JP2019060960A - Photosensitive resin composition, photosensitive resin film, semiconductor device, and electronic apparatus - Google Patents

Abstract

To provide a photosensitive resin composition from which a resin film having good surface flatness can be formed, a photosensitive resin film, a semiconductor device with high reliability including the resin film, and an electronic apparatus including the semiconductor device.SOLUTION: The photosensitive resin composition of the present invention comprises a thermosetting resin, a phenolic resin that can react with the thermosetting resin, and a photosensitizer, in which the content of dimers in the phenolic resin is 3 mass% or less. It is preferable that the content of trimers in the phenolic resin is 3 mass% or less. The thermosetting resin is preferably an epoxy resin.SELECTED DRAWING: Figure 1

Description

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

  For the semiconductor element, a resin film made of a resin material is used for applications such as a protective film, an interlayer insulating film, and a planarization 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, warpage of the semiconductor chip tends to occur.

  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. Thereby, the target pattern can be formed with high accuracy.

  Then, development of the resin composition which can manufacture the resin film which has photosensitivity and can be thickened is furthered.

  For example, Patent Document 1 discloses a photosensitive resin composition which is excellent in light transmittance and can suppress warpage of a semiconductor chip by optimizing the molecular structure and reducing the residual stress. The photosensitive resin composition is in the form of a liquid, is applied onto a substrate by spin coating, and is then dried and subjected to exposure processing and development processing. Thereby, patterning corresponding to the exposure pattern is performed.

JP 2003-209104 A

  On the other hand, the photosensitive resin composition is accompanied by shrinkage upon curing. The curing shrinkage increases as the film thickness of the applied photosensitive resin composition increases. For this reason, when the substrate to be applied contains unevenness, the thickness of the photosensitive resin composition varies depending on the unevenness, so the curing shrinkage amount of the photosensitive resin composition in the convex portion and the concave portion The flatness of the surface of the resin film formed after curing decreases. As a result, for example, when laminating a rewiring layer or the like on a resin film, inclination or the like occurs in the rewiring layer, which causes a problem that positional accuracy and dimensional accuracy of the rewiring layer are lowered.

  An object of the present invention is to provide a photosensitive resin composition and a photosensitive resin film capable of forming a resin film having good surface flatness, a highly reliable semiconductor device provided with the resin film, and an electron provided with the semiconductor device To provide equipment.

Such an object is achieved by the present invention of the following (1) to (8).
(1) Thermosetting resin,
A phenolic resin capable of reacting with the thermosetting resin;
A photosensitizer,
Including
The photosensitive resin composition characterized in that the content of the dimer in the phenolic resin is 3% by mass or less.

(2) The photosensitive resin composition as described in said (1) which contains an adhesion | attachment adjuvant further.
(3) The photosensitive resin composition according to the above (1) or (2), wherein the thermosetting resin is an epoxy resin.

(4) A photosensitive resin film comprising the photosensitive resin composition according to any one of (1) to (3) above.
(5) The photosensitive resin film as described in said (4) whose thickness is 100-1000 micrometers.

(6) Semiconductor chip,
A resin film containing a cured product of the photosensitive resin composition according to any one of the above (1) to (3), provided at least on the surface of the semiconductor chip;
A semiconductor device comprising:

  (7) The semiconductor device according to (6), wherein the resin film is provided to embed the semiconductor chip.

  (8) An electronic device comprising the semiconductor device according to (6) or (7).

  According to the present invention, a photosensitive resin composition and a photosensitive resin film capable of forming a resin film having good surface flatness can be obtained.

Further, according to the present invention, a highly reliable semiconductor device provided with the resin film can be obtained.
Further, according to the present invention, an electronic device provided with the above semiconductor device can be obtained.

It is a longitudinal section showing an embodiment of a semiconductor device of the present invention. It is the elements on larger scale of the area | region enclosed by the chain line of FIG. It is a figure for demonstrating the method to manufacture the semiconductor device shown in FIG. It is a figure for demonstrating the method to manufacture the semiconductor device shown in FIG. It is a figure for demonstrating the method to manufacture the semiconductor device shown in FIG. It is a figure which shows an example of the melt viscosity curve of the photosensitive resin composition. It is a longitudinal cross-sectional view which shows typically the structure of the test piece for hardening shrinkage evaluation.

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

<Semiconductor device>
First, prior to the description of the photosensitive resin composition, an embodiment of the semiconductor device of the present invention will be described.

  FIG. 1 is a longitudinal sectional view showing an embodiment of a semiconductor device of the present invention. FIG. 2 is a partially enlarged view of a region surrounded by a dashed line in FIG. In the following description, the upper side in FIG. 1 is referred to as “upper” and the lower side 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 them, the through electrode substrate 2 includes an organic insulating layer 21 (resin film), a plurality of through wires 22 penetrating the upper surface to the lower surface of the organic insulating layer 21, and a semiconductor chip 23 embedded in the organic insulating layer 21. A lower wiring layer 24 provided on the lower surface of the organic insulating layer 21, an upper wiring layer 25 provided on the upper surface of the organic insulating layer 21, and a solder bump 26 provided on the lower surface of the lower wiring layer 24; Have.

  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. A sealing layer 34 in which 33 is embedded and solder bumps 35 provided on the lower surface of the package substrate 31 are provided.

  The semiconductor package 3 is stacked on the through electrode substrate 2. Thus, 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 it is not necessary to use a thick substrate such as an organic substrate including a core layer in the through electrode substrate 2, the height can be easily reduced. For this reason, it can contribute also to size reduction of the electronic device which incorporates the semiconductor device 1.

  In addition, since the through electrode substrate 2 and the semiconductor package 3 having semiconductor chips different from each other are stacked, the mounting density per unit area can be increased. Therefore, it is possible to achieve both size reduction and high performance.

Hereinafter, the through electrode substrate 2 and the semiconductor package 3 will be described in more detail.
Lower layer wiring layer 24 and upper layer wiring layer 25 provided in through electrode substrate 2 shown in FIG. 2 each include an insulating layer, a wiring layer, a through wiring, and the like. Thereby, the lower interconnection layer 24 and the upper interconnection layer 25 include interconnections inside and on the surface, and mutual electrical connection is achieved through the through interconnections 22 penetrating the organic insulating layer 21.

