester diacyl chloride and the diamine are subjected to a condensation reaction in the presence of a basic compound to form the polyamic acid ester (A). Examples include methods for manufacturing. Another example is a method of producing polyamic acid ester (A) by subjecting a tetracarboxylic acid diester and a diamine to a condensation reaction in the presence of an organic dehydrating agent.

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 even more preferably 7,000 to 20,000.

(B1) Photoinitiator When the resin composition used to form the protective layer and the insulating layer is a negative photosensitive resin, a photoinitiator is added. Examples of photoinitiators include benzophenone, methyl o-benzoylbenzoate, 4-benzoyl-4'-methyldiphenylketone, dibenzylketone, and benzophenone derivatives such as fluorenone, 2,2'-diethoxyacetophenone, and 2,2'-diethoxyacetophenone. -Acetophenone derivatives such as hydroxy-2-methylpropiophenone, thioxanthone derivatives such as 1-hydroxycyclohexylphenylketone, 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, 2,6-di(4'-diazidobenzal)-4-methylcyclohexanone, and 2,6'-di(4'-diazidobenzal)cyclohexanone, etc. 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 biimidazole, and titanocenes are used. Among these, the above oximes are preferred in terms of photosensitivity.

The amount of these photoinitiators added is preferably 1 to 40 parts by weight, more preferably 2 to 20 parts by weight, per 100 parts by weight of the polyamic acid ester (A). By adding 1 part by mass or more of a photoinitiator to 100 parts by mass of polyamic acid ester (A), excellent photosensitivity can be achieved. Further, by adding 40 parts by mass or less, thick film curability is excellent.

(B2) Photoacid generator When the resin composition used to form the protective layer and the insulating layer is a positive photosensitive resin, a photoacid generator is added. By containing a photoacid generator, acid is generated in the ultraviolet-exposed area, and the solubility of the exposed area in an alkaline aqueous solution increases. Thereby, it can be used as a positive photosensitive resin composition.

Examples of the photoacid generator include quinonediazide compounds, sulfonium salts, phosphonium salts, diazonium salts, and iodonium salts. Among these, quinonediazide compounds are preferably used because they exhibit an excellent dissolution inhibiting effect and can provide a highly sensitive positive photosensitive resin composition. Further, two or more kinds of photoacid generators may be contained.

(C) Additives The above transmittance can be adjusted by the polymer structure and also by the type or amount of additives. For example, the desired transmittance can be adjusted by adjusting the type and/or amount of the additive that can adjust the colorability of the insulating layer. As the additive that can adjust the colorability of the insulating layer, dyes and pigments are preferable, and dyes are more preferable from the viewpoint of solubility in the resin composition. The content of the dye and/or pigment may be more than 0.5 to 10 parts by weight, 0.7 to 7 parts by weight, and 0.1 to 5 parts by weight based on the resin composition.

Dyes include azine, azomethine, anthracene, quinacridone, dioxazine, diketopyrrolopyrrole, anthrapyridone, isoindolinone, indanthrone, perinone, perylene, indigo, and thioindigo. , quinophthalone type, quinoline type, and triphenylmethane type. From the viewpoint of elongation of the cured film, azine dye derivatives and anthracene dyes are preferred.

Examples of azine dye derivatives include C.I. I. Solvent Black 5, C. I. Solvent Black 7, and C. I. A black azine-based condensation mixture as described in Color Index as Acid Black 2 can be mentioned. Such azine dye derivatives can be obtained, for example, by oxidizing and dehydrating condensation of aniline, aniline hydrochloride, and nitrobenzene at a reaction temperature of 160 to 180° C. in the presence of iron chloride.

As the anthracene dye derivative, the anthracene dye derivative shown below is particularly preferable because it shows good heat resistance and there is little change in the coloring property of the film before and after the heating (curing) step. That is, as the anthracene dye derivative, anthracene oil-soluble dyes are preferable, and specifically, C.I. I. Solvent Blue 11, 12, 13, 14, 26, 35, 36, 44, 45, 48, 49, 58, 59, 63, 68, 69, 70, 78, 79, 83, 87, 90, 94, 97, 98, 101, 102, 104, 105, 122, 129, and 132;
C. I. Disperse Blue 14, 35, 102, and 197; C. I. Solvent Green 3, 19, 20, 23, 24, 25, 26, 28, 31, 33, and 65;
C. I. Solvent Violet Available in color indexes of 13, 14, 15, 26, 30, 31, 33, 34, 36, 37, 38, 40, 41, 42, 45, 47, 48, 51, 59, and 60 Dyes are preferred. Among them, compounds represented by the following formulas are preferably used.

Examples of the pigment include red pigments such as red lead and iron oxide red, yellow pigments such as yellow lead and zinc yellow, blue pigments such as ultramarine blue, Prussian blue, and YInMn blue, and black pigments such as carbon black. Among these, carbon black is preferred from the viewpoint of transmittance at a wavelength of 532 nm.

Further, in order to improve the resolution of the relief pattern, a monomer having a photopolymerizable unsaturated bond may be optionally blended. Such monomers include
Monoacrylates, diacrylates, monomethacrylates, and dimethacrylates of ethylene glycol;
Monoacrylates, diacrylates, monomethacrylates, and dimethacrylates of polyethylene glycol;
Monoacrylates, diacrylates, monomethacrylates, and dimethacrylates of propylene glycol;
Monoacrylates, diacrylates, monomethacrylates, and dimethacrylates of polypropylene glycol;
Monoacrylates, diacrylates, triacrylates, monomethacrylates, dimethacrylates, and trimethacrylates of glycerol;
Diacrylates and dimethacrylates of cyclohexane; diacrylates and dimethacrylates of 1,4-butanediol;
Diacrylates and dimethacrylates of 1,6-hexanediol; diacrylates and dimethacrylates of neopentyl glycol;
Monoacrylates, diacrylates, monomethacrylates, and dimethacrylates of bisphenol A;
benzene trimethacrylate; isobornyl acrylate and isobornyl methacrylate; acrylamide and its derivatives; methacrylamide and its derivatives; trimethylolpropane triacrylate and trimethylolpropane trimethacrylate;
Mention may be made of compounds such as diacrylates, triacrylates, tetraacrylates, dimethacrylates, trimethacrylates, and tetramethacrylates of pentaerythritol; and ethylene oxide or propylene oxide adducts of these compounds. Among these, tetraethylene glycol dimethacrylate is preferred from the viewpoint of developability.

The polyimide precursor composition may contain a crosslinking agent. As the crosslinking agent, use a crosslinking agent that can crosslink the (A) photosensitive resin or that can itself form a crosslinked network when the polyimide precursor composition is exposed and developed and then heat cured. be able to. By using a crosslinking agent, the heat resistance and chemical resistance of the cured film (insulating layer) can be further strengthened.
Examples of such compounds include compounds containing a methoxymethyl group and compounds containing a methylol group. Among them, the following formula:
A compound represented by is preferable from the viewpoint of developability and heat resistance.

