JPWO2019044817A1 - Negative photosensitive resin composition, semiconductor device and electronic device - Google Patents

Abstract

The negative photosensitive resin composition of the present invention includes a thermosetting resin, a photopolymerization initiator, and a coupling agent containing an acid anhydride as a functional group. Among these, it is preferable that the thermosetting resin contains a polyfunctional epoxy resin. Moreover, it is preferable that content of a polyfunctional epoxy resin is 40-80 mass% with respect to the non-volatile component of a negative photosensitive resin composition. Moreover, it is preferable that a coupling agent is a compound containing the alkoxy silyl group which has a succinic anhydride as a functional group.

Description

  The present invention relates to a negative photosensitive resin composition, a semiconductor device, and an electronic apparatus.

  For semiconductor elements, resin films made of resin materials are used for applications such as protective films, interlayer insulating films, and planarization films. Further, depending on the mounting method of the semiconductor element, it is required to increase the thickness of these resin films. However, when the resin film is thickened, the warp of the semiconductor chip becomes significant.

  On the other hand, a technique for forming a pattern on a resin film by imparting photosensitivity and light transmittance to the resin film is known. Thereby, the target pattern can be accurately formed.

  Therefore, development of a resin composition capable of producing a resin film having photosensitivity and capable of being thickened has been advanced.

  For example, Patent Document 1 discloses a photosensitive resin composition that has excellent light transmittance and can suppress warpage of a semiconductor chip by optimizing the molecular structure and reducing residual stress.

  The photosensitive resin composition is also used for the purpose of forming an insulating portion for embedding wiring in a resin film formed of the photosensitive resin composition to insulate the wiring.

JP 2003-209104 A

  On the other hand, a resin film used for mounting a semiconductor element is required to have adhesion to a semiconductor chip or wiring. For this reason, the adhesiveness with respect to an inorganic material and a metal material is important for the resin film.

  However, since the conventional resin film has low adhesion to inorganic materials and metal materials, there is a problem that reliability after mounting cannot be sufficiently improved.

  An object of the present invention is to provide a photosensitive resin composition capable of forming a resin film having good adhesion to an inorganic material and a metal material, a semiconductor device including the resin film, and an electronic device including the semiconductor device. It is in.

Such an object is achieved by the present inventions (1) to (11) below.
(1) a thermosetting resin;
A photopolymerization initiator;
A coupling agent containing an acid anhydride as a functional group;
A negative photosensitive resin composition comprising:

  (2) The negative photosensitive resin composition according to (1), wherein the thermosetting resin contains a solid component at room temperature.

(3) The negative photosensitive resin composition according to (1) or (2), wherein the thermosetting resin includes a polyfunctional epoxy resin.
(4) The negative photosensitive resin composition according to (3), wherein a content of the polyfunctional epoxy resin is 40 to 80% by mass with respect to a nonvolatile component of the photosensitive resin composition.

  (5) The negative photosensitive resin composition according to any one of (1) to (4), wherein the coupling agent is a compound containing an alkoxysilyl group.

  (6) The negative photosensitive resin composition according to any one of (1) to (5), wherein the acid anhydride is succinic anhydride.

(7) The negative photosensitive resin composition according to any one of (1) to (6), wherein the negative photosensitive resin composition further contains a solvent.
(8) The negative photosensitive resin composition according to (7), wherein the negative photosensitive resin composition is dissolved in the solvent to form a varnish.

(9) a semiconductor chip;
A resin film comprising a cured product of the negative photosensitive resin composition according to any one of (1) to (8), provided on the semiconductor chip;
A semiconductor device comprising:

  (10) The semiconductor device according to (9), wherein a redistribution layer electrically connected to the semiconductor chip is embedded in the resin film.

  (11) An electronic apparatus comprising the semiconductor device according to (9) or (10).

  ADVANTAGE OF THE INVENTION According to this invention, the negative photosensitive resin composition which can form the resin film with favorable adhesiveness with respect to an inorganic material and a metal material is obtained.

Moreover, according to this invention, a semiconductor device provided with the said resin film is obtained.
In addition, according to the present invention, an electronic apparatus including the semiconductor device can be obtained.

FIG. 1 is a longitudinal sectional view showing a first embodiment of a semiconductor device of the present invention. FIG. 2 is a partially enlarged view of a region surrounded by a chain line in FIG. FIG. 3 is a diagram showing an example of a method for manufacturing the semiconductor device shown in FIG. FIG. 4 is a diagram showing an example of a method for manufacturing the semiconductor device shown in FIG. FIG. 5 is a longitudinal sectional view showing a second embodiment of the semiconductor device of the present invention. 6 is a partially enlarged view of a region surrounded by a chain line in FIG. FIG. 7 is a process diagram showing a method of manufacturing the semiconductor device shown in FIG. FIG. 8 is a diagram for explaining a method of manufacturing the semiconductor device shown in FIG. FIG. 9 is a diagram for explaining a method of manufacturing the semiconductor device shown in FIG. FIG. 10 is a diagram for explaining a method of manufacturing the semiconductor device shown in FIG.

  Hereinafter, the negative photosensitive resin composition, the semiconductor device, and the electronic device of the present invention will be described in detail based on preferred embodiments shown in the accompanying drawings.

First, prior to description of a negative photosensitive resin composition and a photosensitive resin film including the negative photosensitive resin composition, a first embodiment of a semiconductor device of the present invention to which these are applied will be described.

<< First Embodiment >>
1. Semiconductor Device FIG. 1 is a longitudinal sectional view showing a first embodiment of a semiconductor device of the present invention. FIG. 2 is a partially enlarged view of a region surrounded by a chain line in FIG. In the following description, the upper side in FIG. 1 is referred to as “upper” and the lower side is referred to as “lower”.

  A semiconductor device 1 shown in FIG. 1 has a so-called package-on-package structure including a through electrode substrate 2 and a semiconductor package 3 mounted thereon.

  Among these, the through electrode substrate 2 includes an organic insulating layer 21 (resin film), a plurality of through wires 22 penetrating from the upper surface to the lower surface of the organic insulating layer 21, and a semiconductor chip 23 embedded in the organic insulating layer 21. A lower wiring layer 24 provided on the lower surface of the organic insulating layer 21, an upper wiring layer 25 provided on the upper surface of the organic insulating layer 21, and a solder bump 26 provided on the lower surface of the lower wiring layer 24. I have. In the semiconductor device 1 of the present embodiment, the organic insulating layer 21 is provided at least on the surface of the semiconductor chip 23 and includes a photosensitive resin composition or a cured product of a photosensitive resin film described later.

  On the other hand, the semiconductor package 3 includes a package substrate 31, a semiconductor chip 32 mounted on the package substrate 31, a bonding wire 33 that electrically connects the semiconductor chip 32 and the package substrate 31, and a semiconductor chip 32 and a bonding wire. The sealing layer 34 in which 33 is embedded, and the solder bump 35 provided on the lower surface of the package substrate 31 are provided.

  The semiconductor package 3 is stacked on the through electrode substrate 2. Thereby, the solder bumps 35 of the semiconductor package 3 and the upper wiring layer 25 of the through electrode substrate 2 are electrically connected.

  Such a semiconductor device 1 has high reliability because the adhesion of the organic insulating layer 21 to the through wiring 22 and the semiconductor chip 23 is good.

  Further, since it is not necessary to use a thick substrate such as an organic substrate including a core layer in the through electrode substrate 2, it is possible to easily reduce the height. For this reason, it can also contribute to size reduction of the electronic device incorporating the semiconductor device 1.

  In addition, since the through electrode substrate 2 provided with different semiconductor chips and the semiconductor package 3 are stacked, the mounting density per unit area can be increased. Also from this viewpoint, the semiconductor device 1 can be downsized.

Hereinafter, the through electrode substrate 2 and the semiconductor package 3 will be described in more detail.
A lower wiring layer 24 and an upper wiring layer 25 included in the through electrode substrate 2 shown in FIG. 2 include an insulating layer, a wiring layer, a through wiring, and the like, respectively. Thereby, the lower wiring layer 24 and the upper wiring layer 25 include wiring inside and on the surface, and are electrically connected so as to penetrate through the through wiring in the thickness direction.

  Among these, the wiring layer included in the lower wiring layer 24 is connected to the semiconductor chip 23 and the solder bump 26. For this reason, the lower wiring layer 24 functions as a rewiring layer of the semiconductor chip 23, and the solder bump 26 functions as an external terminal of the semiconductor chip 23.

  In addition, the through wiring 22 shown in FIG. 2 is provided so as to penetrate the organic insulating layer 21. Thereby, the lower wiring layer 24 and the upper wiring layer 25 can be electrically connected. As a result, the through electrode substrate 2 and the semiconductor package 3 can be stacked, and the function of the semiconductor device 1 can be enhanced.

  Further, the wiring layer included in the upper wiring layer 25 shown in FIG. 2 is connected to the through wiring 22 and the solder bump 35. For this reason, the upper wiring layer 25 is electrically connected to the semiconductor chip 23, functions as a rewiring layer of the semiconductor chip 23, and serves as an interposer interposed between the semiconductor chip 23 and the package substrate 31. Also works. As a result, the density of the rewiring layer can be increased.

  In addition, since the through wiring 22 passes through the organic insulating layer 21, an effect of reinforcing the organic insulating layer 21 can be obtained. For this reason, even when the mechanical strength of the lower wiring layer 24 and the upper wiring layer 25 is low, a decrease in the mechanical strength of the entire through-electrode substrate 2 can be avoided. As a result, the lower wiring layer 24 and the upper wiring layer 25 can be further reduced in thickness, and the semiconductor device 1 can be further reduced in height.