  Among these, the wiring layer included in the lower layer wiring layer 24 is connected to the semiconductor chip 23 and the solder bump 26. Thus, 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.

  Further, as described above, the through wiring 22 shown in FIG. 2 is provided 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. Therefore, the semiconductor device 1 can be highly functional. it can.

  Furthermore, the wiring layer included in the upper wiring layer 25 shown in FIG. 2 is connected to the through wiring 22 and the solder bump 35. Therefore, the upper wiring layer 25 is electrically connected to the semiconductor chip 23 and functions as a rewiring layer of the semiconductor chip 23 and as an interposer interposed between the semiconductor chip 23 and the package substrate 31. Also works.

  Moreover, the effect of reinforcing the organic insulating layer 21 can be obtained by the through wiring 22 penetrating the organic insulating layer 21. Therefore, even when the mechanical strength of the lower wiring layer 24 and the upper wiring layer 25 is low, it is possible to avoid the reduction in the mechanical strength of the entire through electrode substrate 2. As a result, the thickness of the lower wiring layer 24 and the upper wiring layer 25 can be further reduced, and the height of the semiconductor device 1 can be further reduced.

  The through wiring 22 may be provided to penetrate, for example, the organic insulating layer 21 located on the upper surface of the semiconductor chip 23 in addition to the portion illustrated.

  Furthermore, the organic insulating layer 21 is provided (on the surface of the semiconductor chip 23) so as to embed the semiconductor chip 23. Thereby, the effect of protecting the semiconductor chip 23 is enhanced. As a result, the reliability of the semiconductor device 1 can be improved. Moreover, the semiconductor device 1 which can be easily applied to the mounting method like the package on package structure which concerns on this embodiment is obtained.

  The diameter W (see FIG. 2) of the through wiring 22 is not particularly limited, but is preferably about 1 to 100 μm, and more preferably about 2 to 80 μm. Thereby, the conductivity of the through wiring 22 can be secured without impairing the mechanical properties of the organic insulating layer 21.

  The semiconductor package 3 shown in FIG. 1 may be any type of package. For example, Quad Flat Package (QFP), Small Outline Package (SOP), Ball Grid Array (BGA), Chip Size Package (CSP), Quad Flat Non-Leaded Package (QFN), Small Outline Non-leaded Package (SON), The form of LF-BGA (Lead Flame BGA) etc. is mentioned.

  The arrangement of the semiconductor chips 32 is not particularly limited, but as an example in FIG. 1, a plurality of semiconductor chips 32 are stacked. Thereby, the mounting density is increased. The plurality of semiconductor chips 32 may be juxtaposed in the planar direction, or may be juxtaposed in the planar direction while being stacked in the thickness direction.

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

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

  In addition, since the semiconductor chip 23 included in the through electrode substrate 2 and the semiconductor chip 32 included in the semiconductor package 3 are disposed in proximity to each other, it is possible to enjoy advantages such as speeding up and reduction in mutual communication. 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 central processing unit (CPU), a graphics processing unit (GPU), or an application processor (AP), and the other is a dynamic random access (DRAM) In the case of a storage element or the like such as a memory or a flash memory, these elements can be arranged close to each other in the same device. As a result, it is possible to realize the semiconductor device 1 in which high functionalization and miniaturization are compatible.

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

The organic insulating layer 21 contains a cured product of a photosensitive resin composition described later.
The cured product of the photosensitive resin composition according to this embodiment preferably has a glass transition temperature (Tg) of 140 ° C. or higher, more preferably 150 ° C. or higher, and still more preferably 160 ° C. or higher. preferable. As a result, the heat resistance of the organic insulating layer 21 can be enhanced, so that the semiconductor device 1 that can be used even in a high temperature environment, for example, can be realized. The upper limit of the cured product of the photosensitive resin composition may not be particularly set, but is, for example, 250 ° C. or less.

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

  The cured product of the photosensitive resin composition according to this embodiment preferably has a linear expansion coefficient (CTE) of 5 to 80 ppm / ° C., more preferably 10 to 70 ppm / ° C., and 15 to 60 ppm / ° C. More preferably, it is ° C. Thereby, the linear expansion coefficient of the organic insulating layer 21 can be made close to, for example, the linear expansion coefficient of a silicon material. Therefore, for example, the organic insulating layer 21 in which the semiconductor chip 23 is not easily warped can be obtained. As a result, a highly reliable semiconductor device 1 can be obtained.

  The linear expansion coefficient of the cured product of the photosensitive resin composition was measured using a thermomechanical analyzer (TMA) for a predetermined test piece (width 4 mm × length 20 mm × thickness 0.005 to 0.015 mm). It is calculated from the result of measurement under the conditions of start temperature 30 ° C., measurement temperature range 30 to 400 ° C., temperature rising rate 5 ° C./min.

  The cured product of the photosensitive resin composition according to this embodiment preferably has a 5% thermal weight loss temperature Td5 of 300 ° C. or higher, and more preferably 320 ° C. or higher. As a result, weight reduction due to thermal decomposition and the like does not easily occur even at high temperatures, and a cured product having excellent heat resistance can be obtained. For this reason, the organic insulating layer 21 excellent in the durability under high temperature environment is obtained.

  The 5% thermal weight loss temperature Td5 of the cured product of the photosensitive resin composition is calculated from the result of measurement using a differential thermal thermal simultaneous measurement device (TG / DTA) for 5 mg of the cured product. Ru.

  The cured product of the photosensitive resin composition according to the present embodiment preferably has an elongation of 5 to 50%, more preferably 6 to 45%, still more preferably 7 to 40%. . As a result, the elongation rate of the organic insulating layer 21 is optimized, so that, for example, even when the through wiring 22 is provided to penetrate the organic insulating layer 21, the organic insulating layer 21 and the through wiring 22 and It is possible to suppress the occurrence of peeling or the like at the interface of Also in the organic insulating layer 21 itself, the occurrence of cracks and the like can be suppressed.