(D) Solvent Any solvent may be used as long as each component can be dissolved or dispersed therein. Examples include N-methyl-2-pyrrolidone, γ-butyrolactone, acetone, methyl ethyl ketone, dimethyl sulfoxide and the like. These solvents can be used in an amount of 30 to 1500 parts by mass based on 100 parts by mass of the photosensitive resin (A), depending on the coating film thickness and viscosity.

(E) Others In addition, it may contain a sensitizer to improve photosensitivity, an adhesion aid to improve adhesion to the base material, and the like.

(developing)
After exposing the polyimide precursor composition, unnecessary parts are washed away with a developer. In the case of a polyimide precursor composition that is developed with a solvent, the developer used is N,N-dimethylformamide, dimethylsulfoxide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, cyclopentanone, Good solvents such as γ-butyrolactone and acetic esters, mixed solvents of these good solvents and poor solvents such as lower alcohols, water, and aromatic hydrocarbons are used. After development, rinse with a poor solvent or the like if 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.

(thermal curing)
After development, the exposed polyimide precursor composition is heated to ring-close the polyimide precursor and form polyimide. This polyimide becomes the cured relief pattern, ie, the insulating layer.

Generally speaking, the higher the heating temperature for thermosetting the polyimide precursor composition, the higher the Young's modulus tends to be. From the viewpoint of setting the Young's modulus of the insulating layer of this embodiment to a desired value, the heating temperature is preferably 160°C or higher, more preferably 180°C or higher, and particularly preferably 200°C or higher. From the viewpoint of influence on other members, the temperature is preferably 400°C or less.

[Polyimide]
The structure of the cured relief pattern formed from the polyimide precursor composition is expressed by the following general formula (1). That is, at least one of the protective layer and the insulating layer has the following general formula (1):
(In the formula, X ¹ is a tetravalent organic group derived from tetracarboxylic dianhydride, Y ¹ is a divalent organic group derived from diamine, and m is an integer of 1 or more. be.)
It is preferable to include a polyimide having a structure represented by: Preferred X ¹ , Y ¹ and m in general formula (11) are also preferred in the polyimide of general formula (1) for the same reason.

For example, similar to the reason for general formula (11), X ¹ in general formula (1) is preferably a tetravalent organic group containing an aromatic group, and is represented by general formulas (2) to (4) above. A tetravalent organic group containing at least one structure is preferable.
Furthermore, for the same reason as in the general formula (11), X ¹ in the general formula (1) is particularly preferably a tetravalent organic group containing the structure represented by the above general formula (5).

Furthermore, for example, similar to the reason for general formula (11), Y ¹ in general formula (1) is a divalent organic group containing at least one structure represented by the above general formulas (6) to (8). For the same reason as in general formula (11), a divalent organic group containing the structure represented by general formula (9) above is particularly preferred.

In the case of alkali-soluble polyimide, the terminal of the polyimide may be a hydroxyl group.
When the protective layer according to the present embodiment contains polyimide, the peak height near 1380 cm ^-1 and the peak height near 1500 cm ^-1 when IR spectrum measurement is performed using the Attenuated Total Reflection (ATR method) method. The peak height and the peak ratio (peak height near 1380 cm ^-1 / peak height near 1500 cm ^-1 ) are preferably from 1.2 to 2.5. From the viewpoint of chemical resistance, it is preferably 1.3 or more, more preferably 1.4 or more, and particularly preferably 1.5 or more. From the viewpoint of developability, it is preferably 2.4 or less, more preferably 2.3 or less, and particularly preferably 2.2 or less.
The "peak height around 1380 cm ^-1 " here is, for example, the maximum peak height within the range of 1330 to 1430 cm ^-1 , and the "peak height around 1500 cm ^-1 " here is, for example, the maximum peak height within the range of 1330 to 1430 cm -1. , the maximum peak height within the range of 1450 to 1550 cm ^-1 .

When the insulating layer according to the present embodiment includes polyimide, the peak height near 1380 cm ^-1 and the peak height near 1500 cm ^-1 when IR spectrum measurement is performed using the Attenuated Total Reflection (ATR method) method. The peak height and the peak ratio (peak height near 1380 cm ^-1 / peak height near 1500 cm ^-1 ) are preferably 0.2 to 1.0. From the viewpoint of chemical resistance, it is preferably 0.3 or more, more preferably 0.4 or more, and particularly preferably 0.5 or more. From the viewpoint of developability, it is preferably 0.8 or less, more preferably 0.7 or less, and particularly preferably 0.6 or less.
The "peak height around 1380 cm ^-1 " here is, for example, the maximum peak height within the range of 1330 to 1430 cm ^-1 , and the "peak height around 1500 cm ^-1 " here is, for example, the maximum peak height within the range of 1330 to 1430 cm -1. , the maximum peak height within the range of 1450 to 1550 cm ^-1 .

（一般式（１４）中、Ｙ²とＹ³は２価の有機基である。） [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.

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

From the viewpoint of adhesion between the insulating layer and the sealing material, Y ² is preferably a divalent organic group having 1 to 30 carbon atoms, and a chain alkylene group having 1 to 15 carbon atoms (however, a chain alkylene group having 1 to 15 carbon atoms is preferable). Hydrogen atoms of alkylene may be substituted with halogen atoms) are more preferable, and chain alkylene groups having 1 to 8 carbon atoms and in which some or all of the hydrogen atoms are substituted with fluorine atoms are particularly preferable.

（式中、Ｒ₁₀～Ｒ₁₃は、それぞれ独立に、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。）

（式中、Ｒ₁₄～Ｒ₂₁は、それぞれ独立に、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。）

（式中、Ｒ₂₂は、２価の基又は酸素原子であり、Ｒ₂₃～Ｒ₃₀は、それぞれ独立に、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。） Furthermore, from the viewpoint of adhesion between the insulating layer and the sealing material, Y ³ is preferably a divalent organic group containing an aromatic group, more preferably represented by the following general formulas (6) to (8). A divalent organic group containing at least one of the structures shown is preferred.

(In the formula, R ₁₀ to R ₁₃ are each independently a hydrogen atom or a monovalent aliphatic group having 1 to 5 carbon atoms, and may be the same or different.)

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

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

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

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

From the viewpoint of adhesion between the insulating layer and the sealing material, Y ³ is preferably a divalent organic group having 1 to 40 carbon atoms, more preferably a divalent chain aliphatic group having 1 to 40 carbon atoms, Particularly preferred are divalent chain aliphatic groups having 1 to 20 carbon atoms.

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

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, etc., which are used in ordinary acid chloridation reactions of carboxylic acids, can be used.

The dichloride derivative can be synthesized by a method in which a dicarboxylic acid derivative and the above-mentioned halogenating agent are reacted in a solvent, a method in which the reaction is carried out in an excess of the halogenating agent, and then the excess is distilled off.