  Furthermore, the organic insulating layer 21 is provided so as to cover the semiconductor chip 23. Thereby, the effect of protecting the semiconductor chip 23 is enhanced. As a result, the reliability of the semiconductor device 1 can be improved. In addition, the semiconductor device 1 that can be easily applied to a mounting method such as the package-on-package structure according to the present embodiment can be obtained.

  Although the diameter W (refer FIG. 2) of the penetration wiring 22 is not specifically limited, It is preferable that it is about 1-100 micrometers, and it is more preferable that it is about 2-80 micrometers. Thereby, the conductivity of the through wiring 22 can be ensured without impairing the mechanical characteristics of the organic insulating layer 21.

  The semiconductor package 3 shown in FIG. 2 may be any form of package. For example, QFP (Quad Flat Package), SOP (Small Outline Package), BGA (Ball Grid Array), CSP (Chip Size Package), QFN (Quad Flat Non-Leaded Package), SON Examples include LF-BGA (Lead Frame BGA).

  The form of the semiconductor chip 32 is not particularly limited. As an example, the semiconductor chip 32 shown in FIG. 1 is configured by stacking a plurality of chips. For this reason, higher density is achieved. The plurality of chips may be provided side by side in the plane direction, or may be provided in the plane direction while being stacked in the thickness direction.

  The package substrate 31 may be any substrate. For example, the package substrate 31 is a substrate including an insulating layer, a wiring layer, a through wiring, and the like (not shown). Among these, the solder bump 35 and the bonding wire 33 can be electrically connected through the through wiring.

  The sealing layer 34 is made of, for example, a known sealing resin material. By providing such a sealing layer 34, the semiconductor chip 32 and the bonding wire 33 can be protected from an external force or an external environment.

  Note that the semiconductor chip 23 provided in the through electrode substrate 2 and the semiconductor chip 32 provided in the semiconductor package 3 are arranged close to each other, so that benefits such as higher speed of communication and lower loss can be obtained. Can do. From this point of view, for example, one of the semiconductor chip 23 and the semiconductor chip 32 is an arithmetic element such as a CPU (Central Processing Unit), a GPU (Graphics Processing Unit), or an AP (Application Processor), and the other is a DRAM (Dynamic Random Access). If a memory element such as a memory) or a flash memory is used, these elements can be arranged close to each other in the same device, so that the semiconductor device 1 that achieves both high functionality and miniaturization is realized. Can do.

<Organic insulation layer>
Next, the organic insulating layer 21 will be described in detail.

  The organic insulating layer 21 of the present embodiment includes a photosensitive resin composition or a cured product of a photosensitive resin film described later.

  The cured product of the photosensitive resin composition according to the present embodiment (including the cured product of the photosensitive resin film; the same shall apply hereinafter) preferably has a glass transition temperature (Tg) of 140 ° C. or higher, and 150 ° C. or higher. It is more preferable that the temperature is 160 ° C. or higher. Thereby, since the heat resistance of the organic insulating layer 21 can be improved, the semiconductor device 1 that can be used even in a high temperature environment, for example, can be realized. In addition, although the upper limit of the hardened | cured material of the photosensitive resin composition does not need to be set in particular, it is 250 degrees C or less as an example.

  Moreover, the glass transition temperature of the hardened | cured material of the photosensitive resin composition uses a thermomechanical analyzer (TMA) with respect to the predetermined test piece (width 4mm x length 20mm x thickness 0.005-0.015mm). The temperature is calculated from the results of measurement under the conditions of a starting temperature of 30 ° C., a measurement temperature range of 30 to 400 ° C., and a heating rate of 5 ° C./min.

  The cured product of the photosensitive resin composition according to this embodiment preferably has a linear expansion coefficient (CTE) of 5 to 80 ppm / ° C, more preferably 10 to 70 ppm / ° C, and 15 to 60 ppm / ° C. More preferably, it is ° C. Thereby, the linear expansion coefficient of the organic insulating layer 21 can be brought close to the linear expansion coefficient of the silicon material, for example. For this reason, for example, the organic insulating layer 21 that hardly causes the warp of the semiconductor chip 23 or the like is obtained. As a result, a highly reliable semiconductor device 1 can be obtained.

  In addition, the linear expansion coefficient of the hardened | cured material of the photosensitive resin composition used a thermomechanical analyzer (TMA) with respect to the predetermined test piece (width 4mm x length 20mm x thickness 0.005-0.015mm). The temperature is calculated from the results of measurement under the conditions of a starting temperature of 30 ° C., a measurement temperature range of 30 to 400 ° C., and a heating rate of 5 ° C./min.

  The cured product of the photosensitive resin composition according to the present embodiment preferably has a 5% thermal weight loss temperature Td5 of 300 ° C. or higher, and more preferably 320 ° C. or higher. As a result, a weight reduction due to thermal decomposition or the like hardly occurs even at a high temperature, and a cured product having excellent heat resistance can be obtained. For this reason, the organic insulating layer 21 excellent in durability under a high temperature environment is obtained.

  In addition, 5% thermogravimetric decrease temperature Td5 of the cured product of the photosensitive resin composition was calculated from the result of measurement using a differential thermothermal gravimetric apparatus (TG / DTA) for 5 mg of the cured product. The

  The cured product of the photosensitive resin composition according to this embodiment preferably has an elongation of 5 to 50%, more preferably 6 to 45%, and even more preferably 7 to 40%. . Thereby, since the elongation rate of the organic insulating layer 21 is optimized, for example, even when the through wiring 22 is provided so as to penetrate the organic insulating layer 21, the organic insulating layer 21 and the through wiring 22 Peeling or the like can be suppressed from occurring at the interface. In addition, the occurrence of cracks and the like can also be suppressed in the organic insulating layer 21 itself.

  Further, if the elongation rate is lower than the lower limit value, there is a risk that cracks or the like may occur in the organic insulating layer 21 depending on the thickness, shape, or the like of the organic insulating layer 21. On the other hand, when the elongation rate exceeds the upper limit, depending on the thickness or shape of the organic insulating layer 21, the mechanical characteristics of the organic insulating layer 21 may be deteriorated.

  In addition, the elongation rate of the hardened | cured material of the photosensitive resin composition is measured as follows. First, a predetermined test piece (width 6.5 mm × length 20 mm × thickness 0.005 to 0.015 mm) is subjected to a tensile test (tensile speed: 5 mm / min) in an atmosphere at a temperature of 25 ° C. and a humidity of 55%. To implement. The tensile test is performed using a tensile tester (Tensilon RTA-100) manufactured by Orientec Co., Ltd. Next, the tensile elongation percentage is calculated from the result of the tensile test. Here, the tensile test is performed with the number of tests n = 10, and an average value of five times with a large measured value is obtained and used as a measured value.

  The cured product of the photosensitive resin composition according to this embodiment preferably has a tensile strength of 20 MPa or more, and more preferably 30 to 300 MPa. Thereby, the organic insulating layer 21 having sufficient mechanical strength and excellent durability can be obtained.

  In addition, the tensile strength of the hardened | cured material of the photosensitive resin composition is calculated | required from the result of the tensile test acquired by the same method as the measurement of the elongation rate mentioned above.

  The cured product of the photosensitive resin composition according to the present embodiment preferably has a tensile modulus of 0.5 GPa or more, and more preferably 1 to 5 GPa. Thereby, the organic insulating layer 21 having sufficient mechanical strength and excellent durability can be obtained.

  In addition, the elasticity modulus of the hardened | cured material of the photosensitive resin composition is calculated | required from the result of the tensile test acquired by the same method as the measurement of the elongation rate mentioned above.

Moreover, as hardened | cured material as mentioned above, what was hardened on the following conditions is used, for example. First, the photosensitive resin composition is applied onto a silicon wafer substrate with a spin coater or the like, and then dried on a hot plate at 120 ° C. for 5 minutes to obtain a coating film. The entire surface of the obtained coating film is exposed at 700 mJ / cm ² , and PEB (Post Exposure Bake) is performed at 70 ° C. for 5 minutes. Then, a cured film is obtained by heating at 200 ° C. for 90 minutes.

2. Manufacturing Method of Semiconductor Device The semiconductor device 1 according to this embodiment described above can be manufactured, for example, as follows.
3 and 4 are diagrams showing an example of a method for manufacturing the semiconductor device 1 shown in FIG.

[1]
First, as shown in FIG. 3A, a substrate 202 is prepared.

  Although it does not specifically limit as a constituent material of the board | substrate 202, For example, a metal material, a glass material, a ceramic material, a semiconductor material, an organic material etc. are mentioned. As the substrate 202, a semiconductor wafer such as a silicon wafer, a glass wafer, or the like may be used. Note that an electronic circuit may be formed on the substrate 202 as necessary.

[2]
Next, as shown in FIG. 3B, the semiconductor chip 23 is disposed on the substrate 202. In the present manufacturing method, as an example, the plurality of semiconductor chips 23 are arranged while being separated from each other. The plurality of semiconductor chips 23 may be of the same type or different types.

  Note that an interposer (not shown) may be provided between the substrate 202 and the semiconductor chip 23 as necessary. The interposer functions as a rewiring layer of the semiconductor chip 23, for example. Therefore, the interposer may include a pad (not shown) for electrical connection with an electrode of the semiconductor chip 23 described later. Thereby, the pad interval and the arrangement pattern of the semiconductor chip 23 can be converted, and the design freedom of the semiconductor device 1 can be further increased.

  As such an interposer, for example, an inorganic substrate such as a silicon substrate, a ceramic substrate or a glass substrate, an organic substrate such as a resin substrate, or the like is used.

[3]
Next, as illustrated in FIG. 3C, a photosensitive resin layer 210 is disposed on the substrate 202 so as to embed the semiconductor chip 23. As the photosensitive resin layer 210, a photosensitive resin composition or a photosensitive resin film described later is used.