  In addition, when the elongation percentage is below the lower limit value, there is a possibility that a crack or the like is easily generated in the organic insulating layer 21 depending on the thickness, the shape, and the like of the organic insulating layer 21. On the other hand, when the elongation percentage exceeds the upper limit value, the mechanical properties of the organic insulating layer 21 may be deteriorated depending on the thickness, the shape, and the like of the organic insulating layer 21.

  The elongation of the cured product of the photosensitive resin composition is measured as follows. First, a tensile test (tensile speed: 5 mm / min) was performed on a predetermined test piece (width 6.5 mm × length 20 mm × thickness 0.005 to 0.015 mm) in an atmosphere with a temperature of 25 ° C. and a humidity of 55%. To carry out. The tensile test is performed using a tensile tester (Tensilon RTA-100) manufactured by Orientec Co., Ltd. Then, the tensile elongation rate is calculated from the result of the said tensile test. Here, the above-mentioned tensile test is carried out at the number of times of the test n = 10, and the average value of five times where the measured value is large is determined, and this is taken as the elongation of the cured product.

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

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

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

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

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

<Method of Manufacturing Semiconductor Device>
Next, a method of manufacturing the semiconductor device 1 shown in FIG. 1 will be described.
3 to 5 are views for explaining a method of manufacturing the semiconductor device 1 shown in FIG.

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

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

  Next, as shown in FIG. 3B, the semiconductor chip 23 is disposed on the substrate 202. In this manufacturing method, as an example, a plurality of semiconductor chips 23 are provided on the same substrate 202 while being separated from each other. The plurality of semiconductor chips 23 may be of the same type as each other or may be of different types. Alternatively, the substrate 202 and the semiconductor chip 23 may be fixed via an adhesive layer (not shown) such as a die attach film.

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

  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 for such an interposer.

[2] Film Arrangement Step Next, as shown in FIG. 3C, the photosensitive resin film 20 is arranged on the semiconductor chip 23. The photosensitive resin film 20 is a resin film having heat melting property and photosensitivity, which will be described in detail later.

  Next, the photosensitive resin film 20 is heated while being pressed downward. Thus, the photosensitive resin film 20 can be disposed so as to bury the semiconductor chip 23 as shown in FIG. 3D while melting the photosensitive resin film 20. As a result, as shown in FIG. 4E, the photosensitive resin layer 210 in which the semiconductor chip 23 is embedded is obtained.

  When the photosensitive resin film 20 is disposed on the semiconductor chip 23, the photosensitive resin film 20 may be disposed alone, and the photosensitive resin film 20 laminated on the carrier film is pressed to the semiconductor chip 23. You may make it arrange | position so that it may be applied.

  In addition, a known laminating method may be used in this operation. In that case, for example, a vacuum laminator is used. The vacuum laminator may be a batch type or a continuous type. Specifically, using a heat plate which can be pressed with a predetermined pressure and heated to a predetermined temperature in the vacuum chamber, the photosensitive resin film 20 is applied to the adherend placed on the table. A method of pressing is used.

  Although the heating temperature at this time is suitably set according to the constituent material etc. of the photosensitive resin film 20, it is preferable that it is 40-150 degreeC as an example, and it is more preferable that it is 50-140 degreeC, and 60- More preferably, the temperature is 130 ° C. By heating at such a temperature, the embeddability of the semiconductor chip 23 in the photosensitive resin film 20 is improved, and the curing reaction of the photosensitive resin film 20 proceeds with the excessive heating, or the photosensitive resin layer It can suppress that the processability of 210 falls.

  Moreover, although heating time is suitably set according to heating temperature, it is preferable that it is 10 to 100 second as an example.

  The pressure is not particularly limited, but is preferably 0.2 to 5 MPa, and more preferably 0.4 to 1 MPa.

  In addition, when arrange | positioning photosensitive resin so that the semiconductor chip 23 may be embedded, the photosensitive resin layer obtained by the process mentioned later by using the photosensitive resin film 20 (it is formed into a film) containing a photosensitive resin composition. Thickening of the film 210 can be easily achieved. This enables the formation of the photosensitive resin layer 210 that can be easily embedded even in the semiconductor chip 23 having a large thickness. In addition, even when the film is thickened, the curing and shrinkage amount can be relatively easily reduced, and the uniform thickness of the photosensitive resin layer 210 can be easily achieved.

  In addition, in the laminating method, since the photosensitive resin film 20 is pressed by the heat plate, the contact surface of the heat plate can be easily flattened. For this reason, the photosensitive resin layer 210 obtained in the process to be described later has better planarization of the upper surface. Therefore, when the upper wiring layer 25 is further laminated on the upper surface of the photosensitive resin layer 210, many advantages can be obtained in terms of good workability, high precision of lamination position, and the like.

  In addition, although the photosensitive resin film 20 is manufactured by film-forming the varnish-like photosensitive resin composition, specifically, the photosensitive resin composition whose viscosity is adjusted with a solvent etc. Apply on the ground. Then, the photosensitive resin film 20 is obtained by drying the obtained coating film.

  Although the content rate of the solvent in the photosensitive resin film 20 is not specifically limited, It is preferable that it is 10 mass% or less of the photosensitive resin film 20 whole. Thus, the tackiness of the photosensitive resin film 20 can be improved, and the curability of the photosensitive resin film 20 can be enhanced. In addition, the generation of voids due to the volatilization of the solvent can be suppressed.

  The drying conditions include, for example, heating at a temperature of 80 to 150 ° C. for 5 to 30 minutes.

  In the above description, the photosensitive resin layer 210 is formed using the photosensitive resin film 20. However, a photosensitive resin composition in the form of a varnish is applied so as to embed the semiconductor chip 23 and dried. The conductive resin layer 210 may be formed.

  After that, the photosensitive resin layer 210 formed in this manner may be subjected to a pre-exposure heat treatment, if necessary. Thereby, the molecules contained in the photosensitive resin layer 210 can be stabilized, and the reaction in the exposure process described later can be stabilized.