Examples of the dicarboxylic acid used in the dicarboxylic acid derivative include isophthalic acid, terephthalic acid, 2,2-bis(4-carboxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 4,4 '-Dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether (4,4'-diphenyl ether dicarboxylic acid), 4,4'-dicarboxytetraphenylsilane, bis(4-carboxyphenyl)sulfone, 2,2-bis (p-carboxyphenyl)propane, 5-tert-butyl isophthalic acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,6-naphthalene dicarboxylic acid, malonic acid, dimethylmalonic acid, ethyl Malonic 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, hexadecafluoro Sebacic 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, tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, triacontanedioic acid, hentriacontanedioic acid, dotriacontanedioic acid, Examples include diglycolic acid and dicyclopentadienecarboxylic acid. 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)propane, 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-amino- Examples include 3-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane. A mixture of these may be used.

(B2) Photoacid generator The photoacid generator has the function of increasing the solubility of the light irradiated area in an aqueous alkaline solution. Examples of the photoacid generator 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 The preferred types and/or amounts of additives are the same as those described in the section of the polyimide precursor composition.

(D) Solvent Any solvent that can dissolve or disperse each component may be used.

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

(developing)
After exposing the polybenzoxazole precursor composition, unnecessary portions are washed away with a developer. Preferred examples of the developer used include alkaline aqueous solutions such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide.

Although the above description focused on a positive type polybenzoxazole precursor composition, a negative type polybenzoxazole precursor composition may also be used.

(thermal curing)
After development, the polybenzoxazole precursor composition is heated to ring-close the polybenzoxazole precursor and form a polybenzoxazole. This polybenzoxazole becomes the cured relief pattern, that is, the insulating layer 6.

The heating temperature for thermosetting the polybenzoxazole precursor composition is preferably a low temperature from the viewpoint of influence on other members. 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.

（式中、ＵとＶは、２価の有機基である。）
の構造を含む前記ポリベンゾオキサゾールを含む。 [Polybenzoxazole]
The structure of the cured relief pattern formed from the polybenzoxazole precursor composition is expressed by the following general formula (10):

(In the formula, U and V are divalent organic groups.)
The polybenzoxazole has the structure:

U in the general formula (10) is the same as Y ² in the general formula (14), and V in the general formula (10) is the same as Y ³ in the general formula (14). Preferable Y ² and Y ³ of general formula (14) are also preferable in the polybenzoxazole of general formula (10) for the same reason.

For example, for the same reason as in general formula (14), U in general formula (10) is preferably a divalent organic group having 1 to 30 carbon atoms, and a hydrogen atom having 1 to 8 carbon atoms. Particularly preferred is a chain alkylene group in which part or all of is substituted with a fluorine atom.
Further, similar to the reason for general formula (14), V in general formula (10) is preferably a divalent organic group containing an aromatic group, and is represented by the above general formulas (6) to (8). A divalent organic group containing at least one structure represented by the above general formula (9) is more preferable, and a divalent organic group containing at least one structure represented by the above general formula (9) is particularly preferable.
Further, for the same reason as in general formula (14), V in general formula (10) is preferably a divalent organic group having 1 to 40 carbon atoms, and a divalent chain aliphatic group having 1 to 40 carbon atoms is preferable. More preferred.

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

Among these, phenolic resins are preferred, and novolak-type phenolic resins are particularly preferred, since they are low in cost and have small volumetric shrinkage during curing.

Phenol 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 a base. The phenolic resin obtained when an acid catalyst is used is particularly referred to as a novolac type phenolic resin.

Examples of phenol derivatives include phenol, cresol, ethylphenol, propylphenol, butylphenol, amylphenol, benzylphenol, adamantanephenol, benzyloxyphenol, xylenol, catechol, resorcinol, ethylresorcinol, hexylresorcinol, hydroquinone, pyrogallol, and phlorog. 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 Examples include benzoic acid.

Examples of 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.

It is preferable that component (A) contains (a) a phenol resin having no unsaturated hydrocarbon group, and (b) a modified phenol 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.

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

(b) Modified phenolic resin having an unsaturated hydrocarbon group is generally a compound having phenol or its derivative and an unsaturated hydrocarbon group (preferably one having 4 to 100 carbon atoms) (hereinafter referred to simply as "unsaturated hydrocarbon resin" in some cases). (hereinafter referred to as "unsaturated hydrocarbon group-modified phenol derivatives") with aldehydes, or phenol resins and unsaturated hydrocarbons. It is a reaction product with a group-containing compound.

The phenol derivative mentioned here can be the same as the phenol derivative mentioned above as the raw material for the phenol resin as 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. In addition, from the viewpoint of compatibility in a resin composition and flexibility of a cured film, the unsaturated hydrocarbon group-containing compound preferably has 8 to 80 carbon atoms, and more preferably has 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. The acids include arachidonic acid, eicosapentaenoic acid, sardine acid and docosahexaenoic acid. Among these, esters of unsaturated fatty acids having 8 to 30 carbon atoms and monovalent to trivalent alcohols having 1 to 10 carbon atoms are particularly preferred; Particularly preferred are esters with glycerin.

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 sunflower seed oil, cashew seed oil, sasanqua 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. Furthermore, processed vegetable oils obtained by processing these vegetable oils may also be used.

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

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

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

By polycondensing the unsaturated hydrocarbon group-modified phenol derivative produced by the above reaction with aldehydes, a phenol resin modified with an unsaturated hydrocarbon group-containing compound is produced. As the aldehydes, the same ones as those mentioned above as the aldehydes used to obtain the phenol 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 an acid or a base, and more preferably an acid catalyst. Examples of acid catalysts include hydrochloric acid, sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid, and oxalic acid. These acid catalysts can be used alone or in combination of two or more.

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

Phenol resins modified with unsaturated hydrocarbon group-containing compounds can also be obtained by polycondensing the above-mentioned unsaturated hydrocarbon group-modified phenol derivatives with aldehydes together with compounds other than phenol, such as m-xylene. . 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 phenol resin, the same compounds as the above-mentioned unsaturated hydrocarbon group-containing compounds 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 phenol resin and the unsaturated hydrocarbon group-containing compound is 100 parts by mass of the phenol resin to 1 part by mass of the unsaturated hydrocarbon group-containing compound. It is preferably from 100 parts by weight, more preferably from 2 to 70 parts by weight, even more preferably from 5 to 50 parts by weight. If the amount of the unsaturated hydrocarbon group-containing compound is less than 1 part by mass, the flexibility of the cured film tends to decrease, and if it exceeds 100 parts by mass, the possibility of gelation during the reaction increases, and the cured film tends to decrease. The heat resistance of the film tends to decrease. At this time, p-toluenesulfonic acid, trifluoromethanesulfonic acid, etc. may be used as a catalyst, if necessary. Note that a solvent such as toluene, xylene, methanol, tetrahydrofuran, etc. can be used in the reaction.

