JP2020060773A - Negative type photosensitive resin composition, semiconductor device and electronic apparatus - Google Patents

Abstract

To provide a photosensitive resin composition which can form a resin film having good adhesion to an inorganic material, a photosensitive resin film, a semiconductor device including the resin film, and an electronic apparatus including the semiconductor device.SOLUTION: A negative type photosensitive resin composition contains a thermosetting resin, a phenoxy resin, a photopolymerization initiator, and a coupling agent containing an acid anhydride as a functional group. The phenoxy resin preferably contains a component that is solid at normal temperature. The phenoxy resin preferably contains a component having epoxy groups in both terminals of the molecular chain.SELECTED DRAWING: None

Description

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

  A resin film made of a resin material is used for a semiconductor element for applications such as a protective film, an interlayer insulating film, and a flattening film. Further, depending on the mounting method of the semiconductor element, thickening of these resin films is required. However, when the resin film is thickened, the warp of the semiconductor chip becomes remarkable.

  On the other hand, there is known a technique of forming a pattern on a resin film by imparting photosensitivity and light transparency to the resin film. As a result, the target pattern can be formed accurately.

  Therefore, the development of a resin composition that has a photosensitivity and is capable of producing a thick resin film is under way.

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

  The photosensitive resin composition is also used for the purpose of embedding wiring in a resin film formed of the photosensitive resin composition to form an insulating portion for insulating 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. Therefore, it is important for the resin film to have good adhesion to the inorganic material and the metal material.

  However, the conventional resin film has a problem that the reliability after mounting cannot be sufficiently enhanced because the adhesiveness to the inorganic material and the metal material is low.

  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 invention described in (1) to (11) below.
(1) 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-type photosensitive resin composition according to (1) or (2) above, wherein the thermosetting resin contains a polyfunctional epoxy resin.
(4) The negative photosensitive resin composition according to (3), wherein the content of the polyfunctional epoxy resin is 40 to 80% by mass with respect to the nonvolatile components of the photosensitive resin composition.

  (5) The negative photosensitive resin composition according to any one of (1) to (4) above, 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) above, wherein the acid anhydride is succinic anhydride.

(7) The negative photosensitive resin composition according to any one of (1) to (6) above, which 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 containing a cured product of the negative photosensitive resin composition according to any one of (1) to (8), which is provided on the semiconductor chip;
A semiconductor device comprising:

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

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

  According to the present invention, a negative photosensitive resin composition capable of forming a resin film having good adhesion to an inorganic material and a metal material can be obtained.

Further, according to the present invention, a semiconductor device including the resin film can be obtained.
Further, according to the present invention, an electronic device including the above semiconductor device can be obtained.

FIG. 1 is a vertical cross-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 of manufacturing the semiconductor device shown in FIG. FIG. 4 is a diagram showing an example of a method of manufacturing the semiconductor device shown in FIG. FIG. 5 is a vertical 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. 7A to 7D are process diagrams 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 the description of the negative photosensitive resin composition and the photosensitive resin film containing the negative photosensitive resin composition, a first embodiment of the semiconductor device of the present invention to which these are applied will be described.

<< First Embodiment >>
1. Semiconductor Device FIG. 1 is a vertical cross-sectional view showing a first embodiment of the semiconductor device of the present invention. 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 wirings 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 solder bumps 26 provided on the lower surface of the lower wiring layer 24. I have it. 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 for electrically connecting the semiconductor chip 32 and the package substrate 31, a semiconductor chip 32 and a bonding wire. It includes a sealing layer 34 in which 33 is embedded, and solder bumps 35 provided on the lower surface of the package substrate 31.

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

  In such a semiconductor device 1, since the organic insulating layer 21 has good adhesion to the through wiring 22 and the semiconductor chip 23, the reliability is high.

  Further, since it is not necessary to use a thick substrate such as an organic substrate including a core layer for the through electrode substrate 2, it is possible to easily reduce the height. Therefore, it is possible to contribute to the miniaturization of the electronic device including the semiconductor device 1.

  Further, since the through electrode substrate 2 and the semiconductor package 3 having different semiconductor chips 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.
The lower wiring layer 24 and the 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. As a result, the lower wiring layer 24 and the upper wiring layer 25 include wiring inside or on the surface thereof, and are electrically connected so as to penetrate in the thickness direction via the through wiring.

  Of these, the wiring layers included in the lower wiring layer 24 are connected to the semiconductor chip 23 and the solder bumps 26. Therefore, the lower wiring layer 24 functions as a rewiring layer of the semiconductor chip 23, and the solder bumps 26 function as external terminals of the semiconductor chip 23.

  The through wiring 22 shown in FIG. 2 is provided so as to penetrate the organic insulating layer 21. Thus, 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 semiconductor device 1 can be made highly functional.

  Further, the wiring layers included in the upper wiring layer 25 shown in FIG. 2 are connected to the through wirings 22 and the solder bumps 35. Therefore, the upper wiring layer 25 is electrically connected to the semiconductor chip 23, functions as a rewiring layer for 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 redistribution layer can be increased.

  Further, since the penetrating wiring 22 penetrates the organic insulating layer 21, the effect of reinforcing the organic insulating layer 21 can be obtained. Therefore, even if the lower wiring layer 24 and the upper wiring layer 25 have low mechanical strength, it is possible to avoid a decrease in the mechanical strength of the entire through electrode substrate 2. As a result, the lower wiring layer 24 and the upper wiring layer 25 can be made thinner, and the height of the semiconductor device 1 can be further reduced.