  At this time, by using a photosensitive resin film containing a photosensitive resin composition in particular, the photosensitive resin layer 210 can be easily thickened. Thus, the semiconductor chip 23 can be easily embedded without reducing the thickness.

  When forming the photosensitive resin layer 210 using the photosensitive resin film, the photosensitive resin film alone may be attached from above the semiconductor chip 23, and the photosensitive resin film laminated on the carrier film is used as the semiconductor chip. After affixing on 23, you may make it leave the photosensitive resin film by peeling a carrier film.

  Moreover, in the operation | work which affixes the photosensitive resin film, a well-known lamination method may be used. In that case, for example, a vacuum laminator is used. The vacuum laminator may be a batch type or a continuous type.

  Moreover, in the process of affixing the photosensitive resin film, you may make it heat a photosensitive resin film as needed.

  The heating temperature is appropriately set according to the constituent material of the photosensitive resin film, the heating time, and the like, but is preferably about 40 to 150 ° C, more preferably about 50 to 140 ° C, and 60 to 130. More preferably, the temperature is about ° C. By heating at such a temperature, the embedding property of the semiconductor chip 23 in the photosensitive resin film is further improved. As a result, the occurrence of defects such as voids can be suppressed, and the photosensitive resin layer 210 that is further flattened can be efficiently formed.

  When the heating temperature is lower than the lower limit value, the photosensitive resin film is insufficiently melted, so that the embedding property may be lowered depending on the constituent material of the photosensitive resin film. On the other hand, when the heating temperature exceeds the upper limit, there is a possibility that the material may be cured depending on the constituent material of the photosensitive resin film.

  Moreover, although heating time is suitably set according to the constituent material of a photosensitive resin film, heating temperature, etc., it is preferable that it is about 5 to 180 second, and it is more preferable that it is about 10 to 60 second.

  Moreover, in the photosensitive resin film, the semiconductor chip 23 can be embedded by being heated and pressed. The applied pressure at that time is appropriately set according to the constituent material of the photosensitive resin film, but is preferably about 0.2 to 5 MPa, and more preferably about 0.4 to 1 MPa.

  On the other hand, by using a varnish-like photosensitive resin composition, the photosensitive resin layer 210 can be easily flattened.

  In the operation of forming the photosensitive resin layer 210 using the varnish-like photosensitive resin composition, the viscosity is adjusted with a solvent or the like as necessary, and the photosensitive resin layer 210 is applied onto the substrate 202 using various coating apparatuses. Then, the photosensitive resin layer 210 is obtained by drying the obtained coating film. In addition, in order to ensure sufficient thickness so that a semiconductor chip is completely embedded, application | coating and drying of a varnish-like photosensitive resin composition may be repeated in multiple times.

  Examples of the coating device include a spin coater, a spray device, and an ink jet device.

  The film thickness of the photosensitive resin film (film thickness of the photosensitive resin layer 210) is appropriately set according to the film thickness after curing (height H in FIG. 2) and taking into account the curing shrinkage. If it is the thickness which can embed 23, it will not specifically limit. However, it is preferable that it is about 20-1000 micrometers as an example of the film thickness of the photosensitive resin film, it is more preferable that it is about 50-750 micrometers, and it is further more preferable that it is about 100-500 micrometers. By setting the film thickness of the photosensitive resin layer 210 within the above range, the semiconductor chip 23 can be embedded easily, and sufficient mechanical strength is imparted to the cured film of the photosensitive resin layer 210. be able to. As a result, it is possible to form a cured film (organic insulating layer 21) that contributes to the rigidity of the semiconductor device 1 as well as good protection of the semiconductor chip 23.

[4]
Next, as shown in FIG. 3D, a mask 41 is arranged in a predetermined region on the photosensitive resin layer 210. Then, light (active radiation) is irradiated through the mask 41. As a result, the photosensitive resin layer 210 is subjected to an exposure process according to the pattern of the mask 41.

  Thereafter, post-exposure heat treatment is performed as necessary. The conditions for the post-exposure heat treatment are not particularly limited. For example, the heating time is about 50 to 150 ° C. and the heating time is about 1 to 10 minutes.

  FIG. 3D shows a case where the photosensitive resin layer 210 has a so-called negative photosensitivity. In this example, the solubility in the developer is imparted to the region of the photosensitive resin layer 210 corresponding to the non-light-shielding portion of the mask 41.

Thereafter, development processing is performed to form an opening 42 penetrating the photosensitive resin layer 210 corresponding to the non-light-shielding portion of the mask 41 (see FIG. 3E).
Examples of the developer include an organic developer and a water-soluble developer.

  After the development process, the photosensitive resin layer 210 is subjected to a post-development heating process. The conditions for the post-development heat treatment are not particularly limited, but the heating time is about 160 to 250 ° C. and the heating time is about 30 to 180 minutes. Thereby, the photosensitive resin layer 210 can be cured and the organic insulating layer 21 can be obtained while suppressing the thermal effect on the semiconductor chip 23.

[5]
Next, as shown in FIG. 4F, the through wiring 22 is formed in the opening 42 (see FIG. 3E).

  A known method is used to form the through wiring 22, and for example, the following method is used.

  First, a seed layer (not shown) is formed on the organic insulating layer 21. The seed layer is formed on the upper surface of the organic insulating layer 21 together with the inside (side wall and bottom surface) of the opening 42.

  For example, a copper seed layer is used as the seed layer. The seed layer is formed by, for example, a sputtering method.

  The seed layer may be made of the same type of metal as the through wiring 22 to be formed, or may be made of a different kind of metal.

  Next, a resist layer (not shown) is formed on a region other than the opening 42 in the seed layer (not shown). Then, the opening 42 is filled with metal using this resist layer as a mask. For this filling, for example, an electrolytic plating method is used. Examples of the metal to be filled include copper or copper alloy, aluminum or aluminum alloy, gold or gold alloy, silver or silver alloy, nickel or nickel alloy, and the like. In this way, the conductive material is embedded in the opening 42 and the through wiring 22 is formed.

Next, the resist layer (not shown) is removed.
In addition, the formation location of the penetration wiring 22 is not limited to the position shown in the figure. For example, it may be provided at a position penetrating the photosensitive resin layer 210 covering the semiconductor chip 23.

[6]
Next, as shown in FIG. 4G, the upper wiring layer 25 is formed on the upper surface side of the organic insulating layer 21. The upper wiring layer 25 is formed using, for example, a photolithography method and a plating method.

[7]
Next, as shown in FIG. 4H, the substrate 202 is peeled off. As a result, the lower surface of the organic insulating layer 21 is exposed.

[8]
Next, as shown in FIG. 4I, the lower wiring layer 24 is formed on the lower surface side of the organic insulating layer 21. The lower wiring layer 24 is formed using, for example, a photolithography method and a plating method. The lower wiring layer 24 thus formed is electrically connected to the upper wiring layer 25 through the through wiring 22.

[9]
Next, as shown in FIG. 4J, solder bumps 26 are formed on the lower wiring layer 24. Further, a protective film such as a solder resist layer may be formed on the upper wiring layer 25 and the lower wiring layer 24 as necessary.

The through electrode substrate 2 is obtained as described above.
Note that the through electrode substrate 2 shown in FIG. 4 (j) can be divided into a plurality of regions. Therefore, for example, by dividing the through electrode substrate 2 into pieces along the alternate long and short dash line shown in FIG. 4J, a plurality of through electrode substrates 2 can be efficiently manufactured. For example, a diamond cutter or the like can be used for singulation.

[10]
Next, the semiconductor package 3 is disposed on the separated through electrode substrate 2. Thereby, the semiconductor device 1 shown in FIG. 1 is obtained.

  Such a manufacturing method of the semiconductor device 1 can be applied to a wafer level process or a panel level process using a large-area substrate.

  Further, by using the photosensitive resin layer 210 containing the photosensitive resin composition, the semiconductor chip 23 is disposed, the semiconductor chip 23 is embedded, the through wiring 22 is formed, the upper wiring layer 25 is formed, and the lower wiring layer 24 is formed. Can be performed in a wafer level process or a panel level process. Thereby, the manufacturing efficiency of the semiconductor device 1 can be increased and the cost can be reduced.

<< Second Embodiment >>
Next, a second embodiment of the semiconductor device of the present invention will be described.

  FIG. 5 is a longitudinal sectional view showing a second embodiment of the semiconductor device of the present invention. FIG. 6 is a partially enlarged view of a region surrounded by a chain line in FIG. In the following description, the upper side in FIG. 5 is referred to as “upper” and the lower side is referred to as “lower”.

  Hereinafter, the second embodiment of the semiconductor device will be described with a focus on differences from the first embodiment, and description of similar matters will be omitted.

1. Semiconductor Device In the semiconductor device 1 of the second embodiment, the structure of the through wiring formed in the organic insulating layer 21 is different, and the upper wiring layer 25 is formed using a photosensitive resin composition described later. The semiconductor device is the same as the semiconductor device 1 of the first embodiment described above except for the semiconductor device of the first embodiment.

In the semiconductor device 1 of the present embodiment, as shown in FIGS. 5 and 6, a through wiring 221 is provided in the organic insulating layer 21 so as to penetrate the organic insulating layer 21. As a result, the lower wiring layer 24 and the upper wiring layer 25 are electrically connected, and the through electrode substrate 2 and the semiconductor package 3 can be stacked, so that the semiconductor device 1 can have higher functionality. it can. The diameter W (see FIG. 6) of the through wiring 221 is not particularly limited, but can be the same size as the diameter W of the through wiring 22 of the semiconductor device 1 of the first embodiment described above.
The semiconductor device 1 according to this embodiment also includes a through wiring 222 provided so as to penetrate the organic insulating layer 21 located on the upper surface of the semiconductor chip 23 in addition to the through wiring 221. Thereby, electrical connection between the upper surface of the semiconductor chip 23 and the upper wiring layer 25 can be achieved.

