TWI818743B - Semiconductor device and manufacturing method thereof - Google Patents

Abstract

An object of the present invention is to provide a semiconductor device that can protect a semiconductor chip and improve the adhesion between the protective layer side and the insulating layer side in the rewiring layer. The semiconductor device of the present invention includes: a semiconductor wafer 2, a sealing material 3 in contact with the semiconductor wafer 2, a rewiring layer 4 with an area larger than that of the semiconductor wafer 2 in plan view, and a protective layer 8 for protecting the semiconductor wafer 2. The protective layer 8 Disposed between the semiconductor chip 2 and the insulating layer 6 of the rewiring layer 4, the difference between the Young's modulus of the protective layer 8 and the Young's modulus of the insulating layer 6 is 0.8 to 5.0 GPa.

Description

Semiconductor device and manufacturing method thereof

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

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

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

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

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

[Problem to be solved by the invention]

For fan-out semiconductor devices, it is not only required to protect the semiconductor chip from the thermal history generated in subsequent processes, but also requires high adhesion between the protective layer side and the insulating layer side in the rewiring layer. However, the adhesion between the protective layer side and the insulating layer side in the rewiring layer of the previous fan-out semiconductor device is insufficient.

The present invention was made in view of this point, and its object is to provide a semiconductor device that can protect a semiconductor chip and improve the adhesion between the protective layer side and the insulating layer side in the rewiring layer, and a manufacturing method thereof. [Technical means to solve problems]

The inventor found that the above problems can be solved by the following technical means. [1] A semiconductor device comprising: a semiconductor wafer, a sealing material in contact with the semiconductor wafer, a rewiring layer having an area larger than that of the semiconductor wafer in plan view, and a protective layer for protecting the semiconductor wafer; the above protective layer configuration Between the semiconductor chip and the insulating layer of the rewiring layer, the difference between the Young's modulus of the protective layer and the Young's modulus of the insulating layer is 0.8 to 5.0 GPa. [2] For example, the semiconductor device of item 1, wherein the difference in Young's modulus is 1.0 to 5.0 GPa. [3] Such as the semiconductor device of item 1 or 2, wherein the difference in the above-mentioned Young's modulus is 2.0~4.5 GPa. [4] The semiconductor device according to any one of items 1 to 3, wherein surfaces of the semiconductor wafer other than the side on which the protective layer is disposed are covered with the sealing material. [5] The semiconductor device according to any one of items 1 to 4, wherein the protective layer is in contact with at least one of the semiconductor chip and the insulating layer. [6] The semiconductor device according to any one of items 1 to 5, wherein the rewiring layer has an intermediate layer electrically connected to the semiconductor chip, and the insulating layer covering the intermediate layer. [7] The semiconductor device of Item 6, wherein a hole is formed in the protective layer, and the semiconductor chip and the intermediate layer are electrically connected through the hole. [8] The semiconductor device of Item 7, wherein the ratio of the opening area originating from the hole in the surface of the semiconductor chip side of the protective layer is less than half. [9] The semiconductor device according to any one of items 1 to 8, wherein the sealing material is in contact with the insulating layer. [10] The semiconductor device according to any one of items 1 to 9, wherein the sealing material contains epoxy resin. [11] The semiconductor device according to any one of items 1 to 10, wherein the protective layer contains at least one selected from the group consisting of polyimide, polybenzoethazole, and a polymer having a phenolic hydroxyl group. [12] The semiconductor device according to any one of items 1 to 11, wherein the insulating layer contains at least one selected from the group consisting of polyimide, polybenzozoazole, and a polymer having a phenolic hydroxyl group. [13] The semiconductor device according to any one of items 1 to 12, wherein the protective layer contains polyimide, and the IR (infrared radiation, infrared) spectrum is measured using the total reflection measurement method (ATR method) 1380 The crest ratio between the crest height near ^{cm -1} and the crest height near 1500 cm ^-1 (crest height near 1380 cm ^-1 /crest height near 1500 cm ^-1 ) is 1.2 to 2.5. [14] The semiconductor device according to any one of items 1 to 13, wherein the insulating layer contains polyimide, and the peak near 1380 cm ^-1 when the IR spectrum is measured using the total reflection measurement method (ATR method) The crest ratio between the height and the crest height near 1500 cm ^-1 (crest height near 1380 cm ^-1 /crest height near 1500 cm ^-1 ) is 0.2 to 0.9. [15] The semiconductor device according to any one of items 1 to 14, wherein at least one of the above-mentioned protective layer and the above-mentioned insulating layer includes polyimide, and the polyimide includes the structure of the following general formula (1), [ chemical 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 greater than 1). [16] The semiconductor device ^of item ¹⁵ , wherein Organic based. [17] The semiconductor device of item 15 or 16, wherein X ¹ in the above general formula (1) contains at least one structure represented by the following general formula (2) to general formula (4): [Chemical 2] [Chemical 3] [Chemical 4] (In the general formula (4), R ₉ is an oxygen atom, a sulfur atom, or a divalent organic group). [18] The semiconductor device of item 17, wherein X ¹ in the above general formula (1) includes a structure represented by the following general formula (5), [Chemical 5] . [19] The semiconductor device according to any one of items 15 to 18, wherein Y ¹ in the above general formula (1) contains at least one structure represented by the following general formula (6) to general formula (8): [ chemical 6] (In the formula, R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are each independently a hydrogen atom, a monovalent aliphatic group with a carbon number of 1 to 5, or a hydroxyl group, and may be the same or different) [Chemical 7] (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, and may be different from each other or the same) [Chemical 8] (In the formula, R ₂₂ is a divalent radical or an oxygen atom, and R ₂₃ to R ₃₀ are independently a hydrogen atom, a halogen atom, a monovalent aliphatic group with 1 to 5 carbon atoms, or a hydroxyl group, which may be the same or different. ). [20] The semiconductor device according to any one of items 15 to 19, wherein Y ¹ in the above general formula (1) contains a structure represented by the following general formula (9), [Chemical 9] . [21] The semiconductor device of item 12, wherein the insulating layer includes polybenzoethazole, and the polybenzoethazole includes the structure of the following general formula (10), [Chemical 10] (In the general formula (10), U and V are divalent organic groups). [22] The semiconductor device of item 21, wherein U in the above general formula (10) is a divalent organic group having 1 to 30 carbon atoms. [23] The semiconductor device of item 22, wherein U in the general formula (10) is a chain alkylene group having 1 to 8 carbon atoms and a part or all of the hydrogen atoms are substituted with fluorine atoms. [24] The semiconductor device according to any one of items 21 to 24, wherein V in the above general formula (10) is a divalent organic group containing an aromatic group. [25] The semiconductor device of item 24, wherein V in the above general formula (10) includes at least one structure represented by the following general formulas (6) to (8): [Chemical 11] (In the formula, R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are each independently a hydrogen atom and a monovalent aliphatic group having 1 to 5 carbon atoms, and may be the same or different) [Chemical 12] (In the formula, R ₁₄ to R ₂₁ are each independently a hydrogen atom, a halogen atom, and a monovalent organic group having 1 to 5 carbon atoms, and may be different from each other or the same) [Chemical 13] (In the formula, R ₂₂ is a divalent group or an oxygen atom, and R ₂₃ to R ₃₀ are independently a hydrogen atom, a halogen atom, and a monovalent aliphatic group having 1 to 5 carbon atoms, and may be the same or different). [26] The semiconductor device of item 25, wherein V in the above general formula (10) includes a structure represented by the following general formula (9), [Chemical 14] . [27] The semiconductor device according to any one of items 21 to 26, wherein V in the above general formula (10) is a divalent organic group having 1 to 40 carbon atoms. [28] The semiconductor device of item 27, wherein V in the above general formula (10) is a bivalent chain aliphatic group having 1 to 20 carbon atoms. [29] The semiconductor device of item 11, wherein the polymer having a phenolic hydroxyl group includes a novolac-type phenolic resin. [30] The semiconductor device of item 11, wherein the polymer having a phenolic hydroxyl group includes a phenolic resin that does not have an unsaturated hydrocarbon group, and a modified phenolic resin that has an unsaturated hydrocarbon group. [31] The semiconductor device according to any one of items 1 to 30, wherein when the above-mentioned rewiring layer is observed in cross-section, the above-mentioned rewiring layer includes: a first insulating layer, a second insulating layer, and an intermediate layer, and the intermediate layer The layer system is different from the above-mentioned first insulating layer and the above-mentioned second insulating layer, and is arranged between the above-mentioned first insulating layer and the above-mentioned second insulating layer; the Young’s modulus of the above-mentioned protective layer is different from that of the above-mentioned first insulating layer and the above-mentioned second insulating layer. 2. The difference in Young’s modulus of at least one of the insulating layers is 0.8 to 5.0 GPa. [32] The semiconductor device of Item 31, wherein the first insulating layer is in contact with the sealing material, and the difference in Young’s modulus is 0.8 to 5.0 GPa or more. [33] The semiconductor device of item 31 or 32, wherein the above-mentioned second insulating layer has a different composition from the above-mentioned first insulating layer. [34] The semiconductor device according to any one of items 1 to 33, wherein the semiconductor device is a fan-out wafer-level chip size packaging type semiconductor device. [35] A method of manufacturing a semiconductor device, which includes: the step of forming a protective layer on a semiconductor wafer; the step of covering the above-mentioned semiconductor wafer on which the above-mentioned protective layer is formed with a sealing material in such a manner that at least part of the protective layer is exposed; and The step of forming a rewiring layer on the side of the protective layer that has an area larger than the semiconductor chip in plan view and includes an insulating layer; and the difference in Young's modulus of the protective layer and the insulating layer is 0.8 to 5.0 GPa. [36] The manufacturing method of a semiconductor device as in item 35, which includes: a protective layer forming step using at least one compound that can form polyimide, polybenzoethazole, and a polymer with a phenolic hydroxyl group The photosensitive resin composition forms the above protective layer. [37] The manufacturing method of a semiconductor device as in item 36 or 37, which includes: an interlayer insulating film forming step using at least one of polyimide, polybenzoethazole, and a polymer having a phenolic hydroxyl group. A photosensitive resin composition of one compound forms the above-mentioned insulating layer. [38] A rewiring layer disposed on at least one side of the semiconductor wafer and the sealing material in a semiconductor device including a semiconductor wafer, a sealing material, and a protective layer, the sealing material being in contact with the semiconductor wafer, and the protective layer For protecting the above-mentioned semiconductor chip, the above-mentioned rewiring layer includes an intermediate layer electrically connected to the above-mentioned semiconductor chip and an insulating layer connected to the above-mentioned intermediate layer. The difference in Young's modulus of the above-mentioned insulating layer and the above-mentioned protective layer is 0.8. ~5.0 GPa. [Effects of the invention]