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

  The diameter W of the through wiring 22 (see FIG. 2) is not particularly limited, but is preferably about 1 to 100 μm, more preferably about 2 to 80 μm. 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 type 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 Nailed, Sack). Examples thereof include forms such as LF-BGA (Lead Frame BGA).

  The form of the semiconductor chip 32 is not particularly limited, but as an example, the semiconductor chip 32 shown in FIG. 1 is configured by stacking a plurality of chips. Therefore, high density is achieved. The plurality of chips may be arranged side by side in the plane direction, or may be arranged side by side in the plane direction while being stacked in the thickness direction.

  The package substrate 31 may be any substrate, but is, for example, a substrate including an insulating layer, a wiring layer, a through wiring, and the like (not shown). Of these, the solder bumps 35 and the bonding wires 33 can be electrically connected via the through wirings.

  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 and an external environment.

  Since the semiconductor chip 23 included in the through electrode substrate 2 and the semiconductor chip 32 included in the semiconductor package 3 are arranged close to each other, it is possible to enjoy advantages such as high-speed mutual communication and low loss. You can 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), and an AP (Application Processor), and the other is a DRAM (Dynamic Random Access). Memory) or a flash memory or the like, these elements can be arranged close to each other in the same device, so that it is possible to realize the semiconductor device 1 that is both highly functional and compact. You can

<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 glass transition temperature (Tg) of the cured product of the photosensitive resin composition according to the present embodiment (including the cured product of the photosensitive resin film; the same applies hereinafter) is preferably 140 ° C. or higher, and 150 ° C. or higher. Is more preferable, and 160 ° C. or higher is further preferable. As a result, the heat resistance of the organic insulating layer 21 can be increased, so that the semiconductor device 1 that can be used even in a high temperature environment can be realized. The upper limit value of the cured product of the photosensitive resin composition may be set to 250 ° C. or lower as an example, although it is not particularly set.

  Further, the glass transition temperature of the cured product of the photosensitive resin composition was measured using a thermomechanical analyzer (TMA) for a predetermined test piece (width 4 mm x length 20 mm x thickness 0.005 to 0.015 mm). Then, it is calculated from the results of measurement under conditions of a starting temperature of 30 ° C., a measurement temperature range of 30 to 400 ° C., and a temperature rising rate of 5 ° C./min.

  The cured product of the photosensitive resin composition according to the present embodiment preferably has a linear expansion coefficient (CTE) of 5 to 80 ppm / ° C, more preferably 10 to 70 ppm / ° C, and more preferably 15 to 60 ppm /. It is more preferable that the temperature is ° C. As a result, the linear expansion coefficient of the organic insulating layer 21 can be brought close to that of a silicon material, for example. Therefore, for example, the organic insulating layer 21 in which the semiconductor chip 23 is less likely to warp is obtained. As a result, a highly reliable semiconductor device 1 can be obtained.

  The coefficient of linear expansion of the cured product of the photosensitive resin composition was measured using a thermomechanical analyzer (TMA) for a predetermined test piece (width 4 mm x length 20 mm x thickness 0.005 to 0.015 mm). Then, it is calculated from the results of measurement under 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. This makes it possible to obtain a cured product having excellent heat resistance, in which weight loss due to thermal decomposition or the like does not easily occur even at high temperatures. Therefore, the organic insulating layer 21 having excellent durability in a high temperature environment can be obtained.

  The 5% thermogravimetric reduction temperature Td5 of the cured product of the photosensitive resin composition was calculated from the result of measurement using a differential thermogravimetric simultaneous measurement device (TG / DTA) for 5 mg of the cured product. It

  The cured product of the photosensitive resin composition according to the exemplary embodiment preferably has an elongation rate of 5 to 50%, more preferably 6 to 45%, and further preferably 7 to 40%. . As a result, the elongation rate of the organic insulating layer 21 is optimized. Therefore, 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 are It is possible to suppress peeling or the like from occurring at the interface of Further, also in the organic insulating layer 21 itself, it is possible to suppress the occurrence of cracks and the like.

  If the elongation rate is less than the lower limit value, cracks or the like may occur in the organic insulating layer 21 depending on the thickness and shape of the organic insulating layer 21. On the other hand, when the elongation percentage exceeds the upper limit value, the mechanical characteristics of the organic insulating layer 21 may be deteriorated depending on the thickness and shape of the organic insulating layer 21.

  The elongation of the cured product 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 (pulling 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 manufactured by Orientec Co., Ltd. (Tensilon RTA-100). Then, the tensile elongation percentage is calculated from the result of the tensile test. Here, the above-described tensile test is performed with the number of tests n = 10, an average value of 5 times with a large measured value is obtained, and this is used as the measured value.

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

  The tensile strength of the cured product of the photosensitive resin composition is obtained from the result of the tensile test obtained by the same method as the above-described measurement of elongation.

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

  The elastic modulus of the cured product of the photosensitive resin composition is obtained from the result of the tensile test obtained by the same method as the above-described measurement of elongation.

Further, as the above-mentioned cured product, for example, one cured under the following conditions is used. First, the photosensitive resin composition is applied on a silicon wafer substrate by a spin coater or the like, and then dried at 120 ° C. for 5 minutes on a hot plate to obtain a coating film. The obtained coating film is entirely exposed at 700 mJ / cm ² , and PEB (Post Exposure Bake) is performed at 70 ° C. for 5 minutes. Then, it heats at 200 degreeC for 90 minutes, and a hardened film is obtained.