Furthermore, the wiring layer 253 included in the upper wiring layer 25 shown in FIG. 6 is connected to the through wiring 221 and the solder bump 35. For this reason, the upper wiring layer 25 is electrically connected to the semiconductor chip 23, functions as a rewiring layer of the semiconductor chip 23, and serves as an interposer interposed between the semiconductor chip 23 and the package substrate 31. Also works.
The upper wiring layer 25 is formed using a photosensitive resin composition described later, and has a configuration in which the wiring layer 253 is embedded in a resin film of the photosensitive resin composition. In such a semiconductor device 1, since the adhesion of the upper wiring layer 25 to the wiring layer 253 is good, the reliability is increased.

2. Next, a method for manufacturing the semiconductor device 1 shown in FIG. 5 will be described.

  FIG. 7 is a process diagram showing a method of manufacturing the semiconductor device 1 shown in FIG. 8 to 10 are diagrams for explaining a method of manufacturing the semiconductor device 1 shown in FIG.

  The manufacturing method of the semiconductor device 1 of the present embodiment includes a chip placement step S1 for obtaining the organic insulating layer 21 so as to embed the semiconductor chip 23 and the through wirings 221 and 222 provided on the substrate 202, An upper wiring layer forming step S2 for forming the upper wiring layer 25 on the semiconductor chip 23, a substrate peeling step S3 for peeling the substrate 202, a lower wiring layer forming step S4 for forming the lower wiring layer 24, and solder bumps 26 are provided. A solder bump forming step S5 for obtaining the through electrode substrate 2 and a laminating step S6 for laminating the semiconductor package 3 on the through electrode substrate 2 are provided.

  Among them, the upper wiring layer forming step S2 includes the first resin film arranging step S20 in which the photosensitive resin varnish 5 is arranged on the organic insulating layer 21 and the semiconductor chip 23 to obtain the photosensitive resin layer 2510, and the photosensitive resin. A first exposure step S21 for exposing the layer 2510, a first development step S22 for developing the photosensitive resin layer 2510, a first curing step S23 for curing the photosensitive resin layer 2510, and a wiring layer. Wiring layer forming step S24 for forming H.253, second resin film arranging step S25 for arranging the photosensitive resin varnish 5 on the photosensitive resin layer 2510 and the wiring layer 253, and obtaining the photosensitive resin layer 2520, and the photosensitive resin A second exposure step S26 for performing an exposure process on the layer 2520, a second development step S27 for performing a development process on the photosensitive resin layer 2520, and a second curing process for performing a curing process on the photosensitive resin layer 2520. Including the S28, and the through wiring forming step S29 of forming the through wiring 254 to the opening 424 (the through hole), the.

  Hereinafter, each process will be described sequentially. In addition, the following manufacturing methods are examples and are not limited to this.

[1] Chip placement step S1
First, as shown in FIG. 8A, a substrate 202, a semiconductor chip 23 and through wirings 221 and 222 provided on the substrate 202, and an organic insulating layer 21 provided so as to embed these are provided. A chip embedded structure 27 is prepared.

  Although it does not specifically limit as a constituent material of the board | substrate 202, For example, a metal material, a glass material, a ceramic material, a semiconductor material, an organic material etc. are mentioned. As the substrate 202, a semiconductor wafer such as a silicon wafer, a glass wafer, or the like may be used.

  The semiconductor chip 23 is bonded on the substrate 202. In this manufacturing method, as an example, a plurality of semiconductor chips 23 are provided on the same substrate 202 while being separated from each other. The plurality of semiconductor chips 23 may be of the same type or different types. Further, the substrate 202 and the semiconductor chip 23 may be fixed through an adhesive layer (not shown) such as a die attach film.

  Note that an interposer (not shown) may be provided between the substrate 202 and the semiconductor chip 23 as necessary. The interposer functions as a rewiring layer of the semiconductor chip 23, for example. Therefore, the interposer may include a pad (not shown) for electrical connection with an electrode of the semiconductor chip 23 described later. Thereby, the pad interval and the arrangement pattern of the semiconductor chip 23 can be converted, and the design freedom of the semiconductor device 1 can be further increased.

  As such an interposer, for example, an inorganic substrate such as a silicon substrate, a ceramic substrate or a glass substrate, an organic substrate such as a resin substrate, or the like is used.

  The organic insulating layer 21 is a resin film containing a thermosetting resin or a thermoplastic resin as exemplified as a component of the photosensitive resin composition described later.

  Examples of the constituent material of the through wirings 221 and 222 include copper or copper alloy, aluminum or aluminum alloy, gold or gold alloy, silver or silver alloy, nickel or nickel alloy, and the like.

  In addition, you may make it prepare the chip | tip embedded structure 27 produced with the method different from the above.

[2] Upper wiring layer forming step S2
Next, the upper wiring layer 25 is formed on the organic insulating layer 21 and the semiconductor chip 23.

[2-1] First resin film arrangement step S20
First, as shown in FIG. 8B, the photosensitive resin varnish 5 is applied (arranged) on the organic insulating layer 21 and the semiconductor chip 23. Thereby, as shown in FIG.8 (c), the liquid film of the photosensitive resin varnish 5 is obtained. The photosensitive resin varnish 5 is a varnish of a photosensitive resin composition described later.

  Application | coating of the photosensitive resin varnish 5 is performed using a spin coater, a bar coater, a spray apparatus, an inkjet apparatus etc., for example.

  The viscosity of the photosensitive resin varnish 5 is not particularly limited, but is preferably 10 to 700 mPa · s, and more preferably 30 to 400 mPa · s. When the viscosity of the photosensitive resin varnish 5 is within the above range, a thinner photosensitive resin layer 2510 (see FIG. 8D) can be formed. As a result, the upper wiring layer 25 can be made thinner, and the semiconductor device 1 can be easily reduced in thickness.

  The viscosity of the photosensitive resin varnish 5 is, for example, a value measured using a cone plate viscometer (TV-25, manufactured by Toki Sangyo) under the conditions of a rotation speed of 50 rpm and a measurement time of 300 seconds.

  Next, the liquid film of the photosensitive resin varnish 5 is dried. As a result, a photosensitive resin layer 2510 shown in FIG.

  Although the drying conditions of the photosensitive resin varnish 5 are not specifically limited, For example, the conditions heated for 1 to 60 minutes at the temperature of 80-150 degreeC are mentioned.

  In this step, instead of the process of applying the photosensitive resin varnish 5, a process of arranging a photosensitive resin film formed by forming the photosensitive resin varnish 5 into a film may be adopted.

  The photosensitive resin film is produced, for example, by applying the photosensitive resin varnish 5 on the ground of a carrier film or the like with various coating apparatuses, and then drying the obtained coating film.

  Thereafter, pre-exposure heat treatment is performed on the photosensitive resin layer 2510 as necessary. By performing the pre-exposure heat treatment, the molecules contained in the photosensitive resin layer 2510 are stabilized, and the reaction in the first exposure step S21 described later can be stabilized. On the other hand, the heating conditions as described later are performed. By being heated at, the adverse effect on the photoacid generator due to heating can be minimized.

  The temperature of the pre-exposure heat treatment is preferably 70 to 130 ° C, more preferably 75 to 120 ° C, and still more preferably 80 to 110 ° C. If the temperature of the pre-exposure heat treatment is below the lower limit, the purpose of stabilizing the molecule by the pre-exposure heat treatment may not be achieved. On the other hand, when the temperature of the pre-exposure heat treatment exceeds the upper limit, the movement of the photoacid generator becomes too active, and the effect that acid is hardly generated even when light is irradiated in the first exposure step S21 described later. However, there is a risk that the processing accuracy of patterning may be reduced due to the wide range.

  The pre-exposure heat treatment time is appropriately set according to the temperature of the pre-exposure heat treatment, and is preferably 1 to 10 minutes, more preferably 2 to 8 minutes, and still more preferably at the temperature. 3-6 minutes. If the pre-exposure heat treatment time is less than the lower limit, the heating time is insufficient, and the object of stabilization of molecules by the pre-exposure heat treatment may not be achieved. On the other hand, if the pre-exposure heat treatment time exceeds the upper limit, the heating time is too long, so even if the pre-exposure heat treatment temperature is within the above range, the action of the photoacid generator is inhibited. There is a risk that.

  The atmosphere for the heat treatment is not particularly limited, and may be an inert gas atmosphere, a reducing gas atmosphere, or the like.

  In addition, the atmospheric pressure is not particularly limited, and may be under reduced pressure or under pressure, but is considered normal pressure in consideration of work efficiency and the like. The normal pressure refers to a pressure of about 30 to 150 kPa, preferably atmospheric pressure.

[2-2] First exposure step S21
Next, the photosensitive resin layer 2510 is exposed.

  First, as shown in FIG. 8D, a mask 412 is disposed in a predetermined region on the photosensitive resin layer 2510. Then, light (active radiation) is irradiated through the mask 412. Thus, the photosensitive resin layer 2510 is subjected to an exposure process according to the pattern of the mask 412.

  Note that FIG. 8D illustrates a case where the photosensitive resin layer 2510 has a so-called negative photosensitivity. In this example, the solubility in the developer is imparted to the region corresponding to the light shielding portion of the mask 412 in the photosensitive resin layer 2510.

  On the other hand, in the region corresponding to the transmission part of the mask 412, a catalyst such as an acid is generated by the action of the photosensitive agent. The generated acid acts as a catalyst for the reaction of the thermosetting resin in the steps described later.