According to the present invention, it is possible to provide a semiconductor device that can protect a semiconductor chip and improve the adhesion between the protective layer side and the insulating layer side in the rewiring layer, and a manufacturing method thereof.

Hereinafter, one embodiment (hereinafter, abbreviated as "embodiment") of the semiconductor device of the present invention will be described with reference to the drawings. In addition, the present invention is not limited to the following embodiments, and can be implemented with various changes within the scope of the spirit. In this embodiment, the numerical range described using "～" includes the numerical values written before and after "～" within the range. Furthermore, in this embodiment, within the numerical range described in stages, the upper limit or lower limit value described in a certain numerical range may be replaced by the upper limit or lower limit of another numerical range described in stages. . Furthermore, in this embodiment, the upper limit value or the lower limit value described within a certain numerical range may be replaced with the value shown in the embodiment.

(semiconductor device) FIG. 1 is a schematic cross-sectional view of the semiconductor device according to this embodiment. As shown in FIG. 1 , a semiconductor device (semiconductor IC) 1 includes: Semiconductor wafer 2. Sealing material 3 connected to semiconductor chip 2, The rewiring layer 4 has an area larger than that of the semiconductor chip 2 when viewed from above, and Protective layer 8 for protecting the semiconductor chip 2; The protective layer 8 is disposed between the semiconductor chip 2 and the insulating layer (hereinafter, sometimes referred to as "interlayer insulating film") 6 of the rewiring layer 4, The difference between the Young's modulus of the protective layer 8 and the Young's modulus of the insulating layer 6 is 0.8 to 5.0 GPa.

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

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

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

(Rewiring layer) One aspect of this embodiment is a rewiring layer 4 disposed on at least one side of the semiconductor chip 2 and the sealing material 3 in a semiconductor device 2, the semiconductor device 2 having: Semiconductor wafer 2. sealing material 3 connected to the semiconductor chip 2, and The protective layer 8 is used to protect the semiconductor chip 2 . The rewiring layer 4 includes an intermediate layer electrically connected to the semiconductor chip 2 and an insulating layer 6 connected to the intermediate layer. The difference in Young's modulus of the insulating layer 6 and the protective layer 8 is 0.8 to 5.0 GPa. By using such a rewiring layer 4, it is possible to provide a semiconductor device 2 that can protect the semiconductor chip 2 and improve the adhesion between the protective layer 8 side and the insulating layer 6 side in the rewiring layer 4. The rewiring layer 4 is mainly composed of an intermediate layer (for example, the wiring 5 ) and an interlayer insulating film 6 covering the periphery of the wiring 5 . From the viewpoint of preventing accidental conduction with the wiring 5 , the interlayer insulating film 6 is preferably a member with high insulation properties.

Here, the "rewiring layer 4" in this embodiment is a thin film layer having the wiring 5 and the interlayer insulating film 6 as described above, and does not include an interposer or a printed wiring board.

In this embodiment, the film thickness of the rewiring layer 4 can be set to approximately 3 to 30 μm. The film thickness of the rewiring layer 4 may be 1 μm or more, 5 μm or more, or 10 μm or more. In addition, the film thickness of the rewiring layer 4 may be 40 μm or less, 30 μm or less, or 20 μm or less.

When the semiconductor device 1 is viewed from above (viewed in the direction of arrow A), the following figure is shown in FIG. 2 . FIG. 2 is a schematic plan view of the semiconductor device according to this embodiment. Furthermore, the sealing material 3 is omitted.

The semiconductor device 1 shown in FIG. 2 (see FIG. 1 ) is configured such that the area S1 of the rewiring layer 4 is larger than the area S2 of the semiconductor wafer 2 . Although the area S1 of the rewiring layer 4 is not particularly limited, from the viewpoint of increasing the number of external connection terminals, the area S1 of the rewiring layer 4 is preferably at least 1.05 times the area S2 of the semiconductor chip 2, and preferably 1.1 times or more, more preferably 1.2 times or more, especially 1.3 times or more. The upper limit is not particularly limited. The area S1 of the rewiring layer 4 may be 50 times or less, 25 times or less, 10 times or less, or 5 times or less the area S2 of the semiconductor chip 2 . Furthermore, in FIG. 2 , the area of the portion of the rewiring layer 4 covered by the semiconductor chip 2 is also included in the area S1 of the rewiring layer 4 .

In addition, the outer 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 have similar external shapes to a rectangle, and the shapes may also be shapes other than a rectangular shape.

The rewiring layer 4 may be one layer or a plurality of two or more layers. The rewiring layer 4 includes the wiring 5 and the interlayer insulating film 6 filling the spaces between the wirings 5. The rewiring layer 4 may also include a layer composed only of the interlayer insulating film 6 or a layer composed only of the wiring 5.

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

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

As shown in FIG. 1 , the sealing material 3 is preferably in direct contact with the semiconductor wafer 2 and the rewiring layer 4 . Thereby, the sealing property from the surface of the semiconductor chip 2 to the surface of the rewiring layer 4 can be effectively improved. Moreover, it is preferable that the surface of the semiconductor wafer 2 other than the surface on which the protective layer 8 is disposed is covered with the sealing material 3 . Thereby, the sealing property of the semiconductor wafer 2 can be easily improved.

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

(protective layer)

In this embodiment, the difference between the Young's modulus of the interlayer insulating film 6 and the Young's modulus of the protective layer 8 is 0.8 to 5.0 GPa. Here, the Young's modulus can be measured by a known method such as the method described in the following Examples. Regarding the above situation, when measuring Young's modulus, the method described in the Examples is preferably used. On the other hand, it is assumed that depending on the form or type of the sample, measurement by the method described in the Examples cannot be performed or that measurement by the method described in the Examples is impractical. In this case only, Young's modulus can be derived by other methods. As other methods, well-known methods based on conditions and techniques commonly thought of by those in the field are used. An example is a method of deriving Young's modulus from the indentation elastic modulus obtained by a nanoindentation test.

If the difference in Young's modulus is 0.8 to 5.0 GPa, the protective performance of the semiconductor chip 2 is good, the adhesion between the interlayer insulating film 6 and the wiring 5 in the wiring layer 4 is good, and the interlayer insulating film 6 and the protective layer 8 have good adhesion. Excellent adhesion. Although the reasons for these are not certain, the present inventors speculate as follows. Along with miniaturization, semiconductor wafers are required to have a low dielectric constant. To this end, increasing the void ratio in semiconductor wafers is one of the effective strategies. However, if the porosity is increased, the semiconductor wafer is likely to be weakened against external impact or the like. Therefore, when manufacturing a semiconductor device having a semiconductor wafer with increased porosity, the semiconductor wafer must be protected from physical impact by a protective layer. In order to protect the semiconductor chip from physical impact damage, a protective layer with a relatively small deformation is preferred. On the other hand, exposure, development, and hardening for forming the interlayer insulating film may cause residual stress at the interface between the wiring and the interlayer insulating film. Interlayer insulating films are often multi-layered. In this case, exposure, development, and hardening are repeated, so the possibility of generating residual stress at the interface between the wiring and the interlayer insulating film is further increased. Therefore, from the viewpoint of alleviating the residual stress, it is preferable to use a protective layer with a large deformation amount. Here, in the semiconductor wafer 2 , the difference in the Young's modulus of the protective layer 8 and the interlayer insulating film 6 is adjusted to 5.0 GPa or less. This can suppress the difference in the degree of molecular deformation, thereby suppressing the difference between the protective layer 8 and the interlayer insulating film 6 . The interface of the interlayer insulating film 6 is peeled off. Furthermore, by adjusting to 0.8 GPa or above, the layers with larger deformation and the layers with smaller deformation can combine their respective functions of protecting the semiconductor chip 2, so the semiconductor chip 2 can be further protected from physical impact damage.

The difference in Young's modulus is preferably 4.5 GPa or less, more preferably 4.0 GPa or less, and particularly preferably 3.5 GPa or less. Moreover, it is not limited as long as it is 0.8 GPa or more, but it is preferably 1.0 GPa or more, more preferably 1.5 GPa or more, further preferably 2.0 GPa or more, particularly preferably 2.5 GPa or more. Thereby, the effect of the present invention can be easily obtained.