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

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

  The constituent material of the substrate 202 is not particularly limited, but examples thereof include a metal material, a glass material, a ceramic material, a semiconductor material, and an organic material. Further, as the substrate 202, a semiconductor wafer such as a silicon wafer, a glass wafer, or the like may be used. Electronic circuits may be formed on the substrate 202 as necessary.

[2]
Next, as shown in FIG. 3B, the semiconductor chip 23 is arranged on the substrate 202. In this 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 may be of different types.

  An interposer (not shown) may be provided between the substrate 202 and the semiconductor chip 23 if 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 electrically connecting to an electrode of the semiconductor chip 23 described later. As a result, the pad spacing and array pattern of the semiconductor chip 23 can be converted, and the degree of freedom in designing the semiconductor device 1 can be further increased.

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

[3]
Next, as shown in FIG. 3C, the photosensitive resin layer 210 is arranged 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, in particular, by using the photosensitive resin film containing the photosensitive resin composition, the photosensitive resin layer 210 can be easily thickened. As a result, the semiconductor chip 23 can be embedded easily without thinning it.

  When the photosensitive resin layer 210 is formed by 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 may be used as the semiconductor chip. After sticking on 23, the photosensitive resin film may be left by peeling off the carrier film.

  Further, in the work of attaching the photosensitive resin film, a known laminating 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.

  In addition, in the process of attaching the photosensitive resin film, the photosensitive resin film may be heated if necessary.

  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. It is more preferable that the temperature is about ° C. By heating at such a temperature, the embeddability of the semiconductor chip 23 in the photosensitive resin film is further enhanced. As a result, the occurrence of defects such as voids can be suppressed, and the photosensitive resin layer 210 that is more planarized can be efficiently formed.

  If the heating temperature is lower than the lower limit value, the photosensitive resin film is insufficiently melted, and thus the embedding property may be lowered depending on the constituent material of the photosensitive resin film and the like. On the other hand, if the heating temperature exceeds the upper limit, it may be cured depending on the constituent material of the photosensitive resin film.

  The heating time is appropriately set depending on the constituent material of the photosensitive resin film, the heating temperature, etc., but is preferably about 5 to 180 seconds, more preferably about 10 to 60 seconds.

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

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

  In the work of forming the photosensitive resin layer 210 using the varnish-shaped photosensitive resin composition, the viscosity is adjusted with a solvent or the like as necessary, and the substrate 202 is coated with various coating devices. Then, the photosensitive resin layer 210 is obtained by drying the obtained coating film. In addition, in order to secure a sufficient thickness so that the semiconductor chip is completely embedded, application and drying of the varnish-shaped photosensitive resin composition may be repeated a plurality of times.

  Examples of the coating device include a spin coater, a spray device, and an inkjet 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 in consideration of curing shrinkage. The thickness is not particularly limited as long as 23 can be embedded. However, as an example of the film thickness of the photosensitive resin film, it is preferably about 20 to 1000 μm, more preferably about 50 to 750 μm, and further preferably about 100 to 500 μm. By setting the film thickness of the photosensitive resin layer 210 within the above range, the semiconductor chip 23 can be easily embedded, 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 the good protection of the semiconductor chip 23.

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

  After that, a post-exposure heat treatment is performed if necessary. The conditions of the post-exposure heat treatment are not particularly limited, but for example, the heating temperature 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 so-called negative type photosensitivity. In this example, the region of the photosensitive resin layer 210 corresponding to the non-light-shielding portion of the mask 41 is given the solubility in the developing solution.

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

  After the development processing, the photosensitive resin layer 210 is subjected to post-development heating processing. The conditions of the post-development heat treatment are not particularly limited, but the heating temperature 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 influence 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 the following method is used, for example.

  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 as well as inside the opening 42 (side wall and bottom surface).

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

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

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

Then, the resist layer (not shown) is removed.
The location where the through wiring 22 is formed is not limited to the illustrated position. 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 by 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 by 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 via 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, if necessary.

Through-electrode substrate 2 is obtained as described above.
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 individual pieces along the alternate long and short dash line shown in FIG. 4 (j), a plurality of through electrode substrates 2 can be efficiently manufactured. In addition, for example, a diamond cutter or the like can be used for individualization.

[10]
Next, the semiconductor package 3 is arranged on the individual through-electrode substrate 2. As a result, the semiconductor device 1 shown in FIG. 1 is obtained.

  Such a method of manufacturing 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 arranged, 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. As a result, the manufacturing efficiency of the semiconductor device 1 can be improved 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 vertical sectional view showing a second embodiment of the semiconductor device of the present invention. Further, 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 focusing on the differences from the first embodiment, and the description of the same matters will be omitted.

1. Semiconductor Device In the semiconductor device 1 of the second embodiment, the configuration 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 according to the first embodiment is the same as the semiconductor device 1 according to the first embodiment described above except that the semiconductor device is different from the semiconductor device according to the first embodiment.