  The temperature of the heat treatment before exposure is not particularly limited, but is preferably 70 to 120 ° C., more preferably 75 to 115 ° C., and still more preferably 75 to 110 ° C. If the temperature of the pre-exposure heat treatment is below the lower limit value, the purpose of the stabilization of molecules by the pre-exposure heat treatment may not be achieved. On the other hand, when the temperature of the pre-exposure heat treatment exceeds the upper limit value, the photoacid generator is activated too much, and the effect that the acid is hardly generated even if light is irradiated in the exposure step described later There is a possibility that the processing accuracy of patterning may be lowered in the development step.

  Further, the time of the pre-exposure heat treatment is appropriately set according to the temperature of the pre-exposure heat treatment, but is preferably about 1 to 30 minutes at the temperature, and more preferably about 2 to 20 minutes. More preferably, it is about 3 to 10 minutes. If the time of the pre-exposure heat treatment is below the lower limit value, the heating time is insufficient, so that the purpose of the stabilization of the molecules by the pre-exposure heat treatment may not be achieved. On the other hand, if the pre-exposure heat treatment time exceeds the upper limit value, the heating time is too long, so even if the pre-exposure heat treatment temperature falls within the above range, the action of the photoacid generator is inhibited. There is a risk of

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

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

  The film thickness of the photosensitive resin film 20 (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, while the semiconductor The thickness is not particularly limited as long as the chip 23 can be embedded, but as an example, it is preferably about 100 to 1000 μm, more preferably about 120 to 750 μm, and still more preferably about 140 to 500 μm. By setting the film thickness of the photosensitive resin film 20 within the above range, a relatively thick semiconductor chip 23 can be easily embedded, and sufficient mechanical strength to the cured film of the photosensitive resin film 20 Can also be granted. As a result, it is possible to form a cured film that contributes to the rigidity of the semiconductor device 1 as well as the good protection of the semiconductor chip 23.

  When the photosensitive resin film 20 laminated on the carrier film is disposed to be pressed against the semiconductor chip 23, the carrier film is peeled off from the photosensitive resin film 20 just before the pre-exposure heat treatment. Is preferred. Thereby, the photosensitive resin film 20 can be protected by the carrier film just before the pre-exposure heat treatment. As a result, damage to the photosensitive resin film 20 and adhesion of foreign matter can be prevented, and the surface flatness can be further enhanced.

  Here, as the photosensitive resin composition contained in the photosensitive resin film 20, those having the following characteristics are preferably used.

  That is, this photosensitive resin composition has a characteristic that the melt viscosity is 5 Pa · s or less when measured under the measurement conditions of a temperature increase rate of 5 ° C./min, a frequency of 0.1 Hz and a heating temperature of 30 to 150 ° C. Is preferable, and it is more preferable to have a characteristic of 4 Pa · s or less, and further preferable to have a characteristic of 3 Pa · s or less. The photosensitive resin composition having such characteristics is, for example, entangled when the photosensitive resin film 20 is disposed on the semiconductor chip 23 as described above and the semiconductor chip 23 is further embedded in the photosensitive resin film 20. Allows air to be expelled effectively. For this reason, generation of voids (air gaps) due to air remaining is suppressed, and formation of a photosensitive resin layer 210 with few voids and high reliability is made possible.

  On the other hand, the lower limit value of the melt viscosity of the photosensitive resin composition is not particularly limited, but it is easy to maintain the shape even if it is melted (do not flow out), or to easily secure a sufficient film thickness If so, it may be set to 0.2 Pa · s or more.

The melt viscosity of the photosensitive resin composition is measured as follows.
First, a photosensitive resin film having a thickness of 150 μm is prepared.

  Next, using a visco-elasticity measuring apparatus ("MARS" manufactured by Thermo Fisher Scientific Co., Ltd.), parallel plate 20 mmφ, gap 0.05 mm, heating rate 5 ° C./min, frequency 0.1 Hz, temperature 30 to 150 ° C. Under the measurement conditions, the melt viscosity curve (the change curve of the melt viscosity with respect to temperature) of the photosensitive resin film is obtained.

  Then, the lowest viscosity in the obtained melt viscosity curve is taken as the melt viscosity of the photosensitive resin composition.

Moreover, in FIG. 6, an example of the melt viscosity curve of the photosensitive resin composition is shown.
The melt viscosity curve shown in FIG. 6 is a curve in which the viscosity decreases with increasing temperature.

  In such a melt viscosity curve, when the slope of the curve at 50 ° C. (ratio of change in viscosity to temperature) is determined, it is preferably −500 to −10 [(Pa · s) / ° C.], −300 to It is more preferably -30 [(Pa · s) / ° C], and even more preferably -150 to -50 [(Pa · s) / ° C]. By setting the slope of the curve within the above range, the embeddability of the semiconductor chip 23 into the photosensitive resin film 20 is further improved, and air entrapment is less likely to occur. That is, by optimizing the reduction rate of the melt viscosity, it is possible to balance the speed at which the photosensitive resin film 20 enters the gap between the semiconductor chips 23 and the speed at which the entrapped air is discharged. The photosensitive resin film 20 in which the semiconductor chip 23 is embedded in a state where there are few voids is obtained.

When the slope of the curve at 50 ° C. is determined, the viscosity μ 48 at 48 ° C. and the viscosity μ 52 at 52 ° C. may be simply determined, and the rate of change of viscosity in the section may be determined by the following equation.
Curve slope = (μ 52-μ 48) / (52-48)

  The melt viscosity of the photosensitive resin composition can be adjusted by the raw material of the photosensitive resin film 20. For example, the melt viscosity can be reduced by adding more liquid resin at normal temperature.

[3] Exposure Step Next, the photosensitive resin layer 210 is exposed.

  First, as shown in FIG. 4F, the mask 41 is disposed in a predetermined area on the photosensitive resin layer 210. Then, light (actinic radiation) is irradiated through the mask 41. Thus, the photosensitive resin layer 210 is exposed according to the pattern of the mask 41.