From the viewpoint of protecting the semiconductor chip 2 from physical impact damage, the Young's modulus of the protective layer 8 is preferably 4.0 GPa or more, more preferably 4.5 GPa or more, and particularly preferably 5 GPa or more. Moreover, from the viewpoint of developability, it is preferably 9.0 GPa or less, more preferably 8.5 GPa or less, even more preferably 8.0 GPa or less. From the viewpoint of absorbing the generated residual stress, the Young's modulus of the interlayer insulating film 6 is preferably 5.0 GPa or less, more preferably 4.5 GPa or less, and particularly preferably 4.0 GPa or less. Furthermore, from the viewpoint of chemical resistance when forming the interlayer insulating film 6, it is preferably 2.0 GPa or more, more preferably 2.5 GPa or more, and particularly preferably 3.0 GPa or more.

The protective layer 8 is provided on the surface of the semiconductor wafer 2 that is not covered by the sealing material 3 . When the semiconductor wafer 2 is viewed from above (viewed in the direction of arrow A in FIG. 1 ) from the side covered by the sealing material 3 , the protective layer 8 becomes the back of the semiconductor wafer 2 and is not observed.

The protective layer 8 is in contact with at least one of the semiconductor wafer 2 and the interlayer insulating film 6 . This makes it easy to better protect the semiconductor wafer 2 . In addition, this structure is an aspect that can easily be expected to improve the adhesion between the protective layer 8 side and the interlayer insulating film 6 side. When the semiconductor device 1 has such an aspect, it is also possible to improve the adhesiveness between the protective layer 8 side and the interlayer insulating film. 6 sides of tightness. Especially in the semiconductor device 1 , from the above point of view, it is more preferable that the protective layer 8 is in contact with both the semiconductor chip 2 and the interlayer insulating film 6 . Furthermore, although it is omitted from the semiconductor device 1 , other members may be interposed between the semiconductor chip 2 and the interlayer insulating film 6 as long as the effects of the present invention can be obtained.

A hole 8a is formed in the protective layer 8, and the semiconductor chip 2 side and the wiring 5 side are electrically connected through the hole 8a. Thereby, it is easy to ensure the electrical connection between the semiconductor chip 2 side and the wiring 5 side, and it is easier to protect the semiconductor chip 2 . A plurality of holes 8a in the protective layer 8 are provided corresponding to the terminals 2a of the semiconductor chip 2, and the terminals 2a are respectively inserted into the plurality of holes 8a.

In the semiconductor device 1, the ratio of the opening area originating from the hole 8a in the surface of the semiconductor chip 2 side in the protective layer 8 is less than half. Thereby, the protection area for protecting the semiconductor wafer 2 can be ensured, so that the semiconductor wafer 2 can be further protected. Here, the "opening area" refers to the total area of the opening entrances on the 2-side surface of the semiconductor wafer.

The Young's modulus of the protective layer 8 and the Young's modulus of the interlayer insulating film 6 are, for example, the Young's modulus of the protective layer 8 is larger. This makes it easy to combine the respective functions of the layer with a large deformation amount (in this case, the protective layer 8 ) and the layer with a small deformation amount (in this case, the interlayer insulating film 6 ) to protect the semiconductor chip 2 . , thereby making it easier to protect the semiconductor wafer 2 . Furthermore, regarding the relationship between the Young's modulus of the protective layer and the Young's modulus of the interlayer insulating film, the Young's modulus of the interlayer insulating film can be made larger.

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

The first interlayer insulating film and the second interlayer insulating film may have the same composition or different compositions. The first interlayer insulating film and the second interlayer insulating film may have the same Young's modulus, or may have different Young's modulus. The first interlayer insulating film and the second interlayer insulating film may have the same film thickness, or may have different film thicknesses. It is preferable if the first interlayer insulating film and the second interlayer insulating film have different compositions, different Young's modulus, and/or different film thicknesses, so that each interlayer insulating film can have different properties.

(Composition of protective layer) The composition of the protective layer is not particularly limited, but for example, a film containing at least one compound selected from the group consisting of polyimide, polybenzoethazole, and a polymer having a phenolic hydroxyl group is preferred.

(Resin composition forming protective layer) The resin composition used to form the protective layer is not particularly limited as long as it is a photosensitive resin composition. Preferably, the resin composition is selected from the group consisting of polyimide precursors, polybenzoethazole precursors, and phenolic hydroxyl groups. A photosensitive resin composition containing at least one compound among the polymers. The resin composition used to form the protective layer may be in liquid form or film form. Moreover, the resin composition used for forming a protective layer may be a negative photosensitive resin composition, or it may be a positive photosensitive resin composition.

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

(Resin composition for forming interlayer insulating film) The resin composition used to form the interlayer insulating film 6 is not particularly limited, as long as it is a photosensitive resin composition, and is preferably selected from the group consisting of polyimide precursors, polybenzoethazole precursors, and A photosensitive resin composition containing at least one compound of a phenolic hydroxyl group polymer. The resin composition used to form the interlayer insulating film 6 may be in a liquid form or in a film form. In addition, the resin composition used to form the interlayer insulating film 6 may be a negative photosensitive resin composition or a positive photosensitive resin composition.

In the present embodiment, the pattern obtained by exposing and developing the photosensitive resin composition is called a relief pattern, and what is obtained by heating and hardening the relief pattern is called a cured relief pattern. This hardened relief pattern becomes the protective layer 8 and the interlayer insulating film 6 .

＜Polyimide precursor composition＞ (A)Photosensitive resin Examples of the photosensitive resin used in the polyamide precursor composition include polyamide, polyamide 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.

[Chemical 15] R ¹ and R ² are each independently a hydrogen atom, a saturated aliphatic group with 1 to 30 carbon atoms, an aromatic group, a monovalent organic group with a carbon-carbon unsaturated double bond, or one of the carbon-carbon unsaturated double bonds. Valence ions. 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 greater than 1. m is preferably 2 or more, more preferably 5 or more.

When R ¹ and R ² in the above general formula (11) exist in the form of monovalent cations, O is negatively charged (existing in the form of -O ^- ). Moreover, X ¹ and Y ¹ may contain a hydroxyl group.

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

[Chemical 16] (In the general formula (12), R ₃ , R ₄ and R ₅ are each independently a hydrogen atom or an organic group having 1 to 5 carbon atoms, and m1 is an integer from 1 to 20).

[Chemical 17] (In the general formula (13), R ₆ , R ₇ and R ₈ are each independently a hydrogen atom or an organic group having 1 to 5 carbon atoms, and m ₂ is an integer of 1 to 20).

A plurality of polyamide esters represented by the general formula (11) may be mixed. In addition, a polyamide ester obtained by copolymerizing polyamide esters represented by the general formula (11) may also be used.

X ¹ is not particularly limited, but from the viewpoint of Young's modulus and chemical resistance, X ¹ is preferably a tetravalent organic group including 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).

[Chemical 18]

[Chemical 19]

[Chemistry 20] (In the general formula (4), R ₉ is any one of an oxygen atom, a sulfur atom, and a divalent organic group).

R ₉ in the general formula (4) is, for example, a divalent organic group having 1 to 40 carbon atoms. R ₉ may also 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).

[Chemistry 21]

Y ¹ is not particularly limited, but from the viewpoint of Young's modulus and chemical resistance, Y ¹ is preferably a divalent organic group including 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).

[Chemistry 22] (In the formula, R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are each independently a hydrogen atom and a monovalent aliphatic group having 1 to 5 carbon atoms, and may be the same or different).

[Chemistry 23] (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).

[Chemistry 24] (In the formula, R ₂₂ is a divalent group or an oxygen atom, and R ₂₃ to R ₃₀ are independently a hydrogen atom, a halogen atom, and a monovalent aliphatic group having 1 to 5 carbon atoms, and may be the same or different).

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

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

[Chemical 25]

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

Examples of the tetracarboxylic dianhydride used as a raw material include: pyromellitic dianhydride (PMDA), diphenyl ether-3,3',4,4'-tetracarboxylic dianhydride (4,4 -Oxydiphthalic dianhydride: ODPA), benzophenone-3,3',4,4'-tetracarboxylic dianhydride, biphenyl-3,3',4,4'-tetracarboxylic Acid dianhydride, diphenyltrine-3,3',4,4'-tetracarboxylic dianhydride, diphenylmethane-3,3',4,4'-tetracarboxylic dianhydride, 2,2-bis (3,4-phthalic anhydride)propane, 2,2-bis(3,4-phthalic anhydride)-1,1,1,3,3,3-hexafluoropropane, etc.; but not Limited to these. Moreover, these may be used individually or in mixture of 2 or more types.

Examples of diamines used as raw materials include p-phenylenediamine (PPD), m-phenylenediamine, 4,4'-diaminodiphenyl ether (DADPE), and 3,4'-diaminodiphenyl ether. Diphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diamino-2,2'-dimethylbiphenyl (m-TB) 4,4'-diamine diphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,4'- Diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide, 4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diamine Biphenyl, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diamine diphenylmethane, 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]benzene, bis[4-( 3-Aminophenoxy)phenyl]terine, 4,4-bis(4-aminophenoxy)biphenyl, 4,4-bis(3-aminophenoxy)biphenyl, bis[4 -(4-Aminophenoxy)phenyl]ether, bis[4-(3-aminophenoxy)phenyl]ether, 1,4-bis(4-aminophenyl)benzene, 1, 3-bis(4-aminophenyl)benzene, 9,10-bis(4-aminophenyl)anthracene, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4 -Aminophenyl)hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl)propane, 2,2-bis[4-(4-aminophenoxy)benzene base) hexafluoropropane, 1,4-bis(3-aminopropyldimethylsilyl)benzene, o-bistoluidine, 9,9-bis(4-aminophenyl)benzene, etc. In addition, part of the hydrogen atoms on the benzene ring may also be substituted. Moreover, these may be used individually or in mixture of 2 or more types.