In the semiconductor device 1 of the present embodiment, as shown in FIGS. 5 and 6, the organic insulating layer 21 is provided with the through wiring 221 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 be made highly functional. it can. The diameter W of the through wiring 221 (see FIG. 6) is not particularly limited, but may be the same as the diameter W of the through wiring 22 of the semiconductor device 1 of the first embodiment described above.
In addition to the through wiring 221, the semiconductor device 1 of the present 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. Thereby, the upper surface of the semiconductor chip 23 and the upper wiring layer 25 can be electrically connected.

Further, 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. Therefore, the upper wiring layer 25 is electrically connected to the semiconductor chip 23, functions as a rewiring layer for 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 structure in which the wiring layer 253 is embedded in the 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 high.

2. Method of Manufacturing Semiconductor Device Next, a method of manufacturing the semiconductor device 1 shown in FIG. 5 will be described.

  7A to 7C are process diagrams showing a method of manufacturing the semiconductor device 1 shown in FIG. 8 to 10 are views for explaining a method of manufacturing the semiconductor device 1 shown in FIG. 5, respectively.

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

  Among them, in the upper wiring layer forming step S2, 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 varnish A first exposure step S21 for performing an exposure process on the layer 2510, a first development step S22 for performing a development process on the photosensitive resin layer 2510, a first curing step S23 for performing a curing process on the photosensitive resin layer 2510, and a wiring layer A wiring layer forming step S24 for forming 253, a second resin film arranging step S25 for arranging the photosensitive resin varnish 5 on the photosensitive resin layer 2510 and the wiring layer 253 to obtain the photosensitive resin layer 2520, and a 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 step 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 step will be sequentially described. The following manufacturing method is an example, and the present invention is not limited to this.

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

  The constituent material of the substrate 202 is not particularly limited, but examples thereof include a metal material, a glass material, a ceramic material, a semiconductor material, and an organic material. Further, 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 onto the substrate 202. In this manufacturing method, as an example, a plurality of semiconductor chips 23 are placed side by side on the same substrate 202 while being separated from each other. The plurality of semiconductor chips 23 may be of the same type or may be of different types. Alternatively, the substrate 202 and the semiconductor chip 23 may be fixed to each other via an adhesive layer (not shown) such as a die attach film.

  An interposer (not shown) may be provided between the substrate 202 and the semiconductor chip 23 if 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 electrically connecting to an electrode of the semiconductor chip 23 described later. As a result, the pad spacing and array pattern of the semiconductor chip 23 can be converted, and the degree of freedom in designing the semiconductor device 1 can be further increased.

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

  The organic insulating layer 21 is, for example, a resin film containing a thermosetting resin or a thermoplastic resin as mentioned 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 a copper alloy, aluminum or an aluminum alloy, gold or a gold alloy, silver or a silver alloy, nickel or a nickel alloy, and the like.

  The chip embedded structure 27 manufactured by a method different from the above may be prepared.

[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 arranging 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. As a result, as shown in FIG. 8C, a liquid coating of the photosensitive resin varnish 5 is obtained. The photosensitive resin varnish 5 is a varnish of a photosensitive resin composition described later.

  The photosensitive resin varnish 5 is applied by using, for example, a spin coater, a bar coater, a spray device, an inkjet device, or the like.

  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 thinned.

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

  Next, the liquid coating of the photosensitive resin varnish 5 is dried. As a result, the photosensitive resin layer 2510 shown in FIG. 8D is obtained.

  The drying condition of the photosensitive resin varnish 5 is not particularly limited, but examples thereof include a condition of heating at a temperature of 80 to 150 ° C. for 1 to 60 minutes.

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

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

  Thereafter, if necessary, the photosensitive resin layer 2510 is subjected to a pre-exposure heating treatment. By performing the pre-exposure heating 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, while the heating conditions described below are used. By being heated at 1, the adverse effect of heating on the photo-acid generator can be minimized.

  The temperature of the pre-exposure heat treatment is preferably 70 to 130 ° C, more preferably 75 to 120 ° C, and further preferably 80 to 110 ° C. When the temperature of the pre-exposure heat treatment is lower than the lower limit value, the purpose of stabilizing the molecules by the pre-exposure heat treatment may not be fulfilled. On the other hand, if the temperature of the pre-exposure heat treatment exceeds the upper limit value, the movement of the photo-acid generator becomes excessively active, and the acid is less likely to be generated even when irradiated with light in the first exposure step S21 described later. However, the processing accuracy of patterning may be reduced due to the wide area.

  The time of the pre-exposure heat treatment is appropriately set according to the temperature of the pre-exposure heat treatment, but at the temperature, it is preferably 1 to 10 minutes, more preferably 2 to 8 minutes, and further preferably. It is set to 3 to 6 minutes. If the pre-exposure heat treatment time is shorter than the lower limit value, the heating time will be insufficient, and thus the purpose of stabilizing molecules by the pre-exposure heat treatment may not be achieved. On the other hand, when the pre-exposure heat treatment time exceeds the upper limit value, the heating time is too long, so that even if the pre-exposure heat treatment temperature falls within the range, the action of the photo-acid generator is inhibited. There is a risk that

  Further, the atmosphere for the heat treatment is not particularly limited, and may be an inert gas atmosphere, a reducing gas atmosphere, or the like, but in consideration of work efficiency and the like, the atmosphere is the atmosphere.