The phenolic hydroxyl groups remaining in the phenolic resin modified with the unsaturated hydrocarbon group-containing compound produced by the above method are further reacted with a polybasic acid anhydride. Thereby, an acid-modified phenol resin can also be used as the component (b). By acid-modifying with a polybasic acid anhydride, a carboxy group is introduced, and the solubility of component (b) in an alkaline aqueous solution (developer) is further improved.

The polybasic acid anhydride may have an acid anhydride group formed by dehydration condensation of the carboxyl groups of a polybasic acid having a plurality of carboxyl groups. Examples of polybasic acid anhydrides include phthalic anhydride, succinic anhydride, octenyl succinic anhydride, 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 ethertetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, pyromellitic anhydride, and benzophenonetetracarboxylic dianhydride Examples include aromatic tetrabasic acid dianhydrides such as anhydrides. These may be used alone or in combination of two or more. Among these, the polybasic acid anhydride is preferably a dibasic acid anhydride, and more preferably one or more selected from the group consisting of tetrahydrophthalic anhydride, succinic anhydride, and hexahydrophthalic anhydride. . In this case, there is an advantage that a resist pattern having a better shape can be formed.

Further, (A) the alkali-soluble resin having a phenolic hydroxyl group can further contain a phenol resin that has been acid-modified by reacting with a polybasic acid anhydride. When component (A) contains a phenol resin acid-modified with a polybasic acid anhydride, the solubility of 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, pentadecenyl succinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methyltetrahydro anhydride. Dibasic acid anhydrides such as phthalic acid, methylhexahydrophthalic anhydride, nadic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, tetrabromophthalic anhydride, trimellitic anhydride, Biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, diphenyl ethertetracarboxylic dianhydride, butanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid Examples include aliphatic dianhydrides and aromatic tetrabasic acid dianhydrides. These may be used alone or in combination of two or more. 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 the photoacid generator 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 The preferred types and/or amounts of additives are the same as those described in the section of the polyimide precursor composition.

(D) Solvent Any solvent that can dissolve or disperse each component may be used.

(E) Others It may contain a thermal crosslinking agent, a sensitizer, an adhesion aid, a surfactant, a dissolution promoter, a crosslinking promoter, and the like. Among these, by containing a thermal crosslinking agent, when the photosensitive resin film after pattern formation is heated and cured, the thermal crosslinking agent component reacts with the component (A) to form a crosslinked structure. This enables curing at low temperatures and prevents film brittleness and film melting. Specifically, as the thermal crosslinking agent component, a compound having a phenolic hydroxyl group, a compound having a hydroxymethylamino group, and a compound having an epoxy group can be preferably used.

(developing)
After exposing the polymer having phenolic hydroxyl groups, unnecessary parts are washed away with a developer. As the developer used, for example, an alkaline aqueous solution such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylammonium hydroxide (TMAH) is preferably used. .

(thermal curing)
After development, the polymers having phenolic hydroxyl groups are thermally crosslinked by heating the polymers having phenolic hydroxyl groups. This crosslinked polymer becomes the cured relief pattern, that is, the insulating layer 6.

The heating temperature for thermosetting the polymer having a phenolic hydroxyl group is preferably a low temperature from the viewpoint of influence on other members. 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 devices>
The method for manufacturing a semiconductor device of this embodiment is as follows:
A first step of preparing a semiconductor chip;
The first redistribution layer has a larger area than the semiconductor chip in a plan view in the thickness direction, and includes an intermediate layer electrically connected to the semiconductor chip, and an insulating layer in contact with the intermediate layer. a second step of disposing one rewiring layer on one side of the semiconductor chip;
a third step of covering the prepared semiconductor chip with a sealing material so that the other side of the semiconductor chip is exposed;
A second redistribution layer having a larger area than the semiconductor chip in a plan view in the thickness direction, and including an intermediate layer electrically connected to the semiconductor chip, and an insulating layer in contact with the intermediate layer. a fourth step of disposing a rewiring layer on the other side of the semiconductor chip,
At least one of the insulating layer in the first redistribution layer and the insulating layer in the second redistribution layer has a single layer structure or a multilayer structure, and at least one layer constituting the layer structure has a thickness of The region 6a has a transmittance of 0.5 to 50% at a wavelength of 532 nm when converted to a wavelength of 10 μm.
In the second step and the fourth step, the chip may be mounted on the rewiring layer after the rewiring layer is formed, or the rewiring layer may be formed based on the semiconductor chip.

Here, in the second step, it is preferable to arrange the rewiring layer 4 having the above-mentioned region 6a, and from the viewpoint of visibility of the alignment mark that can be formed on the rewiring layer 4, the outermost layer of the rewiring layer 4 is formed. It is more preferable to form the insulating layer 6 as the region 6a. The third step includes forming a protective layer 8 on the semiconductor chip 2 (protective layer forming step), and sealing the semiconductor chip 2 with the protective layer 8 formed thereon so that at least a portion of the protective layer 8 is exposed. It is preferable to include a step of covering with material 3 (sealing structure forming step). The fourth step preferably includes a step of disposing the rewiring layer 4 on the protective layer 8 side (rewiring layer forming step).

A method for manufacturing a semiconductor device in this embodiment will be explained using FIG. 3. FIG. 3 shows an example of the manufacturing process of the semiconductor device 2 of this embodiment. In the following description, the photosensitive resin composition may be of positive type or negative type.

(1) First step In FIG. 3A1, a pre-processed wafer 10 is prepared. A photosensitive resin composition (a photosensitive composition for forming a protective layer) is applied to the wafer 10 and exposed and developed to form a relief pattern (protective layer forming step). In FIG. 3B1, the wafer 10 on which the relief pattern is formed is diced to form a plurality of semiconductor chips 2. In FIG. As described above, the semiconductor chip 2 is prepared (first step).

(2) Second step In FIG. 3A2, carrier C is prepared. The carrier C is made of glass, for example. An adhesive layer C1 may be formed on the carrier C to temporarily fix the semiconductor package. A photosensitive resin composition (a photosensitive composition for forming an insulating layer) is applied onto the adhesive layer C1, and exposed and developed to form a relief pattern (relief pattern forming step). A relief pattern is formed through exposure and development of the photosensitive resin composition, and this is heated to form a cured relief pattern (insulating layer forming step). Furthermore, wiring is formed in locations where the cured relief pattern is not formed (wiring formation step). A multilayer insulating layer may be formed by repeating the insulating layer forming process and the wiring forming process. As described above, the rewiring layer 4 (first rewiring layer 4A) having a larger area than the semiconductor chip 2 in plan view in the thickness direction is arranged on one side of the semiconductor chip 2 (second step).