In the synthesis of the polyamide ester (A), it is generally preferred to use a method in which the tetracarboxylic acid diester obtained by performing the esterification reaction of the following tetracarboxylic dianhydride is directly subjected to a condensation reaction with a diamine. .

The alcohols used in the esterification reaction of the above-mentioned tetracarboxylic dianhydride are alcohols having olefinic double bonds. Specific examples include, but are not limited to, 2-hydroxyethyl methacrylate, 2-methacryloxyethyl alcohol, glyceryl diacrylate, and glyceryl dimethacrylate. These alcohols can be used individually or in mixture of 2 or more types.

Regarding the specific synthesis method of the polyamide ester (A) used in this embodiment, a previously known method can be used. An example of the synthesis method is the method shown in International Publication No. 00/43439. That is, the method of temporarily converting the tetracarboxylic acid diester into the tetracarboxylic acid diester dichloride and the diamine in the presence of a basic compound can be exemplified. Condensation reaction to produce polyamide ester (A). Furthermore, a method of producing polyamide ester (A) by subjecting a tetracarboxylic acid diester and a diamine to a condensation reaction in the presence of an organic dehydrating agent can also be exemplified.

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

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

(B1) Photoinitiator When the resin composition used to form the protective layer and the interlayer insulating film is a negative photosensitive resin, a photoinitiator is added. As the photoinitiator, for example, benzophenone, methyl o-benzoyl benzoate, 4-benzoyl-4'-methyldiphenyl ketone, dibenzyl ketone, and benzyl ketone can be used. Benzophenone derivatives; 2,2'-diethoxyacetophenone, 2-hydroxy-2-methylpropiophenone and other acetophenone derivatives; 1-hydroxycyclohexyl phenyl ketone, 9-oxosulfide 𠮿 , 2-Methyl 9-oxosulfide𠮿 , 2-isopropyl 9-oxosulfide𠮿 , and diethyl 9-oxosulfide𠮿 Etc. 9-oxysulfur𠮿 Derivatives; benzoyl derivatives such as benzoyl, benzoyl dimethyl ketal and benzoyl-β-methoxyethyl acetal; benzoin derivatives such as benzoin methyl ether; 2,6-bis( Diazides such as 4'-benzylidenediazide)-4-methylcyclohexanone and 2,6'-bis(4'-benzylidenediazide)cyclohexanone; 1- Phenyl-1,2-butanedione-2-(O-methoxycarbonyl)oxime, 1-phenylpropanedione-2-(O-methoxycarbonyl)oxime, 1-phenylpropanedione -2-(O-ethoxycarbonyl)oxime, 1-phenylpropanedione-2-(O-benzoyl)oxime, 1,3-diphenylglycerol-2-(O-ethyl Oximes such as oxycarbonyl) oxime, 1-phenyl-3-ethoxyglycerone-2-(O-benzoyl) oxime; N-arylglycines such as N-phenylglycine ; Peroxides such as benzoyl peroxide; aromatic biimidazole, and titanocene, etc. Among these, the above-mentioned oximes are preferred in terms of sensitivity.

The added amount of these photoinitiators is preferably 1 to 40 parts by mass, and more preferably 2 to 20 parts by mass relative to 100 parts by mass of polyamide ester (A). The photoinitiator is excellent in sensitivity by adding 1 part by mass or more of a photoinitiator based on 100 parts by mass of polyamide ester (A). In addition, 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 interlayer insulating film is a positive photosensitive resin, a photoacid generator is added. By containing a photoacid generator, an acid is generated in the ultraviolet-exposed part, and the solubility of the exposed part in an alkaline aqueous solution is increased. 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 phosphonium salts. Among them, a quinonediazide compound can be preferably used in terms of exhibiting an excellent dissolution-inhibiting effect and obtaining a highly sensitive positive-type photosensitive resin composition. Moreover, two or more types of photoacid generators may be included.

(C)Additives The difference in Young's modulus of the protective layer and the interlayer insulating film can be adjusted by the polymer structure, and can also be adjusted by the type and amount of additives. If additives are used that interact with the polymer molecular chain and have a relatively planar structure, the Young's modulus can be increased. As additives for increasing Young's modulus, for example, N-(4-bromophenyl)phthalimide, N-(4-chlorophenyl)phthalimide, biphenyl, etc. can be used . In addition, the Young's modulus can also be increased by adding a compound having two or more cross-linking sites and cross-linking the compound. The number of cross-linked sites is preferably 2 or more, more preferably 3 or more. Examples of the cross-linking site include (meth)acrylic acid groups, alkoxymethyl groups, epoxy sites, oxetane sites, and benzodiazepine sites. Examples of additives that reduce Young's modulus include compounds having flexible structures such as ethylene oxide chains and propylene oxide chains. Regarding the amount of additives, it can be adjusted appropriately according to the target Young's modulus difference.

(D)Solvent It is not particularly limited as long as it is a solvent that can dissolve or disperse each component. Examples thereof include N-methyl-2-pyrrolidone, γ-butyrolactone, acetone, methyl ethyl ketone, dimethyl styrene, and the like. These solvents can be used in the range of 30 to 1500 parts by mass based on 100 parts by mass of the (A) photosensitive resin, depending on the thickness and viscosity of the coating film.

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

In addition, it may also contain a sensitizer for increasing the sensitivity, an adhesive agent for improving the adhesion with the base material, etc.

(Develop) After the polyimide precursor composition is exposed, the useless parts are rinsed with a developer. There is no particular limitation on the developer used. In the case of a polyimide precursor composition that is developed using a solvent, N,N-dimethylformamide, dimethylsterine, N, Good solvents such as N-dimethylacetamide, N-methyl-2-pyrrolidinone, cyclopentanone, γ-butyrolactone, acetate esters, etc. These good solvents are compatible with lower alcohols, water, and aromatic hydrocarbons. Mixed solvents such as poor solvents, etc. After development, rinse and clean with a poor solvent if necessary.

In the case of a polyimide precursor composition for development using an alkaline aqueous solution, an aqueous solution of tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, Sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate Aqueous solutions of alkaline compounds such as ester, cyclohexylamine, ethylenediamine, hexamethylenediamine, etc.

(heat hardening) The developed and exposed polyimide precursor composition is heated to close the ring of the polyimide precursor to form polyimide. This polyimide becomes a hardened relief pattern, that is, an interlayer insulating film.

The heating temperature for thermosetting the polyimide precursor composition is not particularly limited. Generally, the higher the thermosetting temperature, the greater the Young's modulus. From the viewpoint of making the Young's modulus of the protective layer of this embodiment a desired value, it is preferably 250°C or higher, more preferably 280°C or higher, and particularly preferably 300°C or higher. Moreover, from the viewpoint of making the Young's modulus of the interlayer insulating film of this embodiment 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 the influence on other members, the temperature is preferably 400°C or lower.

＜Polyimide＞ The structure of the hardened relief pattern formed from the above polyimide precursor composition is the following general formula (1). That is, at least one of the protective layer and the interlayer insulating film contains polyimide, and the polyimide has a structure of the following general formula (1).

[Chemical 26]

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

In the case of alkali-soluble polyimide, the terminal of the polyimide can also be set to a hydroxyl group. When the protective layer of this embodiment contains polyimide, when the IR spectrum is measured using the Attenuated Total Reflection (ATR method), the peak height near 1380 cm ^-1 and 1500 cm ^-1 The crest ratio of nearby crest heights (crest height near 1380 cm ^-1 /crest height near 1500 cm ^-1 ) is preferably 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 "wave crest height near 1380 cm ^-1 " mentioned here is, for example, the maximum wave crest height in the range of 1330 to 1430 cm ^-1 . The "wave crest height near 1500 cm ^-1 " mentioned here is, for example, 1450 to 1550 cm. The maximum wave crest height within the range of ^-1 .

When the interlayer insulating film of this embodiment contains polyimide, when the IR spectrum is measured using the Attenuated Total Reflection (ATR method), the peak height near 1380 cm ^-1 and 1500 cm ^- The crest ratio of the crest height near ¹ (crest height near 1380 cm ^-1 /crest height near 1500 cm ^-1 ) is preferably 0.2 to 0.9. 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, 0.8 or less is preferred, 0.7 or less is more preferred, and 0.6 or less is particularly preferred. The "wave crest height near 1380 cm ^-1 " mentioned here is, for example, the maximum wave crest height in the range of 1330 to 1430 cm ^-1 . The "wave crest height near 1500 cm ^-1 " mentioned here is, for example, 1450 to 1550 cm. The maximum wave crest height within the range of ^-1 .

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

[Chemical 27] (In the general formula (14), Y ² and Y ³ are divalent organic groups).

From the viewpoint of the adhesion between the interlayer insulating film and the sealing material, Y ² is preferably a divalent organic group having 1 to 30 carbon atoms, and more preferably a chain alkylene group having 1 to 15 carbon atoms (wherein, chain The hydrogen atom of the alkylene group may be substituted with a halogen atom), and a chain alkylene group having 1 to 8 carbon atoms in which part or all of the hydrogen atoms are substituted with fluorine atoms is particularly preferred.