  Further, the atmospheric pressure is not particularly limited, and may be under reduced pressure or increased pressure, but is normal pressure in consideration of work efficiency and the like. The normal pressure means a pressure of about 30 to 150 kPa, and 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 arranged in a predetermined region on the photosensitive resin layer 2510. Then, light (actinic radiation) is emitted through the mask 412. As a result, the photosensitive resin layer 2510 is exposed 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 type photosensitivity. In this example, the solubility in the developing solution is imparted to the region of the photosensitive resin layer 2510 corresponding to the light shielding portion of the mask 412.

  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 photosensitizer. The generated acid acts as a catalyst for the reaction of the thermosetting resin in the process described below.

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. This can prevent underexposure and overexposure in the photosensitive resin layer 2510. As a result, high patterning accuracy can be finally achieved.
After that, the photosensitive resin layer 2510 is subjected to post-exposure heat treatment, if 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, further preferably 55 to 120 ° C, particularly preferably 60 to 110 ° C. To be done. By performing the 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 will be promoted, and the patterning processing accuracy may decrease. However, if it is within the above range, such a concern can be reduced.

  When the temperature of the post-exposure heat treatment is lower than the lower limit value, the action of a catalyst such as an acid cannot be sufficiently enhanced, and thus the reaction rate of the thermosetting resin may decrease or it may take time. There is. On the other hand, when the temperature of the post-exposure heat treatment exceeds the upper limit value, the diffusion of acid is promoted (widened), and the 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, but at the temperature, preferably 1 to 30 minutes, more preferably 2 to 20 minutes, and further preferably. It is set to 3 to 15 minutes. By performing the post-exposure heat treatment for such a time, the thermosetting resin can be sufficiently reacted, and the acid diffusion can be suppressed to prevent the patterning processing accuracy from being lowered.

  The atmosphere for the post-exposure heat treatment is not particularly limited, and may be an inert gas atmosphere, a reducing gas atmosphere, or the like, but it is in the atmosphere in consideration of work efficiency and the like.

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

[2-3] First developing step S22
Next, the photosensitive resin layer 2510 is developed. As a result, an opening 423 penetrating the photosensitive resin layer 2510 is formed in a region of the mask 412 corresponding to the light shielding part (see FIG. 9E).
Examples of the developing solution include organic developing solutions and water-soluble developing solutions.

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

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

  Note that surface modification treatment such as plasma treatment may be performed before the formation of the wiring layer 253.

[2-6] Second resin film arranging 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 arranged so as to cover the wiring layer 253.

  After that, if necessary, the photosensitive resin layer 2520 is subjected to a pre-exposure heat treatment. The processing conditions are, for example, the conditions described in the first resin film placement 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.

  After that, the photosensitive resin layer 2520 is subjected to post-exposure heat treatment, if necessary. The processing conditions are, for example, the conditions described in the first exposure step S21.

[2-8] Second developing step S27
Next, the photosensitive resin layer 2520 is developed. The processing conditions are, for example, the conditions described in the first developing step S22. Thus, the opening 424 penetrating the photosensitive resin layers 2510 and 2520 is formed (see FIG. 9H).

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

  Although the upper wiring layer 25 has two layers of the organic insulating layer 251 and the organic insulating layer 252 in this embodiment, it 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, and 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.

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

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

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

Then, the resist layer (not shown) is removed. Further, the seed layer (not shown) on the organic insulating layer 252 is removed. For this, for example, a flash etching method can be used.
The formation location 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 forming step S4
Next, as shown in FIG. 10K, 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 thus formed is electrically connected to the upper wiring layer 25 through the penetrating wiring 221.

[5] Solder bump forming 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, if necessary.
Through-electrode substrate 2 is obtained as described above.

  The through electrode substrate 2 shown in FIG. 10L can be divided into a plurality of regions. Therefore, for example, by dividing the through electrode substrate 2 into individual pieces along the alternate long and short dash line shown in FIG. 10L, a plurality of through electrode substrates 2 can be efficiently manufactured. In addition, for example, a diamond cutter or the like can be used for individualization.

[6] Laminating step S6
Next, the semiconductor package 3 is arranged on the individual through-electrode substrate 2. As a result, the semiconductor device 1 shown in FIG. 5 is obtained.

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

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

  The photosensitive resin composition according to the present embodiment includes a thermosetting resin, a photopolymerization initiator as a photosensitizer, and a coupling agent containing an acid anhydride as a functional group. Such a photosensitive resin composition forms an organic insulating layer 21 having good adhesiveness 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. Can be formed.

(Thermosetting resin)
The thermosetting resin preferably contains a semi-curing (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. As a result, the organic insulating layers 21, 251, 252 that take advantage of the characteristics of the thermosetting resin are obtained.

  As the thermosetting resin, for example, phenol novolac type epoxy resin, novolac type epoxy resin such as cresol novolac type epoxy resin, cresol naphthol type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl type epoxy resin, phenoxy resin, naphthalene skeleton 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 type epoxy resin, aromatic polyfunctional epoxy resin, aliphatic epoxy resin, aliphatic polyfunctional epoxy resin, alicyclic epoxy resin, polyfunctional Epoxy resin such as cyclic epoxy resin; resin having triazine ring such as urea (urea) resin and melamine resin; unsaturated polyester resin; maleimide resin such as bismaleimide compound; polyurethane resin; diallyl phthalate resin; silicone resin; benzo Oxazine resin; polyimide resin; polyamideimide resin; benzocyclobutene resin, novolac type cyanate resin, bisphenol A type cyanate resin, bisphenol E type cyanate resin, cyanate ester resin such as tetramethylbisphenol F type cyanate resin Can be mentioned. In the thermosetting resin, one kind among them may be used alone, or two or more kinds having different weight average molecular weights may be used in combination, and one kind or two or more kinds thereof and those You may use together with a polymer.