  In addition, in FIG. 4, the case where the photosensitive resin layer 210 has what is called negative photosensitive property is illustrated. In this example, in the photosensitive resin layer 210, the solubility in the developer is given to the region corresponding to the light shielding portion of the mask 41.

  Thereafter, if necessary, a post-exposure heat treatment is performed. Although the conditions of the post-exposure heat treatment are not particularly limited, for example, the heating temperature is about 50 to 150 ° C., and the heating time is about 1 to 10 minutes.

[4] Development Step Next, the photosensitive resin layer 210 subjected to the exposure processing is subjected to a development processing. Thereby, the opening 42 penetrating the photosensitive resin layer 210 is formed in the region corresponding to the light shielding portion of the mask 41 (see FIG. 4G).

As a developing solution, an organic type developing solution, a water-soluble developing solution, etc. are mentioned, for example.
After the development process, the photosensitive resin layer 210 is subjected to a post-development heat treatment, if necessary. Although the conditions of the post-development heat treatment are not particularly limited, the heating temperature is about 160 to 250 ° C., and the heating time is about 30 to 120 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] Step of Forming Through Wiring Next, as shown in FIG. 4H, the through wiring 22 is formed in the opening 42.

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

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

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

  Also, the seed layer may be made of the same kind of metal as the through wire 22 to be formed, or may be made of different kinds of metal.

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

Then, the resist layer not shown is removed. Further, the seed layer (not shown) on the organic insulating layer 21 is removed. For this, for example, a flash etching method can be used.
In addition, the formation location of the penetration wiring 22 is not limited to the position of illustration. For example, it may be provided at a position passing through the photosensitive resin layer 210 covering the semiconductor chip 23.

[6] Upper Wiring Layer Forming Step Next, as shown in FIG. 5I, 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, for example, using a photolithography method and a plating method.

[7] Lower Layer Wiring Layer Forming Step Next, as shown in FIG. 5J, the substrate 202 is peeled off. Thereby, the lower surface of the organic insulating layer 21 is exposed.

  Next, as shown in FIG. 5K, the lower wiring layer 24 is formed on the lower surface side of the organic insulating layer 21. The lower wiring layer 24 is formed using, for example, a photolithography method and a plating method. The lower wiring layer 24 thus formed is electrically connected to the upper wiring layer 25 through the through wiring 22.

[8] Step of Forming Solder Bump Next, as shown in FIG. 5L, the solder bump 26 is formed on the lower wiring layer 24. In addition, a protective film such as a solder resist layer may be formed on the upper wiring layer 25 and the lower wiring layer 24 as necessary.
As described above, the through electrode substrate 2 is obtained.

  The through electrode substrate 2 shown in FIG. 5L can be divided into a plurality of regions. Therefore, for example, the through electrode substrate 2 can be efficiently manufactured by dividing the through electrode substrate 2 along the alternate long and short dash line shown in FIG. 5L. In addition, a diamond cutter etc. can be used for individualization, for example.

[9] Stacking Step Next, the semiconductor package 3 is disposed on the singulated through electrode substrate 2. Thereby, 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 made of the photosensitive resin composition, the arrangement of the semiconductor chip 23, the embedding of the semiconductor chip 23, the formation of the through wiring 22, the formation of the upper wiring layer 25, and the lower wiring layer 24. Can be performed by wafer level process or panel level process. As a result, the manufacturing efficiency of the semiconductor device 1 can be enhanced and the cost can be reduced.

<Photosensitive resin composition>
Next, the photosensitive resin composition (embodiment of the photosensitive resin composition of this invention) used for the method of manufacturing the semiconductor device 1 is demonstrated.

  The photosensitive resin composition is not particularly limited as long as it is a resin composition having photosensitivity and heat melting property, and, for example, a thermosetting resin, a phenol resin capable of reacting with the thermosetting resin, and a photosensitizer. , And a coupling agent.

(Thermosetting resin)
As the thermosetting resin, for example, phenol novolac epoxy resin, novolac epoxy resin such as cresol novolac epoxy resin, cresol naphthol epoxy resin, biphenyl epoxy resin, biphenyl aralkyl epoxy resin, phenoxy resin, naphthalene skeleton Epoxy resin, bisphenol A epoxy resin, bisphenol A diglycidyl ether epoxy resin, bisphenol F epoxy resin, bisphenol F diglycidyl ether epoxy resin, bisphenol S diglycidyl ether epoxy resin, glycidyl ether epoxy resin, cresol Novolak type epoxy resin, aromatic polyfunctional epoxy resin, aliphatic epoxy resin, aliphatic polyfunctional epoxy resin, alicyclic epoxy resin, polyfunctional Epoxy resins such as cyclic epoxy resins; resins having a triazine ring such as urea (urea) resins and melamine resins; unsaturated polyester resins; maleimide resins such as bismaleimide compounds; polyurethane resins; diallyl phthalate resins; silicone resins; Polyamide resin; Polyamide imide resin; Cyanate ester resin such as cyanate resin such as benzocyclobutene resin, novolac type cyanate resin, bisphenol A type cyanate resin, bisphenol E type cyanate resin, tetramethyl bisphenol F type cyanate resin It can be mentioned. Moreover, in the thermosetting resin, one of these may be used alone, or two or more having different weight average molecular weights may be used in combination, and one or two or more of them may be used. You may use together with a polymer.

  Among them, as the thermosetting resin, those containing an epoxy resin are preferably used. Thereby, the photosensitive resin composition with a small cure shrinkage rate can be obtained. Moreover, the photosensitive resin composition which can form the organic insulating layer 21 with a favorable mechanical characteristic is obtained.

  Examples of the epoxy resin include polyfunctional epoxy resins in which two or more epoxy groups are contained in one molecule. These may be used alone or in combination of two or more. By using such a polyfunctional epoxy resin, the film physical properties and processability of the photosensitive resin layer 210 can be enhanced.