In addition, from the viewpoint of the adhesion between the interlayer insulating film and the sealing material, Y ³ is preferably a divalent organic group including an aromatic group, and more preferably includes the following general formula (6) to general formula (8). It represents a divalent organic radical of at least one structure.

[Chemical 28] (In the formula, R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are each independently a hydrogen atom and a monovalent aliphatic group having 1 to 5 carbon atoms, and may be the same or different).

[Chemical 29] (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).

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

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

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

[Chemical 31]

From the viewpoint of the adhesion between the interlayer insulating film and the sealing material, Y ³ is preferably a divalent organic group with a carbon number of 1 to 40, more preferably a divalent chain aliphatic group with a carbon number of 1 to 40, and particularly preferably It is a bivalent chain aliphatic group with 1 to 20 carbon atoms.

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

Dichloride derivatives can be synthesized by acting on dicarboxylic acid derivatives with a halogenating agent. As the halogenating agent, thionite chloride, phosphorus chloride, phosphorus oxychloride, phosphorus pentachloride, etc. used in the general chloride reaction of carboxylic acids can be used.

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

Examples of dicarboxylic acids used as dicarboxylic acid derivatives include isophthalic acid, terephthalic acid, and 2,2-bis(4-carboxyphenyl)-1,1,1,3,3 ,3-Hexafluoropropane, 4,4'-dicarboxybiphenyl, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxytetraphenylsilane, bis(4-carboxyphenyl)sine , 2,2-bis(p-carboxyphenyl)propane, isophthalic 5-tertiary butyric acid, 5-bromoisophthalic acid, 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2 ,6-Naphthalenedicarboxylic acid, malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, Methyl succinic acid, 2,2-dimethyl succinic acid, 2,3-dimethyl succinic acid, dimethyl methyl succinic acid, glutaric acid, hexafluoroglutaric acid, 2-methyl succinic acid Glutaric acid, 3-methylglutaric acid, 2,2-dimethylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, hexanediamine Acid, octafluoroadipic acid, 3-methyladipic acid, octafluoroadipic acid, pimelic acid, 2,2,6,6-tetramethylpimelic acid, suberic acid, dodecafluorooctanedioic acid Acid, azelaic acid, sebacic acid, hexafluorosebacic acid, 1,9-azelaic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, decacanedioic acid Hexacanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, eicosanedioic acid, hexadecanedioic acid, behenedioic acid, tricosanedioic acid, Tetracosanedioic acid, pentacosanedioic acid, hexacosanedioic acid, heptacosanedioic acid, octacosanedioic acid, nonacosanedioic acid, triacontanedioic acid, hexadecanedioic acid Monoalkanedioic acid, triacontanedioic acid, diglycolic acid, dicyclopentadiene carboxylic acid, etc. These can also be used in combination.

Examples of the hydroxyl-containing diamine include: 3,3'-diamino-4,4'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxybiphenyl, Bis(3-amino-4-hydroxyphenyl)propane, bis(4-amino-3-hydroxyphenyl)propane, bis(3-amino-4-hydroxyphenyl)propane, bis(4-amine hydroxy-3-hydroxyphenyl)trine, 2,2-bis(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis( 4-Amino-3-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane, etc. These can also be used in combination.

(B2) Photoacid generator The photoacid generator has the function of increasing the solubility of the alkaline aqueous solution in the light-irradiated part. Examples of the photoacid generator include naphthoquinone diazonium compounds, aryl diazonium salts, diaryl ionium salts, triarylsulfonium salts, and the like. Among them, naphthoquinone diazonium compounds are preferred because of their high sensitivity.

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

(D)Solvent It is not particularly limited as long as it is a solvent that can dissolve or disperse each component.

(E)Others The polybenzoethazole precursor composition may include cross-linking agents, sensitizers, adhesion auxiliaries, thermal acid generators, etc.

(Develop) After exposing the polybenzoethazole precursor composition, the useless portions are rinsed with a developer. The developer used is not particularly limited, and examples thereof include sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, and tetramethylamine. Alkaline aqueous solutions such as ammonium chloride are preferred.

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

(heat hardening) After development, the polybenzoethazole precursor composition is heated, thereby closing the ring of the polybenzoethazole precursor to form polybenzoethazole. This polybenzoconazole becomes the hardened relief pattern, that is, the interlayer insulating film 6 .

The heating temperature used to thermally harden the polybenzoethazole precursor composition is not particularly limited. From the viewpoint of the influence on other components, the heating temperature is preferably a lower temperature. The heating temperature is preferably 250°C or lower, more preferably 230°C or lower, more preferably 200°C or lower, especially 180°C or lower.

＜Polybenzoethazole＞ The structure of the hardened relief pattern formed from the above-mentioned polybenzoethazole precursor composition is the following general formula (10).

[Chemical 32]

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

＜Polymer with phenolic hydroxyl group＞ (A)Photosensitive resin Photosensitive resin is a resin with phenolic hydroxyl groups in its molecules and is soluble in alkali. Specific examples thereof include vinyl polymers containing a monomer unit having a phenolic hydroxyl group such as poly(hydroxystyrene), phenolic resins, poly(hydroxyamide), and poly(hydroxyphenylene) ether. , polynaphthol.

Among these, phenol-based resins are preferred in terms of low cost and small volume shrinkage during hardening, and novolac-type phenolic resins are particularly preferred.

Phenolic resin is a condensation product of phenol or its derivatives and aldehydes. Polycondensation is carried out in the presence of catalysts such as acid or alkali. The phenolic resin obtained when an acid catalyst is used is particularly called a novolak type phenolic resin.

Examples of phenol derivatives include: phenol, cresol, ethylphenol, propylphenol, butylphenol, amylphenol, benzylphenol, adamantanephenol, benzyloxyphenol, xylenol, o- Hydroquinone, resorcinol, ethylresorcinol, hexylresorcinol, hydroquinone, pyrogallol, phloroglucinol, 1,2,4-trihydroxybenzene, rose acid , bisphenol, 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-diiso Propylbenzene, 9,9-bis(4-hydroxy-3-methylphenyl)benzene, 2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane, 2,2-bis(2- Hydroxy-5-biphenyl)propane, dihydroxybenzoic acid, etc.

Examples of the aldehyde compound include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, pivaldehyde, butyraldehyde, valeraldehyde, hexanal, trioxane, glyoxal, cyclohexanal, and diphenyl acetaldehyde. , ethyl butyl aldehyde, benzaldehyde, glyoxylic acid, 5-norphenyl-2-carboxylic aldehyde, malondialdehyde, succinic aldehyde, glutaraldehyde, salicylaldehyde, naphthaldehyde, terephthalaldehyde, etc.

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

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

(b) Modified phenolic resin having an unsaturated hydrocarbon group is usually phenol or a derivative thereof and a compound having an unsaturated hydrocarbon group (preferably one with a carbon number of 4 to 100) (hereinafter, sometimes abbreviated to " The reaction product of "unsaturated hydrocarbon group-containing compound" (hereinafter referred to as "unsaturated hydrocarbon group-modified phenol derivative") and aldehydes, or the reaction product of phenolic resin and unsaturated hydrocarbon group-containing compound.

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

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

Examples of compounds containing unsaturated hydrocarbon groups include unsaturated hydrocarbons having 4 to 100 carbon atoms, polybutadiene having carboxyl groups, epoxidized polybutadiene, linolenic alcohol, oleyl alcohol, unsaturated fatty acids and unsaturated fatty acid esters. . Preferable unsaturated fatty acids include: crotonic acid, myristic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, codoleic acid, erucic acid, tetracosyl acid, and nylonic acid. Sesoleic acid, alpha-linolenic acid, eleostearic acid, stearidonic acid, arachidonic acid, eicosapentaenoic acid, herring acid and docosahexaenoic acid. Among these, esters of unsaturated fatty acids with 8 to 30 carbon atoms and monohydric to trihydric alcohols with 1 to 10 carbon atoms are particularly preferred, and particularly preferred are esters of unsaturated fatty acids with 8 to 30 carbon atoms and trihydric alcohols with 1 to 10 carbon atoms. Glycerol ester of alcohol.

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

Among the above-mentioned vegetable oils, in the reaction between phenol or its derivatives or phenolic resin and vegetable oil, it is preferable to use a non-drying oil from the viewpoint of preventing gelation associated with excessive reaction and thereby improving the yield. . 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 dry oil. Among dry oils, tung oil, linseed oil, soybean oil, walnut oil and safflower oil are preferred, and tung oil and linseed are more preferred in terms of more effectively and reliably exerting the effects of the present invention. Oil.

These unsaturated hydrocarbon group-containing compounds may be used individually by 1 type or in combination of 2 or more types.

When preparing component (b), first, the above-mentioned phenol derivative and the above-mentioned unsaturated hydrocarbon group-containing compound are reacted to prepare an unsaturated hydrocarbon group-modified phenol derivative. The above reaction is preferably carried out at 50 to 130°C. From the viewpoint of improving the flexibility of the cured film (resist pattern), the reaction ratio between the phenol derivative and the unsaturated hydrocarbon group-containing compound is preferably 100 parts by mass of the phenol derivative, and the unsaturated hydrocarbon group-containing compound is preferably 1 to 100 parts by mass, more preferably 5 to 50 parts by mass. If the unsaturated hydrocarbon group-containing compound is less than 1 part by mass, the 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 also be used as a catalyst if necessary.