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

Further, as the epoxy resin, a trifunctional or higher-functional polyfunctional epoxy resin may be used.
The polyfunctional epoxy resin is not particularly limited, but 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 to 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.

  Further, the thermosetting resin is particularly a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a triphenylmethane type epoxy resin, a dicyclopentadiene type epoxy resin, a bisphenol A type epoxy resin, and a tetramethylbisphenol F type epoxy resin. It is preferable to include one or more epoxy resins selected from the group consisting of, more preferably to include a polyfunctional epoxy resin, and even more preferably to include a polyfunctional aromatic epoxy resin. Since such a thermosetting resin is rigid, the organic insulating layers 21, 251, and 252 have good curability, high heat resistance, and a relatively low thermal expansion coefficient.

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

  When the solid resin at room temperature and the liquid resin at room temperature are used together, the amount of the liquid resin at room temperature is preferably about 5 to 150 parts by mass with respect to 100 parts by mass of the solid resin at room temperature. The amount is more preferably about 100 parts by mass, further preferably about 15 to 80 parts by mass. When the ratio of the liquid resin is less than the lower limit value, the embedding property of the semiconductor chip 23 in 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 value, the tack when the photosensitive resin composition is formed into a film is deteriorated, and the mechanical strength of the organic insulating layers 21, 251, 252 which are cured products is lowered. There is a risk of

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

  On the other hand, as the liquid resin at room temperature, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, alkyl glycidyl ether, butane tetracarboxylic acid tetra (3,4-epoxycyclohexylmethyl) modified ε-caprolactone, 3 ′, 4′-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 2-ethylhexylglycidyl ether, trimethylolpropane polyglycidyl ether and the like can be mentioned. These may be used alone or in combination.

  In addition, the resin that is liquid at room temperature preferably contains both an aromatic compound and an aliphatic compound. A photosensitive resin composition containing such a compound is imparted with appropriate flexibility mainly when formed into a film by an aliphatic compound, and retains shape retention when formed into a film mainly by an aromatic compound. Is given. As a result, a photosensitive resin film having both flexibility and shape retention can be obtained.

  Further, a cured product of the photosensitive resin composition, which contains both a resin that is solid at room temperature and a resin that is liquid at room temperature, or the resin that is liquid at room temperature contains both an aromatic compound and an aliphatic compound, etc. In the above, the glass transition temperature can be raised without impairing the patterning property, or the linear expansion coefficient can be lowered without impairing the patterning property.

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

  The content of the epoxy resin is not particularly limited, but is preferably about 40 to 80% by mass, more preferably about 45 to 75% by mass, and more preferably 50 to 70% by mass based on the entire solid content of the photosensitive resin composition. It is more preferable that the amount is about mass%. By setting the content of the epoxy resin within the above range, the patterning property of the photosensitive resin layers 210, 2510, 2520 containing the photosensitive resin composition is enhanced, and the heat resistance of the organic insulating layers 21, 251, 252 and The mechanical strength can be sufficiently increased.

  The solid content of the photosensitive resin composition refers to the non-volatile content in the photosensitive resin composition, and refers to the balance excluding volatile components such as water and solvent. Further, in the present embodiment, the content of the photosensitive resin composition with respect to the entire solid content refers to the content of the photosensitive resin composition with respect to the entire solid content of the photosensitive resin composition excluding the solvent.

(Curing agent)
Further, the photosensitive resin composition of the present invention may contain a 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 phenol resin include novolac type phenol resin, resol type phenol resin, trisphenylmethane type phenol resin, aryl alkylene type phenol resin, and the like. Among these, novolac type phenol resin is particularly preferably used. As a result, the photosensitive resin layers 210, 2510, 2520 having good curability and good developing characteristics are obtained.

  The addition amount of the curing agent is not particularly limited, but is preferably 25 parts by mass or more and 100 parts by mass or less, more preferably 30 parts by mass or more and 90 parts by mass, and 35 parts by mass with respect to 100 parts by mass of the resin. It is more preferable that the amount is not less than 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)
Moreover, the photosensitive resin composition may further contain a thermoplastic resin. Thereby, the moldability of the photosensitive resin composition can be further enhanced, and the flexibility of the cured product of the photosensitive resin composition can be further enhanced. As a result, it is possible to obtain the organic insulating layers 21, 251, 252 in which thermal stress or the like is unlikely to occur.

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

  Among these, phenoxy resin is preferably used as the thermoplastic resin. The phenoxy resin is also called polyhydroxypolyether and has a characteristic that the molecular weight is larger than that of the epoxy resin. By including such a phenoxy resin, it is possible to suppress deterioration of flexibility of a cured product of the photosensitive resin composition.

  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 a phenoxy resin copolymerized with an S-type phenoxy resin, and one or a mixture of two or more of these is used.

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

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

  As the phenoxy resin, those that are solid at room temperature are preferably used. 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.

  The weight average molecular weight of the thermoplastic resin is not particularly limited, but is preferably about 10,000 to 100,000, and more preferably about 20,000 to 80,000. By using such a relatively high molecular weight thermoplastic resin, good flexibility can be imparted to the cured product and sufficient solubility in a solvent can be imparted.