The exposure amount in the exposure treatment is not particularly limited, but is preferably 100 to 2000 mJ / cm ^2, and more preferably 200~1000mJ / cm ^2. Thereby, underexposure and overexposure in the photosensitive resin layer 2510 can be suppressed. As a result, finally, high patterning accuracy can be realized.
Thereafter, the post-exposure heat treatment is performed on the photosensitive resin layer 2510 as necessary.

  The temperature of the post-exposure heat treatment is not particularly limited, but is preferably 50 to 150 ° C, more preferably 50 to 130 ° C, still more preferably 55 to 120 ° C, and particularly preferably 60 to 110 ° C. Is done. By performing post-exposure heat treatment at such a temperature, the catalytic action of the generated acid is sufficiently enhanced, and the thermosetting resin can be reacted sufficiently in a shorter time. On the other hand, if the temperature is too high, the diffusion of the acid is promoted and the patterning processing accuracy may be lowered. However, such a concern can be reduced if the temperature is within the above range.

  If the temperature of the post-exposure heat treatment is below the lower limit, the action of a catalyst such as an acid cannot be sufficiently enhanced, and the reaction rate of the thermosetting resin may be reduced or may take time. There is. On the other hand, when the temperature of the post-exposure heat treatment exceeds the upper limit, acid diffusion is promoted (widened), and patterning processing accuracy may be reduced.

  On the other hand, the time of the post-exposure heat treatment is appropriately set according to the temperature of the post-exposure heat treatment, and is preferably 1 to 30 minutes, more preferably 2 to 20 minutes, and still more preferably at the temperature. 3-15 minutes. By performing post-exposure heat treatment in such a time, the thermosetting resin can be sufficiently reacted, and acid diffusion can be suppressed to prevent patterning processing accuracy from being lowered.

  Further, the atmosphere of the post-exposure heat treatment is not particularly limited, and may be an inert gas atmosphere, a reducing gas atmosphere, or the like.

  In addition, the atmospheric pressure of the post-exposure heat treatment is not particularly limited, and may be under reduced pressure or under pressure, but is considered normal pressure in consideration of work efficiency and the like. Thereby, the pre-exposure heat treatment can be performed relatively easily. The normal pressure refers to a pressure of about 30 to 150 kPa, preferably atmospheric pressure.

[2-3] First development step S22
Next, the photosensitive resin layer 2510 is developed. Thus, an opening 423 that penetrates the photosensitive resin layer 2510 is formed in a region corresponding to the light shielding portion of the mask 412 (see FIG. 9E).
Examples of the developer include an organic developer and a water-soluble developer.

[2-4] First curing step S23
After the development process, the photosensitive resin layer 2510 is subjected to a curing process (post-development heating process). Although the conditions for the curing treatment are not particularly limited, the heating time is about 160 to 250 ° C. and the heating time is about 30 to 240 minutes. Thereby, the photosensitive resin layer 2510 can be cured and the organic insulating layer 251 can be obtained while suppressing the thermal effect on the semiconductor chip 23.

[2-5] Wiring layer forming step S24
Next, a wiring layer 253 is formed over the organic insulating layer 251 (see FIG. 9F). The wiring layer 253 is formed by, for example, obtaining a metal layer by using a vapor phase film forming method such as a sputtering method or a vacuum deposition method, and then patterning the metal layer by a photolithography method and an etching method.

  Prior to the formation of the wiring layer 253, surface modification treatment such as plasma treatment may be performed.

[2-6] Second resin film arrangement step S25
Next, as shown in FIG. 9G, a photosensitive resin layer 2520 is obtained in the same manner as in the first resin film arranging step S20. The photosensitive resin layer 2520 is disposed so as to cover the wiring layer 253.

  Thereafter, pre-exposure heat treatment is performed on the photosensitive resin layer 2520 as necessary. The processing conditions are, for example, the conditions described in the first resin film arranging step S20.

[2-7] Second exposure step S26
Next, the photosensitive resin layer 2520 is exposed. The processing conditions are, for example, the conditions described in the first exposure step S21.

  Thereafter, post-exposure heat treatment is performed on the photosensitive resin layer 2520 as necessary. The processing conditions are, for example, the conditions described in the first exposure step S21.

[2-8] Second development step S27
Next, the photosensitive resin layer 2520 is subjected to development processing. The processing conditions are, for example, the conditions described in the first development step S22. Thereby, the opening part 424 which penetrates the photosensitive resin layers 2510 and 2520 is formed (refer FIG.9 (h)).

[2-9] Second curing step S28
After the development process, the photosensitive resin layer 2520 is subjected to a curing process (post-development heating process). The curing conditions are, for example, the conditions described in the first curing step S23. Thereby, the photosensitive resin layer 2520 is cured to obtain the organic insulating layer 252 (see FIG. 10I).

  In the present embodiment, the upper wiring layer 25 has two layers of the organic insulating layer 251 and the organic insulating layer 252, but may have three or more layers. In this case, after the second curing step S28, a series of steps from the wiring layer forming step S24 to the second curing step S28 may be repeatedly added.

[2-10] Through-wiring forming step S29
Next, the through wiring 254 shown in FIG. 10I is formed in the opening 424.

  A known method is used to form the through wiring 254. For example, the following method is used.

  First, a seed layer (not shown) is formed on the organic insulating layer 252. The seed layer is formed on the upper surface of the organic insulating layer 252 together with the inner surface (side surface and bottom surface) of the opening 424.

  For example, a copper seed layer is used as the seed layer. The seed layer is formed by, for example, a sputtering method.

  Further, the seed layer may be made of the same type of metal as the through wiring 254 to be formed, or may be made of a different kind of metal.

  Next, a resist layer (not shown) is formed on a region other than the opening 424 in the seed layer (not shown). Then, the opening 424 is filled with metal using this resist layer as a mask. For this filling, for example, an electrolytic plating method is used. Examples of the metal to be filled include copper or copper alloy, aluminum or aluminum alloy, gold or gold alloy, silver or silver alloy, nickel or nickel alloy, and the like. In this manner, the conductive material is embedded in the opening 424, and the through wiring 254 is formed.

Next, the resist layer (not shown) is removed. Further, a seed layer (not shown) on the organic insulating layer 252 is removed. For this, for example, a flash etching method can be used.
Note that the formation position of the through wiring 254 is not limited to the illustrated position.

[3] Substrate peeling step S3
Next, as shown in FIG. 10J, the substrate 202 is peeled off. As a result, the lower surface of the organic insulating layer 21 is exposed.

[4] Lower wiring layer formation step S4
Next, as shown in FIG. 10 (k), the lower wiring layer 24 is formed on the lower surface side of the organic insulating layer 21. The lower wiring layer 24 may be formed by any method, for example, may be formed in the same manner as the above-described upper wiring layer forming step S2.

  The lower wiring layer 24 formed in this way is electrically connected to the upper wiring layer 25 through the through wiring 221.

[5] Solder bump formation step S5
Next, as shown in FIG. 10L, solder bumps 26 are formed on the lower wiring layer 24. Further, a protective film such as a solder resist layer may be formed on the upper wiring layer 25 and the lower wiring layer 24 as necessary.
The through electrode substrate 2 is obtained as described above.

  Note that the through electrode substrate 2 illustrated in FIG. 10L can be divided into a plurality of regions. Therefore, for example, by dividing the through electrode substrate 2 into pieces along the alternate long and short dash line shown in FIG. 10 (L), a plurality of through electrode substrates 2 can be efficiently manufactured. For example, a diamond cutter or the like can be used for singulation.

[6] Lamination process S6
Next, the semiconductor package 3 is disposed on the separated through electrode substrate 2. Thereby, the semiconductor device 1 shown in FIG. 5 is obtained.

  Such a manufacturing method of the semiconductor device 1 can be applied to a wafer level process or a panel level process using a large-area substrate. Thereby, the manufacturing efficiency of the semiconductor device 1 can be increased and the cost can be reduced.

<Negative photosensitive resin composition>
Next, each component of the negative photosensitive resin composition (hereinafter, also simply referred to as “photosensitive resin composition”) according to the present embodiment will be described. The photosensitive resin composition of the present invention may be a varnish solution or a film.

  The photosensitive resin composition according to the present embodiment includes a thermosetting resin, a photopolymerization initiator as a photosensitive agent, and a coupling agent containing an acid anhydride as a functional group. Such a photosensitive resin composition is formed of the organic insulating layer 21 having good adhesion to inorganic materials and metal materials such as the semiconductor chip 23, the through wirings 22, 221, 222, and the wiring layer 253 by the action of the coupling agent. Formation becomes possible.

(Thermosetting resin)
The thermosetting resin preferably includes a semi-cured (solid) thermosetting resin at room temperature (25 ° C.), for example. Such a thermosetting resin is melted by being heated and pressed during molding, and is cured while being molded into a desired shape. Thereby, the organic insulating layers 21, 251, and 252 utilizing the characteristics of the thermosetting resin are obtained.

  Examples of thermosetting resins include phenol novolac type epoxy resins, cresol novolac type epoxy resins such as cresol novolak type epoxy resins, cresol naphthol type epoxy resins, biphenyl type epoxy resins, biphenyl aralkyl type epoxy resins, phenoxy resins, and naphthalene skeletons. Type epoxy resin, bisphenol A type epoxy resin, bisphenol A diglycidyl ether type epoxy resin, bisphenol F type epoxy resin, bisphenol F diglycidyl ether type epoxy resin, bisphenol S diglycidyl ether type epoxy resin, glycidyl ether type epoxy resin, cresol Novolac epoxy resin, aromatic polyfunctional epoxy resin, aliphatic epoxy resin, aliphatic polyfunctional epoxy resin, alicyclic epoxy resin, polyfunctional Epoxy resins such as cyclic epoxy resins; resins having a triazine ring such as urea (urea) resins and melamine resins; unsaturated polyester resins; maleimide resins such as bismaleimide compounds; polyurethane resins; diallyl phthalate resins; silicone resins; Oxazine resin; polyimide resin; polyamideimide resin; benzocyclobutene resin, novolac type cyanate resin, bisphenol A type cyanate resin, bisphenol E type cyanate resin, cyanate ester resins such as cyanate resin such as tetramethylbisphenol F type cyanate resin, etc. Can be mentioned. In the thermosetting resin, one of these may be used alone, or two or more having different weight average molecular weights may be used in combination. You may use together with a polymer.