By condensing the unsaturated hydrocarbon group-modified phenol derivative produced by the above reaction with aldehydes, a phenol-based resin modified with an unsaturated hydrocarbon group-containing compound is produced. The aldehydes that can be used are the same ones described above as the aldehydes used to obtain the phenolic resin.

The reaction between the above-mentioned aldehydes and the above-mentioned unsaturated hydrocarbon-modified phenol derivative is a condensation polymerization reaction, and previously known synthesis conditions of phenolic resins can be used. The reaction is preferably carried out in the presence of a catalyst such as acid or alkali, and more preferably an acid catalyst is used. Examples of the acid catalyst include hydrochloric acid, sulfuric acid, formic acid, acetic acid, p-toluenesulfonic acid, and oxalic acid. These acid catalysts can be used individually by 1 type or in combination of 2 or more types.

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

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

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

The unsaturated hydrocarbon group-containing compound that reacts with the phenolic resin can be the same as the above-mentioned unsaturated hydrocarbon group-containing compound.

The reaction between the phenolic resin and the compound containing unsaturated hydrocarbon groups is usually preferably carried out at 50 to 130°C. In addition, as the reaction ratio between the phenolic resin and the unsaturated hydrocarbon group-containing compound, from the viewpoint of improving the flexibility of the cured film (resist pattern), it is preferable that the reaction ratio between the phenolic resin and the unsaturated hydrocarbon group-containing compound is 100 parts by mass of the phenolic resin. The amount of the hydrocarbon group compound is 1 to 100 parts by mass, more preferably 2 to 70 parts by mass, and still more preferably 5 to 50 parts by mass. If the unsaturated hydrocarbon group-containing compound is less than 1 part by mass, the flexibility of the cured film will tend to decrease. If it exceeds 100 parts by mass, the possibility of gelation during the reaction will tend to increase, and hardening will occur. The film's heat resistance tends to decrease. At this time, p-toluenesulfonic acid, trifluoromethanesulfonic acid, etc. may also be used as catalysts if necessary. Furthermore, solvents such as toluene, xylene, methanol, and tetrahydrofuran can also be used in the reaction.

The polybasic acid anhydride is further reacted with the phenolic hydroxyl group remaining in the phenolic resin modified with the unsaturated hydrocarbon group-containing compound produced by the above method. Thereby, an acid-modified phenolic resin can also be used as the component (b). Acid modification is performed using polybasic acid anhydride to introduce carboxyl groups, thereby further improving the solubility of component (b) in an alkaline aqueous solution (developer).

The polybasic acid anhydride is not particularly limited as long as it has an acid anhydride group formed by dehydration condensation of carboxyl groups of a polybasic acid containing a plurality of carboxyl groups. Examples of the polybasic acid anhydride include phthalic anhydride, succinic anhydride, octenylsuccinic anhydride, pentadecenylsuccinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, Hydrophthalic anhydride, methyl tetrahydro phthalic anhydride, methyl hexahydro phthalic anhydride, tetrahydrophthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride Dibasic acid anhydrides such as methylene tetrahydrophthalic anhydride, tetrabromophthalic anhydride and trimellitic anhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, diphenyl ether tetracarboxylic acid Aromatic tetracarboxylic dianhydrides such as dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyromellitic acid dianhydride and benzophenone tetracarboxylic dianhydride. These can be used individually by 1 type or in combination of 2 or more types. Among these, the polybasic acid anhydride is preferably a dibasic acid anhydride, and more preferably at least one selected from the group consisting of tetrahydrophthalic anhydride, succinic anhydride and hexahydrophthalic anhydride. In this case, there is an advantage that a resist pattern with a better shape can be formed.

Moreover, (A) the alkali-soluble resin which has a phenolic hydroxyl group may further contain the phenolic resin which acid-modified it by reacting a polybasic acid anhydride. By making component (A) contain a phenolic resin modified with a polybasic acid anhydride acid, 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, octenylsuccinic anhydride, pentadecenylsuccinic anhydride, maleic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, Hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetrahydropthalic anhydride, 3,6-endomethylenetetrahydrophthalic anhydride, methyl Endomethylene tetrahydrophthalic anhydride, tetrabromophthalic anhydride, trimellitic anhydride and other dianhydrides, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, diphenyl ether tetracarboxylic acid Acid dianhydride, butane tetracarboxylic acid dianhydride, cyclopentane tetracarboxylic acid dianhydride, pyromellitic acid dianhydride, benzophenone tetracarboxylic acid dianhydride and other aliphatic and aromatic tetracarboxylic acid dianhydrides. These can be used individually by 1 type or in combination of 2 or more types. Among these, the polybasic acid anhydride is preferably a dibasic acid anhydride, and more preferably one or more types selected from the group consisting of, for example, tetrahydrophthalic anhydride, succinic anhydride, and hexahydrophthalic anhydride.

(B2) Photoacid generator Examples of the photoacid generator include naphthoquinone diazonium compounds, aryl diazonium salts, diaryl ionium salts, triarylsulfonium salts, and the like. Among them, naphthoquinone diazonium compounds are preferred because of their high sensitivity.

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

(D)Solvent It is not particularly limited as long as it is a solvent that can dissolve or disperse each component.

(E)Others It can include thermal cross-linking agents, sensitizers, adhesion assistants, dyes, surfactants, dissolution accelerators, cross-linking accelerators, etc. Among them, by containing a thermal crosslinking agent, when the photosensitive resin film after pattern formation is heated and hardened, the thermal crosslinking agent component reacts with the component (A) to form a crosslinked structure. Thereby, it can be hardened at low temperature, and the film can be prevented from being fragile and melting. As the thermal crosslinking agent component, specifically, compounds having a phenolic hydroxyl group, a compound having a hydroxymethylamine group, and a compound having an epoxy group can be used as preferred ones.

(Develop) After exposing the polymer having phenolic hydroxyl groups, the useless parts are rinsed with a developer. The developer used is not particularly limited. For example, sodium hydroxide, potassium hydroxide, sodium silicate, ammonia, ethylamine, diethylamine, triethylamine, triethanolamine, hydrogen Tetramethylammonium oxide (TMAH) and other alkaline aqueous solutions.

(heat hardening) After development, the polymers having phenolic hydroxyl groups are heated, whereby the polymers having phenolic hydroxyl groups are thermally cross-linked with each other. The cross-linked polymer becomes the hardened relief pattern, that is, the interlayer insulating film 6 .

The heating temperature for thermally hardening the polymer having a phenolic hydroxyl group is not particularly limited. From the viewpoint of the influence on other members, the heating temperature is preferably a lower temperature. The heating temperature is preferably 250°C or lower, more preferably 230°C or lower, more preferably 200°C or lower, especially 180°C or lower.

(Method for manufacturing semiconductor device) The manufacturing method of the semiconductor device of this embodiment includes: (Protective layer forming step), which is a step of forming a protective layer on a semiconductor wafer; (Sealing material forming step), which is a step of covering the semiconductor wafer on which the protective layer is formed with a sealing material in such a manner that at least a portion of the protective layer is exposed; and (Rewiring layer forming step), which is a step of forming a rewiring layer on the side of the protective layer that has an area larger than the semiconductor wafer in plan view and includes an interlayer insulating film; The difference in Young's modulus of the protective layer and the interlayer insulating film is 1.0 to 5.0 GPa. The manufacturing method of the semiconductor device in this embodiment will be described using FIG. 3 . FIG. 3 shows an example of manufacturing steps of the semiconductor device according to this embodiment. In FIG. 3A , the wafer 10 having completed the previous steps is prepared. Thereafter, a photosensitive resin composition (photosensitive composition for forming a protective layer) is applied and exposed and developed to form a relief pattern (protective layer forming step). Next, as shown in FIG. 3B , the above-mentioned wafer is cut to form a plurality of semiconductor wafers 2 . The semiconductor wafer 2 prepared in the above manner is attached to the support 11 at specific intervals as shown in FIG. 3C .

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

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

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

Next, in FIG. 3G , a plurality of external connection terminals 7 corresponding to each semiconductor wafer 2 are formed (bump formation), and each semiconductor wafer 2 is cut off. Thereby, as shown in FIG. 3H, a semiconductor device (semiconductor IC) 1 can be obtained. In this embodiment, a plurality of fan-out semiconductor devices 1 can be obtained through the manufacturing method shown in FIG. 3 .

In this embodiment, in the interlayer insulating film forming step, it is preferable to use a photosensitive resin composition that can form at least one compound that can form polyimide, polybenzoethazole, and a polymer having a phenolic hydroxyl group. Form an interlayer insulating film. [Example]

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

Hereinafter, Examples performed in order to clarify the effects of the present invention will be described.

(Polymer A-1: Synthesis of polyimide precursor) 4,4'-oxydiphthalic dianhydride (ODPA) as tetracarboxylic dianhydride was added to a 2 liter capacity separable flask. Furthermore, 2-hydroxyethyl methacrylate (HEMA) and γ-butyrolactone were added and stirred at room temperature. While stirring, pyridine was added to obtain a reaction mixture. After the heat generated by the reaction ends, the mixture is cooled to room temperature and left to stand for 16 hours.

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

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

(Synthesis of polymers A-2 to A-5) Except for changing the tetracarboxylic dianhydride and the diamine as shown in Table 1 below, the reaction was carried out in the same manner as described for the above-mentioned polymer A-1 to obtain a polyimide precursor (polymer). A-2～A-5).