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

  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. It is more preferably 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, it is possible to enhance the balance of mechanical properties of the cured product of the photosensitive resin composition.

  When 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 compounding 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 decrease depending on the components contained in the photosensitive resin composition and the compounding ratio thereof. .

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

  Examples of the photoacid generator include onium salt compounds. Specifically, diazonium salts, iodonium salts such as diaryliodonium salts, sulfonium salts such as triarylsulfonium salts, triarylpyrylium thiocyanates, dialkylphenacylsulfonium salts, dialkylhydroxyphenylphosphonium salts, etc. Examples thereof include cationic photopolymerization initiators.

Since the photosensitive composition is in contact with the metal, the photosensitizer is preferably one that does not generate hydrogen fluoride due to decomposition, such as a methide salt type or a borate salt type.
In particular, a triarylsulfonium salt having a borate anion as a counter anion is preferably used as the photosensitizer. Since such a triarylsulfonium salt contains a borate anion having a low corrosiveness with respect to a metal as a counter anion, corrosion of metal materials such as the through wirings 22, 221, 222 and the wiring layer 253 is prevented for a longer period of time. Can be prevented. As a result, the reliability of the semiconductor device 1 can be further increased.

  The amount of the photosensitizer added is not particularly limited, but is preferably about 0.3 to 5% by mass, and preferably about 0.5 to 4.5% by mass based on the total solid content of the photosensitive resin composition. More preferably, it is still more preferably about 1 to 4% by mass. By setting the addition amount of the photosensitizer within the above range, the patterning property of the photosensitive resin layers 210, 2510, 2520 containing the photosensitive resin composition is improved and the long-term storage property of the photosensitive resin composition is improved. be able to.

  The photosensitizer may be one that imparts negative-type photosensitivity to the photosensitive resin composition or one that imparts positive-type photosensitivity. The negative type is preferable in view of the fact that the can be formed with high precision.

(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 makes it possible to form 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 can be obtained.

  In such an acid anhydride-containing coupling agent, the acid anhydride, which is a functional group, dissolves the inorganic oxide and forms a coordinate bond with a cation (such as a metal cation).

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

  Therefore, it is considered that a photosensitive resin composition having good adhesion to the inorganic material and the 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 abbreviated as “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. By using such a coupling agent, a photosensitive resin composition having a better adhesiveness to an inorganic material and a metal material, a good sensitivity, and an excellent patterning property can be obtained.

  Specific examples of the compound containing an alkoxysilyl group include 3-trimethoxysilylpropyl succinic anhydride, 3-triethoxysilylsilyl succinic anhydride, 3-dimethylmethoxysilylpropyl succinic anhydride, and 3-dimethylethoxy. Succinic anhydrides such as silylpropylsuccinic anhydride, 3-trimethoxysilylpropylcyclohexyldicarboxylic acid anhydride, 3-triethoxysilylpropylcyclohexyldicarboxylic acid anhydride, 3-dimethylmethoxysilylpropylcyclohexyldicarboxylic acid anhydride, Dicarboxylic acid anhydrides such as 3-dimethylethoxysilylpropylcyclohexyldicarboxylic acid anhydride, 3-trimethoxysilylpropylphthalic acid anhydride, 3-triethoxysilylpropylphthalic acid 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, an 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-mentioned adhesiveness and patterning property are further improved.

  Although the silane coupling agent is listed here, a titanium coupling agent, a zirconium coupling agent, or the like may be used.

  The addition amount of the acid anhydride-containing coupling agent is not particularly limited, but is preferably about 0.3 to 5 mass% of the total solid content of the photosensitive resin composition, and 0.5 to 4.5 mass%. The amount is more preferably about 1 to 4% by mass, further preferably about 1 to 4% by mass. By setting the addition amount of the acid anhydride-containing coupling agent within the above range, the adhesion to inorganic materials and metal materials such as the through wirings 22, 221, 222, the wiring layer 253 and the semiconductor chip 23 is particularly good. The 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 for a long period of time.

  If the addition amount of the acid anhydride-containing coupling agent is less than the lower limit value described above, the adhesion to the inorganic material and the metal material may decrease depending on the composition of the acid anhydride-containing coupling agent and the like. 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 and the like, the photosensitivity and mechanical properties of the photosensitive resin composition may decrease. is there.

  In addition to the acid anhydride-containing coupling agent, other coupling agent may be further added.

  Examples of other coupling agents include coupling agents having a functional group such as amino group, epoxy group, acryl group, methacryl group, mercapto group, vinyl group, ureido group, and sulfide group. These may be used alone or in combination.

  Of 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 can be mentioned.

  Examples of the epoxy group-containing coupling agent include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidylpropyl. Trimethoxysilane etc. are mentioned.

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

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

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

  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, and 5 to More preferably, it is about 100% by mass. By setting the addition amount within this range, another action is added by addition of another coupling agent without impairing the above-mentioned action by the acid anhydride-containing coupling agent. As a result, the effects produced by both coupling agents can be compatible.

(Other additives)
Other additives may be added to the photosensitive resin composition, if necessary. Examples of other additives include antioxidants, fillers such as silica, surfactants, sensitizers and film forming agents.

  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. This solvent can be used without particular limitation as long as it can dissolve the respective constituent components of the photosensitive resin composition and does not react with the respective constituent components.

  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 be in the form of varnish.