One aspect of the second step will be described using the rewiring layer shown in FIG. 1(b) as an example.
First, a non-permanent material pattern using a predetermined non-permanent material is formed on the pattern of the insulating layer (the third insulating layer 6-3 shown in FIG. 1(b)) on the adhesive layer C1. Thereafter, the wiring 5-2 is formed by plating or the like.
After removing the non-permanent material pattern, a photosensitive resin composition is applied onto the insulating layer 6-3 so as to cover the wiring 5-2. After the applied photosensitive resin composition is exposed to light, developed, and cured, an insulating layer (second insulating layer 6 shown in FIG. 1(b)) having a pattern in which the wiring 5-2 is exposed at the bottom of the pattern is formed. -2).
Thereafter, the wiring 5-1 is formed between the patterns of the insulating layer 6-2, and the above steps are repeated to manufacture the rewiring layer shown in FIG. 1(b), which is one aspect of this embodiment. Can be done. Note that the non-permanent material pattern can be produced using a conventionally known photosensitive resin composition.

Here, the insulating layer in contact with the adhesive layer C1 corresponds to the outermost layer of the first redistribution layer 4A, and this insulating layer is configured as the region 6a. In the figure, the wiring exposed on the surface of the first rewiring layer 4A on the semiconductor chip 2 side is not shown.

(3) Third step In FIG. 3C, the semiconductor chip 2 is first rewired at predetermined intervals so that the first rewiring layer 4A and the side of the semiconductor chip 2 on which the protective layer is not formed are in contact with each other. Paste on layer 4A. Next, a metal pillar (wiring) having a height corresponding to the height of the semiconductor chip 2 is formed on the first rewiring layer 4A, and then a mold is formed from above the semiconductor chip 2 to the first rewiring layer 4A. A resin 12 is applied and molded and sealed as shown in FIG. 3D. The mold resin 12 is polished by a CMP process or the like to the extent that the protective layer 8 of the semiconductor chip 2 and the metal pillars (not shown) are exposed (FIG. 3E). As described above, the semiconductor chip 2 is covered with the sealing material 3 so that the other side of the semiconductor chip 2 is exposed (third step).

(4) Fourth step After that, the photosensitive resin composition 13 is applied to the protective layer 8 side of the semiconductor chip (FIG. 3F), and the rewiring layer 4 (second rewiring layer 4B) is formed in the same manner as described above. Form. As described above, the rewiring layer 4 (second rewiring layer 4B) having a larger area than the semiconductor chip 2 in plan view in the thickness direction is arranged on the other surface side of the semiconductor chip 2 (fourth step).

In this embodiment, the relief pattern forming process, the insulating layer 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 insulating layers in the redistribution layer may be multilayered. Therefore, the rewiring layer forming step may include a plurality of relief pattern forming steps, a plurality of insulating layer forming steps, and a plurality of wiring forming steps.

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. Thereafter, it is peeled off from the adhesive layer C1 formed on the carrier C. Thereby, a semiconductor device (semiconductor IC) 1 can be obtained as shown in FIG. 3H. In this embodiment, a plurality of fan-out type semiconductor devices 1 can be obtained by the manufacturing method shown in FIG.

In the present embodiment, in the above-described insulating layer forming step, the insulating layer is preferably formed from a photosensitive resin composition capable of forming at least one compound of polyimide, polybenzoxazole, and a polymer having a phenolic hydroxyl group.

[Other embodiments]
Although the present embodiment has been described above, the aspects of the present invention are not limited to the above.

For example, although FIG. 1 shows a semiconductor chip 2 including two chips in parallel, the number of semiconductor chips may be one, or it may include three or more chips in parallel. Furthermore, the protective layer 8 can be omitted. In this case, the semiconductor chip and the sealing material form substantially the same surface, and the rewiring layer is arranged on this surface.

FIG. 4 is a schematic cross-sectional view showing another aspect of the semiconductor device according to this embodiment. The illustrated semiconductor device 1A includes a second rewiring layer 4B among a first rewiring layer 4A and a second rewiring layer, and does not include a first rewiring layer. The sealing material 3 is in contact with not only the four side surfaces 2c of the semiconductor chip 2 but also one side 2a, that is, the sealing material 3 covers the surfaces of the semiconductor chip 2 other than the other side 2b. In the semiconductor device 1A, the insulating layer 6 in the second redistribution layer 4B includes the above region 6a, and thereby has the insulating layer 6 with excellent developability, and the insulating layer 6 after green laser irradiation. And the semiconductor device 1A in which the intermediate layer (for example, the wiring 5) has good adhesion is provided.

Regarding the Examples and Comparative Examples, the following materials and measurement methods were employed. The invention is not limited only to the following examples.

(Polymer A-1: polyimide precursor)
4,4'-oxydiphthalic dianhydride (ODPA) as a tetracarboxylic dianhydride was placed in a 2-liter separable flask. 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 exotherm due to the reaction was completed, the mixture was allowed to cool to room temperature and left for 16 hours.

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

The obtained reaction solution was added to ethyl alcohol to obtain a precipitate consisting of a crude polymer. The obtained crude polymer was filtered and dissolved in tetrahydrofuran to obtain a crude polymer solution. The resulting crude polymer solution was dropped into water to precipitate the polymer, and the resulting precipitate was filtered and dried under vacuum to obtain powdery polymer A-1. The weight average molecular weight (Mw) of Polymer A-1 was 22,000.

(Polymer A-2 and Polymer A-3: polyimide precursor)
Except for changing the tetracarboxylic dianhydride and diamine as shown in the table below, the reaction was carried out in the same manner as described in the section of Polymer A-1 to obtain Polymer A-2 and Polymer A-3, respectively. Ta. The weight average molecular weight (Mw) of Polymer A-2 was 21,000, and the weight average molecular weight (Mw) of Polymer A-3 was 23,000.

(Polymer B-1: polybenzoxazole precursor)
Into a 0.5 liter flask equipped with a stirrer and a thermometer, 15.48 g of 4,4'-diphenyl ether dicarboxylic acid and N-methylpyrrolidone were charged as a dicarboxylic acid. After cooling the flask to 5° C., thionyl chloride was added dropwise and the reaction was allowed to proceed for 30 minutes to obtain a solution of dicarboxylic acid chloride. Next, N-methylpyrrolidone was charged into a 0.5 liter flask equipped with a stirrer and a thermometer. After stirring and dissolving 12.9 g of 2,2-bis(3-amino-4-hydroxyphenyl)propane and 2.18 g of m-aminophenol as bisaminophenol, pyridine was added. Then, while maintaining the temperature at 0 to 5°C, a solution of dicarboxylic acid chloride was added dropwise over 30 minutes, and stirring was continued for 30 minutes. The solution was poured into 3 liters of water, the precipitate was collected, washed three times with pure water, and then dried under reduced pressure to obtain Polymer B-1.