Further, as the epoxy resin, a trifunctional or higher polyfunctional epoxy resin may be used.
The thermosetting resin is, in particular, phenol novolac epoxy resin, cresol novolac epoxy resin, triphenylmethane epoxy resin, dicyclopentadiene epoxy resin, bisphenol A epoxy resin, and tetramethyl bisphenol F epoxy resin It is preferable to include one or more epoxy resins selected from the group consisting of, and more preferable to include novolac epoxy resins. Since such a thermosetting resin is an epoxy resin which is polyfunctional and is composed of an aromatic compound, it is possible to obtain an organic insulating layer 21 which is excellent in curability, high in heat resistance, and relatively low in thermal expansion coefficient.

  The content of the thermosetting resin is not particularly limited, but is preferably about 40 to 80% by mass, and more preferably about 45 to 75% by mass, based on the total solid content of the photosensitive resin composition. It is more preferable that the amount is about 70% by mass. By setting the content of the thermosetting resin within the above range, the patterning properties of the photosensitive resin composition can be enhanced, and the heat resistance and mechanical strength of the organic insulating layer 21 can be sufficiently enhanced.

  In addition, solid content of the photosensitive resin composition refers to the non volatile matter in the photosensitive resin composition, and refers to the remainder except volatile components, such as water and a solvent. Moreover, in the present embodiment, the content of the photosensitive resin composition with respect to the entire solid content refers to the content with respect to the entire solid content excluding the solvent in the photosensitive resin composition when the solvent is contained.

  In addition to the thermosetting resin, the photosensitive resin composition may contain a thermoplastic resin. Thereby, the moldability of the photosensitive resin composition can be further enhanced.

  Examples of the thermoplastic resin include acrylic resins, polyamide resins (eg, nylon etc.), thermoplastic urethane resins, polyolefin resins (eg polyethylene, polypropylene etc.), polycarbonate, polyester resins (eg polyethylene terephthalate, polybutylene) Terephthalate etc.), polyacetal, polyphenylene sulfide, polyetheretherketone, liquid crystal polymer, fluorocarbon resin (eg polytetrafluoroethylene, polyvinylidene fluoride etc.), modified polyphenylene ether, polysulfone, polyether sulfone, polyarylate, polyamide imide, poly Ether imide, thermoplastic polyimide, etc. are mentioned. In the photosensitive resin composition, one of these may be used alone, or two or more having different weight average molecular weights may be used in combination, and one or more of them may be used. You may use together with a prepolymer.

  The thermosetting resin preferably contains a solid resin at normal temperature (25 ° C.), and more preferably contains both a resin that is solid at normal temperature and a resin that is liquid at normal temperature (such as liquid epoxy resin described later) . The photosensitive resin composition containing such a thermosetting resin is a cured product that has good embeddability of the semiconductor chip 23 etc. in the photosensitive resin film 20, improvement in tack (stickiness) of the photosensitive resin film 20, and the like. The mechanical strength of a certain organic insulating layer 21 can be compatible. As a result, a highly reliable organic insulating layer 21 is obtained.

(Liquid epoxy resin)
The photosensitive resin composition may contain, as necessary, a liquid epoxy resin which is liquid at normal temperature. Since the liquid epoxy resin functions as a film forming aid (film forming agent), the brittleness of the organic insulating layer 21 can be suppressed.

  As a liquid epoxy resin, what is different from the thermosetting resin mentioned above can be used. Specifically, an epoxy compound which has two or more epoxy groups in the molecule and which is liquid at room temperature 25 ° C. can be used. By using such a liquid epoxy resin, the brittleness of the organic insulating layer 21 can be particularly suppressed. The viscosity of this liquid epoxy resin at 25 ° C. is, for example, 1 to 8000 mPa · s, preferably 5 to 1,500 mPa · s, and more preferably 10 to 1,400 mPa · s.

  As such a liquid epoxy resin, for example, one or more selected from the group consisting of bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, alkyl diglycidyl ether and alicyclic epoxy may be mentioned, It is used 1 type or in combination of 2 or more types. Among these, alkyl diglycidyl ether is preferably used from the viewpoint of reducing cracks after development.

  The epoxy equivalent of the liquid epoxy resin is preferably 100 to 200 g / eq, more preferably 105 to 180 g / eq, and still more preferably 110 to 170 g / eq. Thereby, the brittleness of the organic insulating layer 21 can be particularly suppressed.

  The content of the liquid epoxy resin is not particularly limited, but is preferably about 5 to 40% by mass, and more preferably about 10 to 35% by mass, based on the total solid content of the photosensitive resin composition. More preferably, it is about 30% by mass. Thereby, the physical properties can be balanced while suppressing the brittleness of the organic insulating layer 21.

  The amount of liquid epoxy resin is preferably about 5 to 150 parts by mass, more preferably about 10 to 100 parts by mass, and more preferably 15 to 80 parts by mass with respect to 100 parts by mass of the solid resin at normal temperature. More preferably, When the ratio of the liquid resin is below the lower limit value, the embedding property of the semiconductor chip 23 in the photosensitive resin film 20 may be reduced, or the stability of the photosensitive resin film 20 may be reduced. On the other hand, when the ratio of the liquid resin exceeds the upper limit value, the tack of the photosensitive resin film 20 may be deteriorated, or the mechanical strength of the organic insulating layer 21 which is a cured product may be reduced.

(Phenol resin)
The photosensitive resin composition contains a phenolic resin that can react with the thermosetting resin. The phenol resin can accelerate the polymerization reaction of a thermosetting resin as a curing agent, for example, and can improve the film physical properties and processability of the organic insulating layer 21.

  As a phenol resin, a novolak-type phenol resin, a resol-type phenol resin, a trisphenylmethane-type phenol resin, an aryl alkylene type phenol resin etc. are mentioned, for example. Among these, novolac type phenol resins are particularly preferably used. As a result, a photosensitive resin layer 210 having good curability and good development characteristics can be obtained.

  Moreover, as a phenol resin, Preferably, the polyfunctional phenol resin which has a 2 or more phenolic hydroxyl group in a molecule | numerator can be used. Thereby, the coefficient of thermal expansion of the hardened | cured material of the photosensitive resin composition can be restrained.