(Polymer B-1: Synthesis of polybenzoethazole precursor) To a 0.5-liter flask equipped with a stirrer and a thermometer, 15.48 g of 4,4'-diphenyl ether dicarboxylic acid as a dicarboxylic acid and N-methylpyrrolidone were added. After the flask was cooled to 5°C, thionyl chloride was added dropwise and the reaction was carried out for 30 minutes to obtain a solution of dicarboxylic acid chloride. Next, N-methylpyrrolidone was added to a 0.5-liter flask equipped with a stirrer and a thermometer. After stirring and dissolving 18.30 g of bis(3-amino-4-hydroxyphenyl)hexafluoropropane and 2.18 g of m-aminophenol, pyridine was added. Next, while maintaining the temperature at 0 to 5°C, a solution of dicarboxylic acid chloride was added dropwise over 30 minutes, and then stirring was continued for 30 minutes. The solution was poured into 3 liters of water, and the precipitate was recovered, washed three times with pure water, and dried under reduced pressure to obtain a polymer (polybenzoconazole precursor (polymer B-1)). The mass of the compound used in polymer B-1 is shown in Table 1 below.

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

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

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

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

[Table 1] Table 1 polymer Tetracarboxylic dianhydride (A) Mass of A (g) Diamine(B) Mass of B (g) Polyimide precursor Polymer A-1 4,4'-Oxydiphthalic dianhydride (ODPA) 147.11 4,4'-Diaminodiphenyl ether (DADPE) 92.9 Polymer A-2 4,4'-Oxydiphthalic dianhydride (ODPA) 147.11 4,4'-Diamino-2,2'-dimethylbiphenyl (m-TB) 98.5 Polymer A-3 4,4'-Oxydiphthalic dianhydride (ODPA) 147.11 p-phenylenediamine (PPD) 50.18 Polymer A-4 4,4'-Oxydiphthalic dianhydride (ODPA) 73.6 4,4'-Diamino-2,2'-dimethylbiphenyl (m-TB) 98.5 Pyromellitic dianhydride (PMDA) 51.7 Polymer A-5 Pyromellitic dianhydride (PMDA) 103.4 4,4'-Diamino-2,2'-dimethylbiphenyl (m-TB) 98.5 polymer Dicarboxylic acid(C) Mass of C(g) Diaminophenol(D) Mass of D(g) Polybenzoethazole precursor Polymer B-1 4,4'-diphenyl ether dicarboxylic acid 15.48 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane 18.3 Polymer B-2 sebacic acid 12.13 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane 18.3 Polymer B-3 Dicyclopentadiene dicarboxylic acid 11.3 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane 18.3 polymer Cresol novolak resin (E) Mass of E(g) Modified phenolic resin (F) Mass of F (g) Phenolic resin Polymer C-1 C1 resin 85 C2 resin 15 Polymer C-2 C1 resin 100 C2 resin 0

[Preparation examples 1 to 13] It was prepared as shown in Table 2 shown below, and a solution of the photosensitive resin composition was obtained. Furthermore, the units in Table 2 are parts by mass. The Young's modulus described in the table was measured using the following method.

Regarding the produced photosensitive resin composition, (1) Young's modulus measurement, (2) peak ratio calculation based on the ATR method, and (3) package formation, cracking, and peeling evaluation were performed. The results of each test are shown in Tables 3 and 4 below.

(1)Measurement of Young’s modulus The resin composition prepared in the preparation example was spin-coated on a 6-inch silicon wafer substrate with an aluminum evaporation layer on the surface in such a way that the film thickness after curing became 10 μm, and pre-baked at 110°C for 4 minutes. Thereafter, a vertical curing oven (model name VF-2000B manufactured by Koyo Lindberg Co., Ltd.) was used to perform heat curing treatment for 2 hours at the curing temperature described in the table, thereby producing a wafer on which a resin film was formed. After cutting a 3 mm wide slit in the resin film of the wafer using a wafer cutting machine (DAD 3350 manufactured by DISCO Co., Ltd.), the wafer was immersed in a dilute hydrochloric acid aqueous solution overnight, and the resin film was peeled off and dried. Cut it into a length of 50 mm to make a sample. For the above sample, the Young's modulus was measured using TENSILON (UTM-II-20 manufactured by Orientec) at a test speed of 40 mm/min and an initial load of 0.5 fs.

(2) Calculation of peak ratio based on ATR method Using FT-IR manufactured by Thermo Fisher Scientific, measuring range 4000 to 400 cm was used for the resin film-formed wafer obtained by the same method as (1) above. ^-1 . Measure the number of times 50 times. It is calculated by finding the peak height near 1380 cm ^-1 and the peak height near 1500 cm ^-1 of the cured film.

(3) Package formation, cracking, and peeling evaluation The photosensitive resin composition prepared in the preparation example is applied to the semiconductor wafer that has formed aluminum pad and silicon oxide, and is cured at the curing temperature in the table to form a protective layer. Thereafter, copper pillars are formed, the photosensitive resin composition prepared in the preparation example is applied, and cured at the curing temperature in the table, thereby forming an interlayer insulating film. Thereafter, R4000 series manufactured by Nagase Kasei Co., Ltd., which is an epoxy sealing material, was used for sealing and thermal hardening at 130°C. The above-mentioned epoxy-based sealing resin was polished, and two rewiring layers were formed using the same type of photosensitive resin composition used to form the above-mentioned interlayer insulating film. After the package was reflowed 20 times, the chip was evaluated for cracks and peeling of the protective layer and interlayer insulating film. Wafer crack evaluation; Among 100 wafers, 0 wafers with cracks were evaluated as excellent, 1 to 9 wafers were evaluated as good, 10 to 19 wafers were evaluated as pass, and 20 or more wafers were evaluated as failed. peeling evaluation; Out of 100 packages, 0 packages with peeling were evaluated as excellent, 1 to 9 packages as good, 10 to 19 packages as qualified, and 20 or more packages as failed. Furthermore, the reflow was performed under simulated reflow conditions using a mesh belt continuous baking furnace (manufactured by Koyo Thermo Systems, model name: 6841-20AMC-36), and was heated to a peak temperature of 260°C in a nitrogen atmosphere. The so-called simulated reflow conditions are based on the form of the reflow conditions described in Section 7.6 of IPC/JEDEC J-STD-020A, which is a standard for the U.S. semiconductor industry group regarding the evaluation method of semiconductor devices. The melting point of the solder is assumed to be High temperature of 220℃ and standardized.

[Table 2] Table 2 photoinitiator D-1 photoacid generator D-2 Cross-linking agent E-1 benzo E-2 Pentaerythritol tetraacrylate E-3 Solvent G-1 γ-butyrolactone G-2 DMSO G-3 Propylene glycol monomethyl ether acetate G-4 Ethyl lactate

[table 3] table 3 Deployment example 1 Deployment example 2 Deployment example 3 Deployment example 4 Deployment example 5 Deployment example 6 Deployment example 7 Deployment example 8 Deployment example 9 Deployment example 10 Deployment example 11 Deployment example 12 Deployment example 13 polymer A-1 100 50 A-2 100 50 A-3 100 A-4 100 100 100 A-5 100 B-1 100 B-2 100 B-3 100 C-1 100 C-2 100 photoinitiator D-1 2 2 2 2 2 2 2 2 photoacid generator D-2 10 10 10 15 15 Cross-linking agent E-1 15 E-2 15 E-3 15 15 Solvent G-1 160 160 160 160 160 160 160 160 225 225 225 G-2 40 40 40 40 40 40 40 40 G-3 25 25 25 G-4 120 120 hardening temperature 230℃ 230℃ 230℃ 300℃ 300℃ 300℃ 300℃ 300℃ 230℃ 230℃ 230℃ 230℃ 230℃ Young's modulus (GPa) 3.2 4.1 3.7 4.8 5.9 6.2 5.4 7.6 2.6 2.7 2.5 3.3 3.5 IR peak ratio 0.6 1 0.8 1.4 2.4 2.4 2.4 3 - - - - -

[Table 4] Table 4 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Comparative example 1 Comparative example 2 Comparative example 3 protective layer Deployment example 5 Deployment example 6 Deployment example 7 Deployment example 4 Deployment example 8 Deployment example 5 Deployment example 5 Deployment example 6 Deployment example 6 Deployment example 4 Deployment example 1 Deployment example 4 Deployment example 8 Interlayer insulation film Deployment example 1 Deployment example 1 Deployment example 1 Deployment example 1 Deployment example 1 Deployment example 9 Deployment example 10 Deployment example 12 Deployment example 13 Deployment example 3 Deployment example 1 Deployment example 2 Deployment example 11 Young's modulus difference 2.7 3 2.2 1.6 4.4 3.3 3.2 2.9 2.7 1.1 0 0.7 5.1 Wafer crack evaluation good good qualified qualified Excellent good good good good qualified Unqualified Unqualified Excellent Flaking evaluation good good Excellent Excellent qualified good good good good Excellent Excellent Excellent Unqualified

As is clear from Table 4, according to the results of the photosensitive resin compositions of Examples 1 to 10, wafer cracking and peeling can be suppressed by setting the Young's modulus difference to a fixed range.