(Polymer B-2: polybenzoxazole precursor)
Polymer B-2 was obtained by carrying out the reaction in the same manner as described in the section for Polymer B-1, except that the dicarboxylic acid and bisaminophenol were changed as shown in the table below.

(Polymer C-1: Phenol 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 novolac resin (cresol/formaldehyde novolac resin, m-cresol/p-cresol (mole ratio) = 60/40, polystyrene equivalent weight average molecular weight = 12,000, manufactured by Asahi Yokuzai Kogyo Co., Ltd., product name "EP4020G" )

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

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

[Formulation examples 1 to 16]
A resin composition solution was obtained by blending as shown in the table below. The unit of the amount of each component in the table is parts by mass.

[Example 1]
Preparation of semiconductor device (1) First redistribution layer LTHC manufactured by 3M was formed on a 6-inch glass carrier, and then the resin composition of Formulation Example 1 was applied using a coater developer (D-Spin 60A type, manufactured by SOKUDO). ) and prebaked on a hot plate at 110° C. for 180 seconds to form a coating film with a final thickness of 10 μm. Immediately after the coating film is formed (in this case, less than 5 minutes after the coating film is formed), the coating film is exposed to 1000 mJ/cm using a mask with a test pattern using Prisma GHI (manufactured by Ultratech). cm ² of energy was irradiated. Next, this coating film was coated with a coater developer (Model D-Spin 60A, manufactured by SOKUDO) for a time equal to the time required for the unexposed areas to completely dissolve and disappear, multiplied by 1.4, using cyclopentanone as a developer. A relief pattern was obtained by spray-developing the film and spray-rinsing it with propylene glycol methyl ether acetate for 10 seconds (relief pattern forming step).

The wafer on which the relief pattern has been formed is heat-treated at 230°C for 2 hours in a nitrogen atmosphere using a temperature programmable curing furnace (model VF-2000, manufactured by Koyo Lindberg Co., Ltd.) to form a wafer with a thickness of approximately 10 μm. A cured relief pattern made of resin was obtained (insulating layer forming step). On the obtained cured relief pattern, Ti with a thickness of 200 nm and Cu with a thickness of 2 μm were sputtered in this order using the above-mentioned sputtering device (wiring formation step).

After sputtering, the resin composition of Formulation Example 14 was similarly spin-coated using a coater developer (Model D-Spin 60A, manufactured by SOKUDO), and prebaked on a hot plate at 110° C. for 180 seconds to form a coating film. . The obtained coating film was exposed to an energy of 400 mJ/cm ² , developed in the same manner as described above, and heated in a nitrogen atmosphere using a temperature programmable curing furnace (Model VF-2000, manufactured by Koyo Lindberg Co., Ltd.). By heat-treating at 230° C. for 2 hours, a cured film made of resin with a thickness of about 5 μm was obtained on the cured relief pattern of Formulation Example 1. As a result, a rewiring layer (first rewiring layer) was formed.

(2) Second Rewiring Layer A semiconductor chip was mounted on the rewiring layer, and metal pillars were formed. Then, the semiconductor chip and the metal pillars were covered with an epoxy resin as a molding resin to form a sealing material. The height of the sealing material was adjusted by CMP to expose the protective layer of the semiconductor chip and the metal pillars. Next, the resin composition of Formulation Example 14 was applied to the exposed surface. Then, a cured relief pattern made of resin with a thickness of about 5 μm was obtained using the method described above, and a rewiring layer (second rewiring layer) was formed using the same method.

(3) Electronic components (external connection terminals)
A plurality of external connection terminals corresponding to each semiconductor chip were formed on the opposite side of the second rewiring layer from the sealing material. The semiconductor package was then peeled off from the glass carrier and the semiconductor chips were diced to produce the semiconductor device of Example 1, which was a fan-out type wafer level chip size package.

(4) Electronic components (DRAM)
In the process of Example 1 above, before dicing between each semiconductor chip, the insulating layer (outermost layer ) was able to print alignment marks. Then, while checking the alignment marks, it was possible to suitably stack the DRAM on the insulating layer (outermost layer) in the first redistribution layer. In the process of Example 1 above, after providing the DRAM and external connection terminals, it was possible to dice between each semiconductor chip. The above semiconductor device operated without problems.

Note that, as described above, the present invention is not limited to the layer structure of the rewiring layer in Example 1. For example, even if the number of insulating layers and the number of intermediate layers in the redistribution layer are changed, the effects of the present invention can be achieved because the insulating layer includes the above region.

[Example 2-13, Comparative Example 1-3]
A semiconductor device was manufactured in the same manner as described in Example 1, except that the composition of the insulating layer corresponding to the outermost layer in the rewiring layer of the semiconductor device was changed as shown in the table below.

<Measurement of transmittance>
Aluminum (Al) with a thickness of 100 nm was sputtered onto a 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625 ± 25 μm) using a sputtering device (model L-440S-FHL, manufactured by Canon Anelva Inc.). An Al wafer substrate was prepared. The resin composition described in the section of Formulation Examples was spin coated on the above sputtered Al wafer substrate using a spin coater (Model D-spin 60A, manufactured by SOKUDO), and dried by heating at 110°C for 180 seconds to form a film. A spin-coated film with a thickness of 10 μm±0.2 μm was produced. After that, the entire surface was exposed to ghi rays with an exposure dose of 2000 mJ/cm ² using an aligner (PLA-501F, manufactured by Canon), and a nitrogen atmosphere was applied using a vertical curing furnace (manufactured by Koyo Lindberg, model name VF-2000B). Below, a heat curing treatment was performed at 230° C. for 2 hours to produce a cured film. This cured film was peeled off from the silicon wafer by immersing it in a 10% aqueous hydrochloric acid solution to obtain a film sample.

The transmittance of a laser with a wavelength of 532 nm (green laser) was measured by measuring the above film sample using a UV-1800 device manufactured by Shimadzu Corporation at a medium scanning speed and a sampling pitch of 0.5 nm. The results are shown in the table below.

<Developability>
On a 6-inch silicon wafer (manufactured by Fujimi Electronics Co., Ltd., thickness 625 ± 25 μm), 200 nm thick Ti and 400 nm thick Cu were deposited in this order using a sputtering device (Model L-440S-FHL, manufactured by Canon Anelva). A sputtered Cu wafer substrate was prepared. The resin composition of the formulation example corresponding to the outermost layer described in the Examples section was spin-coated onto the sputtered Cu wafer substrate using a spin coater (Model D-spin 60A, manufactured by SOKUDO), and heated at 110°C. The film was dried by heating for 180 seconds to produce a spin-coated film having a thickness of 10 μm±0.2 μm. This spin-coated film was exposed to light using a same-magnification projection exposure apparatus PrismaGHI S/N5503 (manufactured by Ultratech) using a reticle with a test pattern having a circular pattern with a mask size of 100 μm in diameter.