  The addition amount of the phenol resin 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 or less, with respect to 100 parts by mass of the resin More preferably, it is from 80 parts by weight to 80 parts by weight. By setting the addition amount of the phenol resin in the above range, the organic insulating layer 21 having high heat resistance and a relatively low thermal expansion coefficient can be obtained.

  Here, for the photosensitive resin composition, a phenol resin having a dimer content of 3% by mass or less is used. When such a phenolic resin cures and shrinks a photosensitive resin composition, it contributes so as to suppress the shrinkage rate to a low level. This is considered to be due to the fact that the dimer volatilizes relatively during the multimer, so that it volatilizes at the time of curing and the volume of the component decreases. That is, even if the thickness of the photosensitive resin layer 210 containing a phenolic resin as described above is partially different, the difference in the amount of contraction of each part is suppressed to a small value. For this reason, even if the photosensitive resin layer 210 including portions having different thicknesses is finally cured, it becomes difficult for a level difference to be generated on the surface of the cured film. For example, when the photosensitive resin layer 210 is formed so as to embed the semiconductor chip 23, a step is hardly generated between the part covering the upper surface of the semiconductor chip 23 and the part not covering the upper surface. As a result, the photosensitive resin composition (photosensitive resin film 20) which can form the organic insulating layer 21 (resin film) with favorable surface flatness is obtained.

  Thus, the organic insulating layer 21 having a good surface flatness can suppress the occurrence of distortion in the upper wiring layer 25 when, for example, the upper wiring layer 25 is stacked thereon. For this reason, it is possible to avoid that the electric conductivity of the upper layer wiring layer 25 is lowered or the adhesion between the organic insulating layer 21 and the upper layer wiring layer 25 is lowered.

  Moreover, such a photosensitive resin composition becomes what has high heat resistance (for example, glass transition temperature etc.) of hardened | cured material. Therefore, the organic insulating layer 21 having good heat resistance can be obtained.

  In addition, when content of a dimer exceeds the said upper limit, the cure shrinkage rate of the photosensitive resin composition will become large. For this reason, when the thickness of the photosensitive resin layer 210 is partially different, the difference in the amount of contraction of each part becomes large, and a step is generated on the surface of the cured film. In addition, the heat resistance of the cured product may not be sufficiently improved.

  The content of the dimer is preferably 2.5% by mass or less, more preferably 2% by mass or less.

  On the other hand, the lower limit of the content of the dimer is not particularly limited, but is preferably 0.05% by mass or more, and more preferably 0.10% by mass or more. Thereby, in the preparation of the photosensitive resin composition, excessive purification is not required, and therefore an increase in manufacturing cost can be suppressed. In addition, it is possible to avoid the decrease in the balance of the molecular weight distribution and to suppress the decrease in the physical properties of the organic insulating layer 21 (resin film).

  Moreover, the phenol resin whose content rate of a trimer is preferably 3 mass% or less is used for the photosensitive resin composition. When such a phenolic resin cures and shrinks the photosensitive resin composition, it contributes to further reduce the shrinkage rate. This is considered to be due to the fact that the trimer is likely to volatilize next to the dimer among the multimers, so that it is likely to volatilize during curing and the partial volume thereof is reduced. For this reason, even if the photosensitive resin layer 210 including portions having different thicknesses is finally cured, it becomes difficult for a level difference to be generated on the surface of the cured film.

  In addition, when content of a trimer exceeds the said upper limit, although it changes somewhat with content of a dimer, there exists a possibility that the cure shrinkage rate of the photosensitive resin composition may become large. For this reason, when the thickness of the photosensitive resin layer 210 is partially different, the difference in the amount of contraction of each part becomes large, and there is a possibility that a level difference may occur on the surface of the cured film.

  Also, the content of the trimer is preferably 2.5% by mass or less, more preferably 2% by mass or less.

  On the other hand, the lower limit of the content of the trimer is not particularly limited, but is preferably 0.05% by mass or more, and more preferably 0.10% by mass or more. Thereby, in the preparation of the photosensitive resin composition, excessive purification is not required, and therefore an increase in manufacturing cost can be suppressed. In addition, it is possible to avoid the decrease in the balance of the molecular weight distribution and to suppress the decrease in the physical properties of the organic insulating layer 21 (resin film).

  In addition, content of a dimer and a trimer can be calculated | required by the area method which expresses the area of the dimer and the trimer with respect to the whole area of the molecular weight distribution by gel permeation chromatography (GPC) by percentage, respectively. .

  In addition, the content of the dimer and the trimer can be adjusted, for example, by subjecting the photosensitive resin composition to a process of removing these low molecular weight components. As such treatment, for example, a molecular weight fractionation method by GPC, reprecipitation method, Soxhlet extraction method or the like is used. Also, the same process or different processes may be performed multiple times.

  In addition, the dimer in the present specification is a dinuclear body of a low molecular weight component contained in a phenol resin, and is a phenol containing two benzene rings in one molecule, and is a trimer in the present specification and Is a trinuclear body of low molecular weight components contained in a phenol resin, and is a phenol containing three benzene rings in one molecule.

  The weight average molecular weight of the phenol resin is not particularly limited, but is preferably about 1,000 to 20,000, more preferably about 3,000 to 10,000, 4,500 to 8, More preferably, it is about 000. Thereby, the cure shrinkage rate of the photosensitive resin composition can be kept relatively small, and a photosensitive resin composition having a good melt viscosity can be obtained.

  That is, if the weight average molecular weight is below the lower limit value, the cure shrinkage may increase depending on the content of the dimer or trimer. In addition, the heat resistance and mechanical properties of the cured product may be reduced. On the other hand, when the weight average molecular weight exceeds the above upper limit value, the melt viscosity becomes high, and for example, the embeddability of the semiconductor chip 23 in the photosensitive resin film 20 may be reduced.

  In addition, the weight average molecular weight of a phenol resin can be calculated | required as a weight average molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC).

(Photosensitizer)
As a photosensitizer, a photo-acid generator can be used, for example. As a result, a chemically amplified photosensitive resin composition using an acid generated from the photoacid generator as a catalyst can be obtained. Such a chemically amplified photosensitive resin composition has high sensitivity, and therefore, finer patterning can be realized at high throughput.