Among these, as the thermosetting resin, those containing an epoxy resin are preferably used.
Examples of the epoxy resin include a polyfunctional epoxy resin having two or more epoxy groups in one molecule. Since the polyfunctional epoxy resin has a plurality of epoxy groups in one molecule, the reactivity with the photopolymerization initiator is high. Therefore, even when a relatively small amount of exposure treatment is performed on the resin film of the photosensitive resin composition for a short time, the resin film can be sufficiently cured. Moreover, a polyfunctional epoxy resin may be used independently, or may be used in combination with the various thermosetting resins described above.

Moreover, as an epoxy resin, a polyfunctional epoxy resin more than trifunctional may be used.
Although it does not specifically limit as a polyfunctional epoxy resin, For example, 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4- (2,3-epoxy) Propoxy) phenyl] ethyl] phenyl] propane, phenol novolac type epoxy, tetrakis (glycidyloxyphenyl) ethane, α-2,3-epoxypropoxyphenyl-ω-hydropoly (n = 1-7) {2- (2,3 -Epoxypropoxy) benzylidene-2,3-epoxypropoxyphenylene}, 1-chloro-2,3-epoxypropane / formaldehyde / 2,7-naphthalenediol polycondensate, dicyclopentadiene type epoxy resin and the like. These may be used alone or in combination.

  Thermosetting resins include, among others, phenol novolac type epoxy resins, cresol novolac type epoxy resins, triphenylmethane type epoxy resins, dicyclopentadiene type epoxy resins, bisphenol A type epoxy resins, and tetramethylbisphenol F type epoxy resins. It is preferable to include one or more epoxy resins selected from the group consisting of: more preferably a polyfunctional epoxy resin; and still more preferably a polyfunctional aromatic epoxy resin. Since such a thermosetting resin is rigid, the organic insulating layers 21, 251, 252 having good curability, high heat resistance, and relatively low thermal expansion coefficient can be obtained.

  As described above, the thermosetting resin preferably contains a resin that is solid at normal temperature, and may contain both a resin that is solid at normal temperature and a resin that is liquid at normal temperature. The photosensitive resin composition containing such a thermosetting resin has good embedding property of the semiconductor chip 23 and the like, an improvement in tack (stickiness) when formed into a film, an organic insulating layer 21 that is a cured product, 251 and 252 mechanical strength can be made compatible. As a result, it is possible to obtain organic insulating layers 21, 251, and 252 having high mechanical strength that are flattened while suppressing generation of voids.

  When a resin that is solid at normal temperature and a resin that is liquid at normal temperature are used in combination, the amount of resin that is liquid at normal temperature is preferably about 5 to 150 parts by mass with respect to 100 parts by mass of the resin that is solid at normal temperature. The amount is more preferably about 100 parts by mass, and further preferably about 15 to 80 parts by mass. If the ratio of the liquid resin is lower than the lower limit, the embeddability of the semiconductor chip 23 into the photosensitive resin composition may be reduced, or the stability when formed into a film may be reduced. On the other hand, when the ratio of the liquid resin exceeds the upper limit, tack when the photosensitive resin composition is formed into a film is deteriorated, or the mechanical strength of the organic insulating layers 21, 251, and 252 which are cured products is reduced. There is a risk of doing so.

  Examples of the resin that is solid at room temperature include phenol novolac type epoxy resins, cresol novolac type epoxy resins, and phenoxy resins.

  On the other hand, examples of the liquid resin at room temperature include, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, alkyl glycidyl ether, butanetetracarboxylic acid tetra (3,4-epoxycyclohexylmethyl) modified ε-caprolactone, 3 ′, Examples thereof include 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 2-ethylhexyl glycidyl ether, trimethylolpropane polyglycidyl ether, and the like. These may be used alone or in combination.

  Further, the resin that is liquid at normal temperature preferably contains both an aromatic compound and an aliphatic compound. The photosensitive resin composition containing such a compound is imparted with appropriate flexibility when formed into a film mainly with an aliphatic compound, and has shape retention when formed into a film mainly with an aromatic compound. Is granted. As a result, a photosensitive resin film having both flexibility and shape retention can be obtained.

  Furthermore, it contains both a resin that is solid at room temperature and a resin that is liquid at room temperature, or a resin that is liquid at room temperature contains both an aromatic compound and an aliphatic compound. In this case, the glass transition temperature can be increased without impairing the patterning property, or the linear expansion coefficient can be lowered without impairing the patterning property.

  The amount of the aliphatic compound relative to 100 parts by mass of the aromatic compound is preferably about 5 to 150 parts by mass, more preferably about 10 to 80 parts by mass, and about 15 to 50 parts by mass. Is more preferable. When the ratio of the aliphatic compound is below the lower limit, the flexibility of the film may be lowered depending on the composition of the photosensitive resin composition. On the other hand, when the ratio of the aliphatic compound exceeds the upper limit, depending on the composition of the photosensitive resin composition, the shape retention of the film may be reduced.

  Although content of an epoxy resin is not specifically limited, It is preferable that it is about 40-80 mass% of the whole solid content of the photosensitive resin composition, it is more preferable that it is about 45-75 mass%, and 50-70. More preferably, it is about mass%. By setting the content of the epoxy resin within the above range, the patterning properties of the photosensitive resin layers 210, 2510, and 2520 containing the photosensitive resin composition are improved, and the heat resistance of the organic insulating layers 21, 251, and 252 is increased. The mechanical strength can be sufficiently increased.

  In addition, solid content of the photosensitive resin composition refers to the non-volatile content in the photosensitive resin composition, and refers to the remainder excluding volatile components such as water and solvent. Moreover, in this embodiment, content with respect to the whole solid content of the photosensitive resin composition points out content with respect to the whole solid content except the solvent of the photosensitive resin composition, when a solvent is included.

(Curing agent)
Moreover, the photosensitive resin composition of this invention may contain the hardening | curing agent. The curing agent is not particularly limited as long as it accelerates the polymerization reaction of the thermosetting resin. For example, when the thermosetting resin contains an epoxy resin, a curing agent having a phenolic hydroxyl group is used. Specifically, a phenol resin can be used.

  Examples of the phenolic resin include novolac type phenolic resin, resol type phenolic resin, trisphenylmethane type phenolic resin, arylalkylene type phenolic resin, and the like. Among these, a novolac type phenol resin is particularly preferably used. Thereby, photosensitive resin layers 210, 2510, and 2520 having good curability and good development characteristics are obtained.

  Although the addition amount of a hardening | curing agent is not specifically limited, It is preferable that it is 25 to 100 mass parts with respect to 100 mass parts of resin, It is more preferable that it is 30 to 90 mass parts, 35 masses More preferably, it is at least 80 parts by mass. By setting the addition amount of the curing agent within the above range, the organic insulating layer 21 having high heat resistance and a relatively low thermal expansion coefficient can be obtained.

(Thermoplastic resin)
The photosensitive resin composition may further contain a thermoplastic resin. Thereby, while being able to improve the moldability of the photosensitive resin composition, the flexibility of the hardened | cured material of the photosensitive resin composition can be improved more. As a result, the organic insulating layers 21, 251, and 252 that are less likely to generate thermal stress and the like are obtained.

  Examples of the thermoplastic resin include phenoxy resin, acrylic resin, polyamide resin (eg, nylon), thermoplastic urethane resin, polyolefin resin (eg, polyethylene, polypropylene), polycarbonate, polyester resin (eg, polyethylene terephthalate). , Polybutylene terephthalate, etc.), polyacetal, polyphenylene sulfide, polyether ether ketone, liquid crystal polymer, fluororesin (eg, polytetrafluoroethylene, polyvinylidene fluoride, etc.), modified polyphenylene ether, polysulfone, polyethersulfone, polyarylate, polyamide Examples thereof include imide, polyether imide, and thermoplastic polyimide. In the photosensitive resin composition, one of these may be used alone, two or more having different weight average molecular weights may be used in combination, one or two or more thereof, and A prepolymer may be used in combination.

  Of these, phenoxy resin is preferably used as the thermoplastic resin. The phenoxy resin is also called a polyhydroxy polyether, and has a feature that the molecular weight is larger than that of the epoxy resin. By including such a phenoxy resin, it can suppress that the flexibility of the hardened | cured material of the photosensitive resin composition falls.

  Examples of the phenoxy resin include bisphenol A type phenoxy resin, bisphenol F type phenoxy resin, copolymerized phenoxy resin of bisphenol A type and bisphenol F type, biphenyl type phenoxy resin, bisphenol S type phenoxy resin, biphenyl type phenoxy resin and bisphenol. Examples thereof include copolymerized phenoxy resins with S-type phenoxy resins, and one or a mixture of two or more of these is used.

  Among these, bisphenol A type phenoxy resin or copolymerized phenoxy resin of bisphenol A type and bisphenol F type is preferably used.

  As the phenoxy resin, those having an epoxy group at both ends of the molecular chain are preferably used. According to such a phenoxy resin, when an epoxy resin is used as the thermosetting resin, excellent solvent resistance and heat resistance can be imparted to the cured product of the photosensitive resin composition.

  Moreover, as a phenoxy resin, what is solid at normal temperature is used preferably. Specifically, a phenoxy resin having a nonvolatile content of 90% by mass or more is preferably used. By using such a phenoxy resin, the mechanical properties of the cured product can be improved.