Next, for Formulation Examples 1 to 3 and 8 to 15, the coating film formed on the sputtered Cu wafer was spray developed using a developing machine (Model D-SPIN636, manufactured by Dainippon Screen Co., Ltd.) using cyclopentanone. A circular concave relief pattern was obtained by rinsing with propylene glycol methyl ether acetate. Regarding Formulation Examples 4 to 7, paddle development was performed using a developing machine (D-SPIN, manufactured by Dainippon Screen Co., Ltd.) using a 2.38% tetramethylammonium hydroxide aqueous solution, rinsed with pure and rounded. A punched concave relief pattern was obtained. In addition, the development time of spray development is defined as the time 1.4 times the minimum time for developing the resin composition in the unexposed area in the above 10 μm spin coat film for Formulation Examples 1 to 3 and 8 to 15. However, for Formulation Examples 4 to 7, the time was set to 60 seconds.

To determine whether or not the circular concave relief pattern obtained above with a mask size of 100 μm can be opened, a pattern that satisfies both criteria (I) and (II) below is judged to be acceptable (P:〇), and either A pattern that did not satisfy the following criteria was judged to be a failure (F: ×).
(I) The area of the pattern opening is 1/2 or more of the area of the corresponding pattern mask opening.
(II) No undercut, swelling, and/or bridging is observed in the cross section of the pattern.
Note that (I) was confirmed using FE-SEM (S-4800) manufactured by Hitachi High-Tech Corporation at a magnification of 1K. Concerning (II), confirmation was performed using FIB (JIB-4000) manufactured by JEOL at a magnification of 4K.

<Adhesion evaluation>
A coating film of the resin composition of Formulation Example 1 was formed on the glass carrier on which the release layer was formed so that the final film thickness was 10 microns. Immediately after the coating film is formed (in this case, less than 5 minutes after the coating film is formed), the coating film is exposed to 1000 mJ/cm using Prisma GHI (manufactured by Ultratech) using a mask with a test pattern. cm ² of energy was irradiated. Next, this coating film was coated with a coater developer (Model D-Spin 60A, manufactured by SOKUDO) for a time equal to the time required for the unexposed areas to completely dissolve and disappear, multiplied by 1.4, using cyclopentanone as a developer. and a 10 second rotary spray rinse with propylene glycol methyl ether acetate. As a result, a relief pattern was obtained (relief pattern forming step).

The relief pattern is heat-treated at 230°C for 2 hours in a nitrogen atmosphere using a temperature-programmed curing furnace (VF-2000, manufactured by Koyo Lindberg Co., Ltd.) to form a cured relief made of resin with a thickness of approximately 10 μm. A pattern was obtained (insulating layer formation process).

On the obtained relief pattern, Ti with a thickness of 200 nm and Cu with a thickness of 2 μm were sputtered in this order using the above-mentioned sputtering apparatus (wiring formation step). A coating film was formed on the obtained relief pattern with the resin composition of Formulation Example 13 so that the final coating film was 5 μm, and in the same manner as above, energy was irradiated at an exposure amount of 400 mJ/cm ² . An insulating layer was further formed by spray development and thermosetting.

In the same manner, the resin composition of Formulation Example 13 was coated on the insulating layer, exposed to light, developed, thermally cured, and sputtered to further form an insulating layer (first redistribution layer). Thereafter, a semiconductor chip was mounted on the last formed insulating layer, metal pillars were formed, and the semiconductor chip and metal pillars were covered with an epoxy resin as a molding resin. After exposing the side of the semiconductor chip opposite to the first redistribution layer and the metal pillars by CMP (Chemical Mechanical Polishing) treatment, Formulation Example 13 was applied to the exposed surface in the same manner as above. The resin composition was applied, exposed, developed, thermally cured, and sputtered to form an insulating layer on the surface of the semiconductor chip that was not covered with the sealing material.

The semiconductor package was peeled off from the glass carrier, thereby obtaining a fan-out type package having a cured relief pattern made of the resin composition of Formulation Example 1 in the outermost layer. The outermost layer of the obtained fan-out type package was irradiated with laser at an intensity of 2.4 W using a green laser marker (MD-T1000W, manufactured by Keyence Corporation) to form an alignment mark. After cutting a cross section of the fan-out type package after laser irradiation using an FIB device (manufactured by JEOL Ltd., JIB-4000), the state of adhesion between the insulating layer and the wiring was confirmed. When the area corresponding to the laser irradiation is set as the confirmation range, P (〇) indicates that no peeling occurs in the confirmation range, A (△) indicates that peeling is observed in some areas, and peeling is observed on the entire surface. The result was defined as F(x).

From the above, it was confirmed that the insulating layer obtained using the resin composition of the predetermined formulation example has excellent developability and good adhesion to the intermediate layer after green laser irradiation. For this reason, even in Examples 1 to 14, in which the insulating layer corresponding to the above formulation example was arranged in a predetermined region of the insulating layer of the rewiring layer of the semiconductor device, the portion corresponding to such region is suitable. It can be said that the above-mentioned effects regarding developability and adhesion are achieved.

The present invention is preferably applied to a semiconductor device having a semiconductor chip and a rewiring layer connected to the semiconductor chip, and particularly to a fan-out type wafer level chip size package type semiconductor device.

1, 1A Semiconductor device 2 Semiconductor chip 2a One surface 2b Other surface 2c Four side surfaces 3 Sealing material 4 Rewiring layer 4A First rewiring layer 4B Second rewiring layer 4a First surface 4b Second surface 5, 5 -1,5-2 Wiring 6 Insulating layer 6a Area 6b Other areas 6-1 First insulating layer 6-2 Second insulating layer 6-3 Third insulating layer (outermost layer)
7 External connection terminal 8 Protective layer 9 Terminal 10 Wafer 11 Support 12 Mold resin 13 Photosensitive resin composition C Carrier C1 Adhesive layer D DRAM

Claims (33)