  The varnish-shaped photosensitive resin composition is prepared, for example, by uniformly mixing a raw material and a solvent. The solvent may be added as necessary, and it is possible to form a varnish without using the solvent. After that, it may be subjected to a treatment such as filtration with a filter or defoaming.

  The solid content concentration in the varnish-like photosensitive resin composition is not particularly limited, but is preferably about 20 to 80% by mass. Since the varnish-like photosensitive resin composition having such a solid content concentration has an optimized viscosity, it has a good fluidity that easily penetrates into a narrow gap and does not easily cause film breakage. Becomes

<Photosensitive resin film>
Next, the photosensitive resin film according to this 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-shaped photosensitive resin composition is applied onto a carrier film and then dried.

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

  The content of the solvent in the photosensitive resin film is not particularly limited, but it is preferably 10% by mass or less of the entire photosensitive resin film. This can improve the tack of the photosensitive resin film and enhance the curability of the photosensitive resin film. In addition, the generation of voids due to the volatilization of the solvent can be suppressed.

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

  The photosensitive resin film laminated on the carrier film is useful from the viewpoints of handleability, surface cleanability, and the like. At this time, the carrier film may be in a roll form capable of being wound or in a sheet form.

  Examples of the constituent material of the carrier film include a resin material and a metal material. Among them, examples of the resin material include polyolefin such as polyethylene and polypropylene, polyester such as polyethylene terephthalate and polybutylene terephthalate, polycarbonate, silicone, fluorine resin, polyimide resin and the like. Further, 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 favorably supports the photosensitive resin film and is relatively easy to peel off.

  In addition, a cover film may be provided on the surface of the photosensitive resin film, if necessary. This cover film protects the surface of the photosensitive resin film until it is attached.

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

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

  Since such a semiconductor device has a protective film having excellent chemical resistance, it has high reliability. Therefore, high reliability is also given to the electronic device according to the present embodiment.

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

  The present invention has been described above based on the illustrated embodiments, but the present 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 the ones in which any element is added to the above embodiment.

  In addition to the semiconductor device, the photosensitive resin composition and the photosensitive resin film are used to form structures of display devices such as MEMS (Micro Electro Mechanical Systems) and various sensor structure forming materials, liquid crystal display devices, and organic EL devices. It can also be applied to materials and the like.

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 solutions.

  Next, the prepared solution was filtered with 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 to 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. 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 applied onto a silicon wafer with a spin coater. As a result, a liquid coating having a thickness of 10 μm was obtained.

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

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

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

  First, a notch was made in the photosensitive resin film using a tool. The cuts were made at intervals of 1 mm so as to pass through the photosensitive resin film 10 in length and width. As a result, 100 squares of 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 how many of the 100 squares were 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 in 2.2.1. Table 2 shows the evaluation results.

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

2.2.3 Copper adhesion test (normal temperature)
Adhesion at room temperature in the same manner as in 2.2.1, except that the test piece was used in which the silicon wafer of 2.1 was subjected to an undertreatment with Ti and then a copper wafer having a film thickness of 300 nm was vapor-deposited. The test was conducted. Table 2 shows the evaluation results.

2.2.4 Copper adhesion test (high temperature)
Adhesion at high temperature in the same manner as in 2.2.2 except that a test piece was used in which the silicon wafer of 2.1 was subjected to an underlying treatment with Ti and then a copper wafer having a film thickness of 300 nm was vapor-deposited. The test was conducted. Table 2 shows the evaluation results.

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

Next, the liquid coating was dried on a hot plate at 120 ° C. for 5 minutes to obtain a coating.
Next, the coating film was exposed through a negative pattern mask using an i-line stepper (manufactured by Nikon Corporation, NSR-4425i). Then, a post exposure heat treatment was performed at 70 ° C. for 5 minutes.

  Next, propylene glycol monomethyl ether acetate (PGMEA) at 25 ° C. was used as a developing solution to carry out spray development to dissolve and remove the unexposed portion, followed by rinsing with isopropyl alcohol (IPA).

  Next, it was visually confirmed whether patterning could be performed, and the patterning property was evaluated according to the following evaluation criteria.

<Pattern evaluation criteria>
◯: A pattern could be obtained by dissolving the unexposed area x: A pattern could not be obtained due to total dissolution or insolubility The evaluation results are shown in Table 2.

  As is clear from Table 2, it was revealed that the photosensitive resin films obtained in the respective examples have good adhesiveness to the inorganic material and the metal material.

  The negative photosensitive resin composition of the present invention contains 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, a resin film formed of a negative photosensitive resin composition can be adhered to a semiconductor chip formed of an inorganic material or a metal material and various metal wirings. The property becomes good. Therefore, the reliability of the semiconductor device using such a negative photosensitive resin composition can be improved. Therefore, the present invention has industrial applicability.

Claims (11)

A thermosetting resin,
With phenoxy 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 phenoxy resin contains a component that is solid at room temperature.   The negative photosensitive resin composition according to claim 1, wherein the phenoxy resin contains a component having epoxy groups at both ends of the molecular chain.   The negative photosensitive resin composition according to claim 1, wherein the addition amount of the phenoxy resin is 10 parts by mass or more and 90 parts by mass or less with respect to 100 parts by mass of the thermosetting resin.   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 any one of claims 1 to 5, wherein the acid anhydride is succinic anhydride.   The negative photosensitive resin composition according to claim 1, 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 claim 1, 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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