  Although the weight average molecular weight of a thermoplastic resin is not specifically limited, It is preferable that it is about 10,000-100,000, and it is more preferable that it is about 20,000-80000. By using such a relatively high molecular weight thermoplastic resin, it is possible to impart satisfactory flexibility to the cured product and sufficient solubility in a solvent.

  In addition, the weight average molecular weight of a thermoplastic resin is measured as a polystyrene conversion value of a gel permeation chromatography (GPC) method, for example.

  The addition amount of the thermoplastic resin is not particularly limited, but is preferably 10 parts by mass or more and 90 parts by mass or less, and more preferably 15 parts by mass or more and 80 parts by mass or less with respect to 100 parts by mass of the thermosetting resin. Preferably, it is 20 parts by mass or more and 70 parts by mass or less. By setting the addition amount of the thermoplastic resin within the above range, the balance of mechanical properties of the cured product of the photosensitive resin composition can be increased.

  If the addition amount of the thermoplastic resin is less than the lower limit, depending on the components contained in the photosensitive resin composition and the blending ratio thereof, sufficient flexibility may not be imparted to the cured product of the photosensitive resin composition. There is. On the other hand, if the amount of the thermoplastic resin added exceeds the upper limit, the mechanical strength of the cured product of the photosensitive resin composition may be lowered depending on the components contained in the photosensitive resin composition and the blending ratio thereof. .

(Photosensitive agent)
As the photosensitizer, for example, a photoacid generator can be used. The photoacid generator includes a photoacid generator that generates an acid upon irradiation with actinic rays such as ultraviolet rays and functions as a photopolymerization initiator for the above-described curable resin.

  Examples of the photoacid generator include onium salt compounds. Specifically, iodonium salts such as diazonium salts and diaryl iodonium salts, sulfonium salts such as triarylsulfonium salts, triarylbililium salts, benzylpyridinium thiocyanate, dialkylphenacylsulfonium salts, and dialkylhydroxyphenylphosphonium salts Examples thereof include a cationic photopolymerization initiator.

In addition, since the photosensitive composition contacts a metal, a photosensitive agent that does not generate hydrogen fluoride due to decomposition, such as a methide salt type or a borate salt type, is preferable.
In particular, it is preferable to use a triarylsulfonium salt having a borate anion as a counter anion as a photosensitive agent. Such a triarylsulfonium salt contains a borate anion having low corrosiveness to a metal as a counter anion, so that the metal materials such as the through wirings 22, 221 and 222 and the wiring layer 253 are corroded for a longer period of time. Can be prevented over. As a result, the reliability of the semiconductor device 1 can be further increased.

  Although the addition amount of a photosensitive agent is not specifically limited, It is preferable that it is about 0.3-5 mass% of the whole solid content of the photosensitive resin composition, and it is about 0.5-4.5 mass%. More preferably, it is about 1-4 mass%. By setting the addition amount of the photosensitive agent within the above range, the patterning properties of the photosensitive resin layers 210, 2510, and 2520 containing the photosensitive resin composition are improved, and the long-term storage property of the photosensitive resin composition is improved. be able to.

  The photosensitive agent may be one that imparts negative-type photosensitivity to the photosensitive resin composition, or one that imparts positive-type photosensitivity, but has a high aspect ratio opening. In view of the point that can be formed with high accuracy, the negative type is preferable.

(Coupling agent)
The photosensitive resin composition according to this embodiment has a coupling agent containing an acid anhydride as a functional group. Such a photosensitive resin composition enables formation of a resin film having good adhesion to an inorganic material and a metal material. Thereby, for example, the organic insulating layers 21, 251, 252 having good adhesion to the through wirings 22, 221, 222, the wiring layer 253, and the semiconductor chip 23 are obtained.

  In such an acid anhydride-containing coupling agent, an acid anhydride that is a functional group dissolves an inorganic oxide and coordinates with a cation (metal cation or the like).

  On the other hand, the alkoxy group contained in the acid anhydride-containing coupling agent is hydrolyzed to, for example, silanol. This silanol forms a hydrogen bond with the surface hydroxyl group of the inorganic material.

  Therefore, it is considered that a photosensitive resin composition having good adhesion to an inorganic material and a metal material can be obtained based on these bonding mechanisms.

  As the coupling agent, a coupling agent containing an acid anhydride as a functional group (hereinafter, also referred to as “an acid anhydride-containing coupling agent”) is used.

  Specifically, a compound containing an alkoxysilyl group is preferably used, and an alkoxysilyl group-containing alkylcarboxylic acid anhydride is preferably used. According to such a coupling agent, a photosensitive resin composition having better adhesion to an inorganic material and a metal material, good sensitivity, and excellent patternability can be obtained.

  Specific examples of the compound containing an alkoxysilyl group include 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylsilylpropyl succinic anhydride, 3-dimethylmethoxysilylpropyl succinic anhydride, 3-dimethylethoxy. Succinic anhydride such as silylpropyl succinic anhydride, 3-trimethoxysilylpropyl cyclohexyl dicarboxylic acid anhydride, 3-triethoxysilylpropyl cyclohexyl dicarboxylic acid anhydride, 3-dimethylmethoxysilylpropyl cyclohexyl dicarboxylic acid anhydride, Dicarboxylic anhydrides such as 3-dimethylethoxysilylpropylcyclohexyldicarboxylic anhydride, 3-trimethoxysilylpropylphthalic anhydride, 3-triethoxysilylpropylphthalic anhydride, 3-dimethylmethoxy Lil propyl phthalic anhydride, alkoxysilyl group-containing alkyl carboxylic acid anhydride such as phthalic anhydride, such as 3-dimethyl-ethoxysilylpropyl phthalic anhydride. These may be used alone or in combination.

  Among these, alkoxysilyl group-containing succinic anhydride is preferably used, and 3-trimethoxysilylpropyl succinic anhydride is particularly preferably used. According to such a coupling agent, the molecular length and the molecular structure are optimized, so that the above-described adhesion and patterning properties are further improved.

  In addition, although the silane coupling agent was enumerated here, a titanium coupling agent, a zirconium coupling agent, etc. may be sufficient.

  The addition amount of the acid anhydride-containing coupling agent is not particularly limited, but is preferably about 0.3 to 5% by mass of the total solid content of the photosensitive resin composition, and preferably 0.5 to 4.5% by mass. More preferably, it is about 1 to 4% by mass. By setting the addition amount of the acid anhydride-containing coupling agent within the above range, particularly good adhesion to inorganic materials and metal materials such as through wirings 22, 221, 222, wiring layer 253 and semiconductor chip 23, for example. Organic insulating layers 21, 251, 252 are obtained. This contributes to the realization of the highly reliable semiconductor device 1 such that the insulating properties of the organic insulating layers 21, 251, 252 are maintained over a long period of time.

  In addition, when the addition amount of an acid anhydride containing coupling agent is less than the said lower limit, there exists a possibility that the adhesiveness with respect to an inorganic material and a metal material may fall depending on a composition etc. of an acid anhydride containing coupling agent. On the other hand, when the addition amount of the acid anhydride-containing coupling agent exceeds the upper limit, depending on the composition of the acid anhydride-containing coupling agent, the photosensitivity and mechanical properties of the photosensitive resin composition may be reduced. is there.

  In addition to such an acid anhydride-containing coupling agent, another coupling agent may be further added.

  Examples of other coupling agents include coupling agents containing amino groups, epoxy groups, acrylic groups, methacryl groups, mercapto groups, vinyl groups, ureido groups, sulfide groups and the like as functional groups. These may be used alone or in combination.

  Among these, examples of the amino group-containing coupling agent include bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and γ-aminopropylmethyl. Diethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ -Aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, N-phenyl-γ-amino-propyltrimethoxysilane and the like.

  Examples of the epoxy group-containing coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-glycidylpropyl. Examples include trimethoxysilane.

  Examples of the acrylic group-containing coupling agent include γ- (methacryloxypropyl) trimethoxysilane, γ- (methacryloxypropyl) methyldimethoxysilane, and γ- (methacryloxypropyl) methyldiethoxysilane.

  Examples of the mercapto group-containing coupling agent include 3-mercaptopropyltrimethoxysilane.

  Examples of the vinyl group-containing coupling agent include vinyl tris (β-methoxyethoxy) silane, vinyltriethoxysilane, and vinyltrimethoxysilane.

  Examples of the ureido group-containing coupling agent include 3-ureidopropyltriethoxysilane.

  Examples of the sulfide group-containing coupling agent include bis (3- (triethoxysilyl) propyl) disulfide and bis (3- (triethoxysilyl) propyl) tetrasulfide.

  The addition amount of the other coupling agent is not particularly limited, but is preferably about 1 to 200% by mass of the acid anhydride-containing coupling agent, more preferably about 3 to 150% by mass, More preferably, it is about 100% by mass. By setting the addition amount within this range, the above-described action by the acid anhydride-containing coupling agent is not impaired, and another action is added by addition of another coupling agent. As a result, it is possible to achieve both effects brought about by both coupling agents.

(Other additives)
Other additives may be added to the photosensitive resin composition as necessary. Examples of other additives include an antioxidant, a filler such as silica, a surfactant, a sensitizer, and a filming agent.

  Examples of the surfactant include a fluorine-based surfactant, a silicon-based surfactant, an alkyl-based surfactant, and an acrylic-based surfactant.

(solvent)
The photosensitive resin composition may contain a solvent. Any solvent can be used without particular limitation as long as it can dissolve each constituent of the photosensitive resin composition and does not react with each constituent.

  Examples of the solvent include acetone, methyl ethyl ketone, toluene, propylene glycol methyl ethyl ether, propylene glycol dimethyl ether, propylene glycol 1-monomethyl ether 2-acetate, diethylene glycol ethyl methyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, benzyl alcohol. , Propylene carbonate, ethylene glycol diacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate and the like. These may be used alone or in combination.