semiconductor chip,
a sealing material in contact with the semiconductor chip;
a rewiring layer disposed on at least one side of the semiconductor chip and the sealing material and having a larger area than the semiconductor chip in a plan view in the thickness direction;
The rewiring layer includes an intermediate layer electrically connected to the semiconductor chip, and an insulating layer in contact with the intermediate layer,
The insulating layer has a single layer structure or a multilayer structure, and at least one layer constituting the layer structure has a transmittance of 0.5 at a wavelength of 532 nm when the thickness of the layer is 10 μm. A semiconductor device comprising an area of ˜50%. The rewiring layer includes a first surface facing the semiconductor chip and a second surface opposite to the first surface, and the region is disposed on the second surface side. The semiconductor device according to claim 1. 2. The semiconductor device according to claim 1, wherein the region is disposed in the outermost layer of the rewiring layer. 2. The semiconductor device according to claim 1, wherein the region is arranged on an extension in the thickness direction of a portion where the intermediate layer and the insulating layer are in contact with each other. When the rewiring layer is a first rewiring layer,
a second redistribution layer disposed on the other side of the semiconductor chip and the sealing material;
The semiconductor device according to claim 1, wherein the region is arranged in a second rewiring layer. A RAM (Random Access Memory) can be arranged on the second surface of the second redistribution layer so as to be electrically connected to the intermediate layer exposed on the second surface,
6. The semiconductor device according to claim 5, wherein the second surface of the first redistribution layer is capable of arranging an external connection terminal so as to be electrically connected to the intermediate layer exposed on the second surface. . The insulating layer has another layer in addition to the layer containing the region,
2. The semiconductor device according to claim 1, wherein the other layer includes another region having a transmittance of more than 50% to 95% at a wavelength of 532 nm when the thickness of the other layer is converted to 10 μm. 2. The semiconductor device according to claim 1, wherein the rewiring layer has three or more layers. The semiconductor device according to claim 1, wherein a plurality of said semiconductor chips are arranged in parallel. The semiconductor device according to claim 1, wherein the sealing material is in contact with the insulating layer. The semiconductor device according to claim 1, wherein the sealing material includes an epoxy resin. The semiconductor device according to claim 1, wherein the insulating layer contains at least one selected from the group consisting of polyimide, polybenzoxazole, and a polymer having a phenolic hydroxyl group. The insulating layer has the following general formula (1):
(In the formula, X ¹ is a tetravalent organic group derived from tetracarboxylic dianhydride, Y ¹ is a divalent organic group derived from diamine, and m is an integer of 1 or more. be.)
2. The semiconductor device according to claim 1, comprising polyimide having a structure represented by: Claim 13, wherein X ¹ in the formula (1) is a tetravalent organic group containing an aromatic ring, and Y ¹ in the formula (1) is a divalent organic group containing an aromatic ring. The semiconductor device described. X ¹ in the formula (1) is represented by the following general formulas (2) to (4):

(In formula (4), R ₉ is an oxygen atom, a sulfur atom, or a divalent organic group.)
14. The semiconductor device according to claim 13, comprising at least one structure represented by: X ¹ in the formula (1) is represented by the following general formula (5):

16. The semiconductor device according to claim 15, comprising a structure represented by: Y ¹ in the above formula (1) is represented by the following general formulas (6) to (8):
(In the formula, R ₁₀ to R ₁₃ are each independently a hydrogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group.)
(In the formula, R ₁₄ to R ₂₁ are each independently a hydrogen atom, a halogen atom, a monovalent organic group having 1 to 5 carbon atoms, or a hydroxyl group.)
(In the formula, R ₂₂ is a divalent group or an oxygen atom, and R ₂₃ to R ₃₀ are each independently a hydrogen atom, a halogen atom, a monovalent aliphatic group having 1 to 5 carbon atoms, or a hydroxyl group. )
14. The semiconductor device according to claim 13, comprising at least one structure represented by: Y ¹ in the formula (1) is represented by the following general formula (9):
14. The semiconductor device according to claim 13, comprising a structure represented by: The insulating layer has the following general formula (10):

(In the formula, U and V are divalent organic groups.)
13. The semiconductor device according to claim 12, comprising the polybenzoxazole having a structure. 20. The semiconductor device according to claim 19, wherein U in the formula (10) is a divalent organic group having 1 to 30 carbon atoms. 20. The semiconductor device according to claim 19, wherein U in the formula (10) is a chain alkylene group having 1 to 8 carbon atoms and in which some or all of the hydrogen atoms are substituted with fluorine atoms. 20. The semiconductor device according to claim 19, wherein V in the formula (10) is a divalent organic group containing an aromatic group. V in the formula (10) is represented by the following general formulas (6) to (8):
(In the formula, R ₁₀ to R ₁₃ are each independently a hydrogen atom or a monovalent aliphatic group having 1 to 5 carbon atoms.)
(In the formula, R ₁₄ to R ₂₁ are each independently a hydrogen atom, a halogen atom, or a monovalent organic group having 1 to 5 carbon atoms.)
(In the formula, R ₂₂ is a divalent group or an oxygen atom, and R ₂₃ to R ₃₀ are each independently a hydrogen atom, a halogen atom, or a monovalent aliphatic group having 1 to 5 carbon atoms. .)
20. The semiconductor device according to claim 19, comprising at least one structure represented by: V in the formula (10) is represented by the following general formula (9):
20. The semiconductor device according to claim 19, comprising a structure represented by: 20. The semiconductor device according to claim 19, wherein V in the formula (10) is a divalent organic group having 1 to 40 carbon atoms. 20. The semiconductor device according to claim 19, wherein V in the formula (10) is a divalent chain aliphatic group having 1 to 20 carbon atoms. 13. The semiconductor device according to claim 12, wherein the polymer having a phenolic hydroxyl group includes a novolac type phenolic resin. 13. The semiconductor device according to claim 12, wherein the polymer having a phenolic hydroxyl group includes a phenol resin having no unsaturated hydrocarbon group and a modified phenol resin having an unsaturated hydrocarbon group. 29. The semiconductor device according to claim 1, wherein the semiconductor device is a fan-out type wafer level chip size package type semiconductor device. A first step of preparing a semiconductor chip;
The first redistribution layer has a larger area than the semiconductor chip in a plan view in the thickness direction, and includes an intermediate layer electrically connected to the semiconductor chip, and an insulating layer in contact with the intermediate layer. a second step of disposing one rewiring layer on one side of the semiconductor chip;
a third step of covering the prepared semiconductor chip with a sealing material so that the other side of the semiconductor chip is exposed;
A second redistribution layer having a larger area than the semiconductor chip in a plan view in the thickness direction, and including an intermediate layer electrically connected to the semiconductor chip, and an insulating layer in contact with the intermediate layer. a fourth step of disposing a second rewiring layer on the other side of the semiconductor chip;
At least one of the insulating layer in the first redistribution layer and the insulating layer in the second redistribution layer has a single layer structure or a multilayer structure, and at least one layer constituting the layer structure is A method for manufacturing a semiconductor device, the semiconductor device having a region having a transmittance of 0.5 to 50% at a wavelength of 532 nm when converted to a thickness of 10 μm. 31. The method of manufacturing a semiconductor device according to claim 30, wherein in the second step, the rewiring layer having the region is provided. 31. The insulating layer forming step includes forming the insulating layer with 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 a semiconductor device. semiconductor chip,
a sealing material in contact with the semiconductor chip;
A rewiring layer disposed on at least one side of the semiconductor chip and the sealing material in a semiconductor device comprising:
The rewiring layer includes an intermediate layer electrically connected to the semiconductor chip, and an insulating layer in contact with the intermediate layer,
The insulating layer has a single layer structure or a multilayer structure, and at least one layer constituting the layer structure has a transmittance of 0.5 at a wavelength of 532 nm when the thickness of the layer is 10 μm. A redistribution layer containing an area of ~50%.

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