Furthermore, the photosensitive resin compositions of Examples 1 to 10 were used to produce a fan-out wafer-level chip-size packaged semiconductor device containing an epoxy resin in the molding resin, and the result was that the device operated without any problem. [Industrial availability]

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

1:Semiconductor device 2:Semiconductor wafer 2a:Terminal 3:Sealing material 4:Rewiring layer 5: Wiring 6: Interlayer insulation film (insulation layer) 7:External connection terminal 8: Protective layer 8a:hole 10:wafer 11:Support 12:Molding resin 13: Photosensitive resin composition

FIG. 1 is a schematic cross-sectional view of the semiconductor device according to this embodiment. FIG. 2 is a schematic plan view of the semiconductor device according to this embodiment. 3A to 3H are examples of manufacturing steps of the semiconductor device according to this embodiment.

1:Semiconductor device

2:Semiconductor wafer

2a:Terminal

3:Sealing material

4:Rewiring layer

5: Wiring

6: Interlayer insulation film (insulation layer)

7:External connection terminal

8: Protective layer

8a:hole

Claims (38)

A semiconductor device having: semiconductor wafers, Sealing material in contact with the above-mentioned semiconductor chip, The area in plan view is larger than the rewiring layer of the above-mentioned semiconductor chip, and A protective layer used to protect the above-mentioned semiconductor chip; The protective layer is disposed between the semiconductor chip and the insulating layer of the rewiring layer, The difference between the Young's modulus of the protective layer and the Young's modulus of the insulating layer is 0.8 to 5.0 GPa. The semiconductor device of claim 1, wherein the difference in Young's modulus is 1.0 to 5.0 GPa. The semiconductor device of claim 1, wherein the difference in Young's modulus is 2.0 to 4.5 GPa. The semiconductor device according to claim 1, wherein the surface of the semiconductor wafer other than the surface on which the protective layer is disposed is covered by the sealing material. The semiconductor device of claim 1, wherein the protective layer is in contact with at least one of the semiconductor chip and the insulating layer. The semiconductor device of claim 1, wherein the rewiring layer has an intermediate layer electrically connected to the semiconductor chip, and the insulating layer covering the intermediate layer. The semiconductor device of claim 6, wherein a hole is formed in the protective layer, and The semiconductor wafer and the intermediate layer are electrically connected through the holes. The semiconductor device of claim 7, wherein the ratio of the opening area originating from the hole in the surface of the semiconductor chip side of the protective layer is less than half. The semiconductor device of claim 1, wherein the sealing material is in contact with the insulating layer. The semiconductor device of claim 1, wherein the sealing material includes epoxy resin. The semiconductor device of claim 1, wherein the protective layer includes at least one selected from the group consisting of polyimide, polybenzoethazole, and a polymer having a phenolic hydroxyl group. The semiconductor device of claim 1, wherein the insulating layer includes at least one selected from the group consisting of polyimide, polybenzoethazole, and a polymer having a phenolic hydroxyl group. The semiconductor device of claim 1, wherein the protective layer contains polyimide, and when the IR spectrum is measured using a total reflection measurement method (ATR method), the peak height near 1380 cm ^-1 and the peak height near 1500 cm ^-1 The crest ratio of the crest height (crest height near 1380 cm ^-1 / crest height near 1500 cm ^-1 ) is 1.2 to 2.5. In the semiconductor device of claim 1, wherein the insulating layer contains polyimide, when the IR spectrum is measured using a total reflection measurement method (ATR method), the peak height near 1380 cm ^-1 and the peak height near 1500 cm ^-1 The crest ratio of the crest height (crest height near 1380 cm ^-1 / crest height near 1500 cm ^-1 ) is 0.2 to 0.9. The semiconductor device of claim 1, wherein at least one of the above-mentioned protective layer and the above-mentioned insulating layer includes polyimide, and the polyimide includes the structure of the following general formula (1), [Chemical 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 greater than 1). The semiconductor device of claim 15, wherein X ¹ in the above general formula (1) is a tetravalent organic group containing an aromatic ring, and Y ¹ in the above general formula (1) is a divalent organic group containing an aromatic ring. . The semiconductor device of Claim 15, wherein X ¹ in the above-mentioned general formula (1) contains at least one structure represented by the following general formulas (2) to (4): [Chemical 3] [Chemical 4] (In the general formula (4), R ₉ is an oxygen atom, a sulfur atom, or a divalent organic group). The semiconductor device of Claim 17, wherein X ¹ in the above general formula (1) includes a structure represented by the following general formula (5), [Chemical Formula 5] . The semiconductor device of Claim 15, wherein Y ¹ in the above general formula (1) includes at least one structure represented by the following general formula (6) to general formula (8): [Chemical Formula 6] (In the formula, R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are each independently a hydrogen atom, a monovalent aliphatic group with a carbon number of 1 to 5, or a hydroxyl group, and may be the same or different) [Chemical 7] (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, and may be different from each other or the same) [Chemical 8] (In the formula, R ₂₂ is a divalent radical or an oxygen atom, and R ₂₃ to R ₃₀ are independently a hydrogen atom, a halogen atom, a monovalent aliphatic group with 1 to 5 carbon atoms, or a hydroxyl group, which may be the same or different. ). The semiconductor device of claim 15, wherein Y ¹ in the above general formula (1) includes a structure represented by the following general formula (9), [Chemical 9] . The semiconductor device of claim 12, wherein the insulating layer includes polybenzoethazole, and the polybenzoethazole includes the structure of the following general formula (10), [Chemical 10] (In the general formula (10), U and V are divalent organic groups). The semiconductor device of claim 21, wherein U in the general formula (10) is a divalent organic group having 1 to 30 carbon atoms. A semiconductor device according to claim 22, wherein U in the general formula (10) is a chain alkylene group having 1 to 8 carbon atoms and a part or all of the hydrogen atoms are substituted with fluorine atoms. The semiconductor device of claim 21, wherein V in the general formula (10) is a divalent organic group containing an aromatic group. The semiconductor device of claim 24, wherein V in the general formula (10) includes at least one structure represented by the following general formulas (6) to (8): [Chemical 11] (In the formula, R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are each independently a hydrogen atom and a monovalent aliphatic group having 1 to 5 carbon atoms, and may be the same or different) [Chemical 12] (In the formula, R ₁₄ to R ₂₁ are each independently a hydrogen atom, a halogen atom, and a monovalent organic group having 1 to 5 carbon atoms, and may be different from each other or the same) [Chemical 13] (In the formula, R ₂₂ is a divalent group or an oxygen atom, and R ₂₃ to R ₃₀ are independently a hydrogen atom, a halogen atom, and a monovalent aliphatic group having 1 to 5 carbon atoms, and may be the same or different). The semiconductor device of Claim 25, wherein V in the above-mentioned general formula (10) includes a structure represented by the following general formula (9), [Chemical Formula 14] . The semiconductor device of claim 21, wherein V in the general formula (10) is a divalent organic group having 1 to 40 carbon atoms. The semiconductor device of claim 27, wherein V in the general formula (10) is a bivalent chain aliphatic group having 1 to 20 carbon atoms. The semiconductor device according to claim 11, wherein the polymer having a phenolic hydroxyl group contains a novolak type phenolic resin. The semiconductor device of claim 11, wherein the polymer having a phenolic hydroxyl group includes a phenolic resin that does not have an unsaturated hydrocarbon group, and a modified phenol resin that has an unsaturated hydrocarbon group. The semiconductor device of claim 1, wherein when the above-mentioned rewiring layer is observed in cross-section, the above-mentioned rewiring layer includes: 1st insulation layer, 2nd insulation layer, and An intermediate layer, which is a different layer from the above-mentioned first insulating layer and the above-mentioned second insulating layer, and is provided between the above-mentioned first insulating layer and the above-mentioned second insulating layer; The difference between the Young's modulus of the protective layer and the Young's modulus of at least one of the first insulating layer and the second insulating layer is 0.8 to 5.0 GPa. The semiconductor device of claim 31, wherein the first insulating layer and the sealing material are in contact with each other, and the difference in Young's modulus is 0.8 to 5.0 GPa or more. The semiconductor device of claim 31, wherein the second insulating layer has a different composition from the first insulating layer. The semiconductor device according to any one of claims 1 to 33, wherein the semiconductor device is a fan-out type wafer level chip size package type semiconductor device. A method of manufacturing a semiconductor device, which includes: The step of forming a protective layer on a semiconductor wafer; The step of covering the above-mentioned semiconductor wafer on which the above-mentioned protective layer is formed with a sealing material in such a manner that at least a portion of the protective layer is exposed; and The step of forming a rewiring layer on the side of the protective layer that has an area larger than that of the semiconductor chip in plan view and includes an insulating layer; and The difference in Young's modulus of the above protective layer and the above insulating layer is 0.8 to 5.0 GPa. The method for manufacturing a semiconductor device according to claim 35, which includes: a protective layer forming step using a photosensitive compound capable of forming at least one compound among polyimide, polybenzoethazole, and a polymer having a phenolic hydroxyl group. The resin composition forms the above protective layer. The method for manufacturing a semiconductor device according to claim 35 or 36, which includes: a step of forming an interlayer insulating film using at least one of polyimide, polybenzoethazole, and a polymer having a phenolic hydroxyl group. The photosensitive resin composition of the compound forms the above-mentioned insulating layer. A rewiring layer disposed on at least one side of the semiconductor wafer and the sealing material in a semiconductor device including a semiconductor wafer, a sealing material, and a protective layer, the sealing material being in contact with the semiconductor wafer, and the protective layer being used Protect the above-mentioned semiconductor chips, The rewiring layer includes an intermediate layer electrically connected to the semiconductor chip and an insulating layer connected to the intermediate layer. The difference in Young's modulus of the insulating layer and the protective layer is 0.8 to 5.0 GPa.