<Photosensitive resin varnish>
The photosensitive resin composition may have a varnish shape.

  The varnish-like photosensitive resin composition is prepared, for example, by uniformly mixing a raw material and a solvent. In addition, a solvent is added as needed and it is also possible to varnish without using a solvent. Moreover, you may use for processes, such as filtration with a filter and defoaming, after that.

  The solid content concentration in the varnish-like photosensitive resin composition is not particularly limited, but is preferably about 20 to 80% by mass. The varnish-like photosensitive resin composition having such a solid content concentration is optimized for viscosity, and thus has good fluidity that easily penetrates into narrow gaps, and hardly causes film breakage. It becomes.

<Photosensitive resin film>
Next, the photosensitive resin film according to the present embodiment will be described.

  As described above, the photosensitive resin film may be formed by forming the photosensitive resin composition into a film, or may be a film obtained by applying the photosensitive resin composition to a carrier film.

  Examples of the latter method for producing a photosensitive resin film include a method in which a varnish-like photosensitive resin composition is applied on a carrier film and then dried.

  Examples of the coating device include a spin coater, a spray device, and an ink jet device.

  Although the content rate of the solvent in a photosensitive resin film is not specifically limited, It is preferable that it is 10 mass% or less of the whole photosensitive resin film. Thereby, while improving the tack of the photosensitive resin film, the curability of the photosensitive resin film can be enhanced. Moreover, generation | occurrence | production of the void by volatilization of a solvent can be suppressed.

  Examples of the drying conditions include conditions of heating at a temperature of 80 to 150 ° C. for 5 to 30 minutes.

  The photosensitive resin film laminated | stacked on the carrier film is useful from viewpoints, such as handleability and surface cleanliness. At this time, the carrier film may be in the form of a roll that can be wound or may be in the form of a single wafer.

  Examples of the constituent material of the carrier film include a resin material and a metal material. Among these, examples of the resin material include polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polycarbonates, silicones, fluorine resins, and polyimide resins. Examples of the metal material include copper or a copper alloy, aluminum or an aluminum alloy, iron or an iron alloy, and the like.

  Among these, a carrier film containing polyester is preferably used. Such a carrier film suitably supports the photosensitive resin film and has a relatively good peelability.

  Moreover, the cover film may be provided in the surface of the photosensitive resin film as needed. This cover film protects the surface of the photosensitive resin film until the pasting operation.

  The constituent material of the cover film is appropriately selected from those listed as the constituent material of the carrier film, but a cover film containing polyester is preferably used from the viewpoint of protection and ease of peeling.

<Electronic equipment>
The electronic apparatus according to the present embodiment includes the semiconductor device according to the present embodiment described above.

  Such a semiconductor device has a high reliability because it includes a protective film having excellent chemical resistance. For this reason, high reliability is also provided to the electronic apparatus according to the present embodiment.

  The electronic device according to the present embodiment is not particularly limited as long as it includes such a semiconductor device. For example, information devices such as mobile phones, smartphones, tablet terminals, and personal computers, communication devices such as servers and routers. And vehicle-mounted devices such as vehicle control computers and car navigation systems.

  As mentioned above, although this invention was demonstrated based on embodiment of illustration, this invention is not limited to these.

  For example, the photosensitive resin composition, the semiconductor device, and the electronic device of the present invention may be those obtained by adding arbitrary elements to the embodiment.

  The photosensitive resin composition and the photosensitive resin film are not only semiconductor devices but also structure forming materials for MEMS (Micro Electro Mechanical Systems) and various sensors, liquid crystal display devices, and organic EL devices. It can also be applied to materials.

Next, specific examples of the present invention will be described.
1. Preparation of photosensitive resin composition (Example 1)
First, the raw materials shown in Tables 1 and 2 were dissolved in propylene glycol monomethyl ether acetate (PGMEA) to prepare a solution.

  Next, the prepared solution was filtered through a polypropylene filter having a pore size of 0.2 μm to obtain a negative photosensitive resin composition.

(Examples 2 to 11)
A photosensitive resin composition was obtained in the same manner as in Example 1 except that the raw materials were changed as shown in Tables 1 and 2.

(Comparative Examples 1-4)
A photosensitive resin composition was obtained in the same manner as in Example 1 except that the raw materials were changed as shown in Tables 1 and 2.

2. 2. Evaluation of photosensitive resin composition 2.1 Preparation of test piece First, a silicon wafer having a size of 8 inches and a thickness of 725 µm was prepared.

  Next, the varnish-shaped photosensitive resin composition was apply | coated with the spin coater on the silicon wafer. As a result, a liquid film having a thickness of 10 μm was obtained.

Next, the liquid coating film was dried at 120 ° C. for 5 minutes on a hot plate to obtain a coating film.
Next, the entire surface of the obtained coating film was exposed at 700 mJ / cm ² .

Next, PEB (Post Exposure Bake) at 70 ° C. for 5 minutes was performed on the exposed coating film.
Next, it heated at 200 degreeC for 90 minute (s), and the test piece which has a cured film was obtained.

2.2 Adhesion test 2.2.1 Silicon adhesion test (room temperature)
Next, the obtained test piece was subjected to an adhesion test according to the cross-cut method defined in JIS K 5600-5-6: 1999 as follows.

  First, a cut was made in the photosensitive resin film using a tool. The cuts were made so as to penetrate the photosensitive resin film 10 by 10 mm vertically and horizontally at 1 mm intervals. As a result, 100 squares each having a 1 mm square were formed from the photosensitive resin film.

Next, a cellophane adhesive tape was attached so as to overlap these 100 squares. Then, the cellophane adhesive tape was peeled off, and the number of the 100 squares peeled off was counted.
The counted results are shown in Table 2.

2.2.2 Silicon adhesion test (high temperature)
The obtained test piece was placed under high temperature and high humidity under the following conditions, and then an adhesion test was conducted in the same manner as 2.2.1. The evaluation results are shown in Table 2.

・ Temperature 85 ℃
・ 85% relative humidity
・ Test time: 24 hours

2.2.3 Copper adhesion test (room temperature)
Adhesion at room temperature in the same manner as 2.2.1, except that the silicon wafer of 2.1 was treated with Ti and then changed to a silicon wafer on which copper having a thickness of 300 nm was deposited. A test was conducted. The evaluation results are shown in Table 2.

2.2.4 Copper adhesion test (high temperature)
Adhesion at high temperature in the same manner as 2.2.2, except that the silicon wafer of 2.1 was treated with a Ti wafer and then changed to a silicon wafer on which copper having a thickness of 300 nm was deposited. A test was conducted. The evaluation results are shown in Table 2.

2.3 Evaluation of patterning property First, as shown in 2.1, a varnish-like photosensitive resin composition was applied onto a silicon wafer with a spin coater. As a result, a liquid film having a thickness of 10 μm was obtained.

Next, the liquid coating film was dried at 120 ° C. for 5 minutes on a hot plate to obtain a coating film.
Next, the exposure process was performed with respect to the coating film using the i line | wire stepper (the Nikon Corporation make, NSR-4425i) through the negative pattern mask. Thereafter, a post-exposure heat treatment was performed at 70 ° C. for 5 minutes.

  Next, using 25 ° C. propylene glycol monomethyl ether acetate (PGMEA) as a developer, the unexposed area was dissolved and removed by spray development, and then rinsed with isopropyl alcohol (IPA).

  Next, whether or not the patterning could be performed was visually confirmed, and the patterning property was evaluated in light of the following evaluation criteria.

<Patternability evaluation criteria>
○: A pattern could be obtained by dissolving the unexposed area. ×: A pattern could not be obtained due to total dissolution or insolubility.

  As is clear from Table 2, it was revealed that the photosensitive resin films obtained in each Example showed good adhesion to inorganic materials and metal materials.

  The negative photosensitive resin composition of the present invention includes a thermosetting resin, a photopolymerization initiator, and a coupling agent containing an acid anhydride as a functional group. By using a coupling agent containing an acid anhydride as a functional group, the resin film formed with a negative photosensitive resin composition adheres to a semiconductor chip or various metal wirings formed of an inorganic material or a metal material. Property is improved. Therefore, the reliability of a semiconductor device using such a negative photosensitive resin composition can be increased. Therefore, the present invention has industrial applicability.

Claims (11)

A thermosetting resin;
A photopolymerization initiator;
A coupling agent containing an acid anhydride as a functional group;
A negative photosensitive resin composition comprising:   The negative photosensitive resin composition according to claim 1, wherein the thermosetting resin contains a solid component at room temperature.   The negative photosensitive resin composition according to claim 1, wherein the thermosetting resin contains a polyfunctional epoxy resin.   The negative photosensitive resin composition according to claim 3, wherein a content of the polyfunctional epoxy resin is 40 to 80% by mass with respect to a nonvolatile component of the photosensitive resin composition.   The negative photosensitive resin composition according to any one of claims 1 to 4, wherein the coupling agent is a compound containing an alkoxysilyl group.   The negative photosensitive resin composition according to claim 1, wherein the acid anhydride is succinic anhydride.   The negative photosensitive resin composition according to any one of claims 1 to 6, wherein the negative photosensitive resin composition further contains a solvent.   The negative photosensitive resin composition according to claim 7, wherein the negative photosensitive resin composition is dissolved in the solvent to form a varnish. A semiconductor chip;
A resin film containing a cured product of the negative photosensitive resin composition according to any one of claims 1 to 8, which is provided on the semiconductor chip;
A semiconductor device comprising:   The semiconductor device according to claim 9, wherein a rewiring layer electrically connected to the semiconductor chip is embedded in the resin film.   An electronic apparatus comprising the semiconductor device according to claim 9.

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