  As a photo-acid generator, what generate | occur | produces an acid by irradiation of active rays, such as an ultraviolet-ray, is mentioned, Specifically, an onium salt compound is mentioned. More specifically, iodonium salts such as diazonium salts and diaryliodonium salts, sulfonium salts such as triarylsulfonium salts, triarylbirylium salts, benzyl pyridinium thiocyanate, dialkyl phenacyl sulfonium salts, dialkyl hydroxyphenyl phosphonium salts, etc. Cationic photopolymerization initiators and the like.

  The photosensitizer is preferably one that does not generate hydrogen fluoride due to decomposition, such as methide salt type and borate salt type, in consideration of contact of the photosensitive resin composition with metal.

  The addition amount of the photosensitizer is not particularly limited, but is preferably about 0.3 to 5% by mass, and about 0.5 to 4.5% by mass of the total solid content of the photosensitive resin composition. It is more preferable that it is 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 layer 210 can be enhanced, and the long-term storage property of the photosensitive resin composition can be improved.

  The photosensitizer may be one which imparts negative photosensitivity to the photosensitive resin composition, or may be one which imparts positive photosensitivity, but an opening with a high aspect ratio. In view of the point that it can be formed with high accuracy, etc., it is preferable to be negative.

(Coupling agent)
The photosensitive resin composition may further contain a coupling agent (adhesion aid). The photosensitive resin composition having a coupling agent enables formation of a resin film having good adhesion to the inorganic material. Thereby, for example, the organic insulating layer 21 having excellent adhesion to the through wiring 22 and the semiconductor chip 23 is obtained.

  As a coupling agent, a coupling agent containing an amino group, an epoxy group, an acryl group, a methacryl group, a mercapto group, a vinyl group, a ureido group, a sulfide group, an acid anhydride etc. as a functional group is mentioned. These may be used alone or in combination of two or more.

  As the amino group-containing coupling agent, for example, bis (2-hydroxyethyl) -3-aminopropyltriethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldiethoxysilane , Γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyl Examples include methyl dimethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, N-phenyl-γ-amino-propyltrimethoxysilane and the like.

  As the epoxy group-containing coupling agent, for example, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidyl propyl Trimethoxysilane etc. are mentioned.

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

  As a mercapto group containing coupling agent, 3-mercapto propyl trimethoxysilane etc. are mentioned, for example.

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

  As a ureido group containing coupling agent, 3-ureido propyl triethoxysilane etc. are mentioned, for example.

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

  In addition, a coupling agent containing an acid anhydride as a functional group is preferably used. The coupling agent containing an acid anhydride as a functional group (hereinafter referred to as “an acid anhydride-containing coupling agent”) is a cation (a metal cation) as the acid anhydride which is a functional group dissolves the inorganic oxide. Coordinate bond).

  On the other hand, the alkoxy group contained in the acid anhydride-containing coupling agent is hydrolyzed to become, for example, silanol. This silanol dehydrates and condenses with the surface hydroxyl group of the inorganic material, and bonds strongly with the surface of the inorganic material by covalent bonding.

  Based on these bonding mechanisms, a photosensitive resin composition having good adhesion to inorganic materials can be obtained.

  As the acid anhydride-containing coupling agent, particularly, alkoxysilylalkylcarboxylic acid anhydride is preferably used. According to such a coupling agent, a photosensitive resin composition having better adhesion to the inorganic material, good sensitivity, and excellent patternability can be obtained.

  Specific examples of alkoxysilylalkylcarboxylic acid anhydrides include 3-trimethoxysilylpropylsuccinic anhydride, 3-triethoxysilylsilylsuccinic anhydride, 3-dimethylmethoxysilylpropylsuccinic anhydride, 3-dimethyl Succinic anhydride such as ethoxysilyl propyl succinic anhydride, 3-trimethoxysilyl propyl cyclohexyl dicarboxylic acid anhydride, 3-triethoxy silyl propyl cyclohexyl dicarboxylic acid anhydride, 3-dimethyl methoxy silyl propyl cyclohexyl dicarboxylic acid anhydride Dicarboxylic acid anhydrides such as 3-dimethylethoxysilylpropylcyclohexyl dicarboxylic acid anhydride, 3-trimethoxysilylpropylphthalic anhydride, 3-triethoxysilylpropylphthalic anhydride, 3-dimethyenic anhydride Methoxysilylpropyl phthalic anhydride, phthalic acid anhydride, such as 3-dimethyl-ethoxysilylpropyl phthalic anhydride, and the like. These may be used alone or in combination of two or more.

  Among these, succinic anhydride is preferably used, and in particular, 3-trimethoxysilylpropyl succinic anhydride is more preferably used. According to such a coupling agent, the molecular length and the molecular structure are optimized, and thus the adhesion and the patterning property described above become better.

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

  The addition amount of the coupling agent is not particularly limited, but is preferably about 0.3 to 5% by mass, and about 0.5 to 4.5% by mass of the total solid content of the photosensitive resin composition. Is more preferable, and about 1 to 4% by mass is more preferable. By setting the addition amount of the coupling agent in the above range, the organic insulating layer 21 having particularly good adhesion to an inorganic material such as the through wiring 22 or the semiconductor chip 23 can be obtained. Thereby, the insulation of the organic insulating layer 21 is maintained for a long period of time, which contributes to the realization of the highly reliable semiconductor device 1.

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

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

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

(solvent)
The photosensitive resin composition may contain a solvent. Any solvent can be used without particular limitation as long as it can dissolve the components of the photosensitive resin composition and does not react with the 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 And propylene carbonate, ethylene glycol diacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, butyl acetate and the like. These may be used alone or in combination of two or more.

<Photosensitive resin varnish>
The photosensitive resin composition according to the present embodiment may be in the form of a varnish.

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

  The solid content concentration in the varnish-like photosensitive resin composition is not particularly limited, but is preferably about 20 to 80% by mass. A varnish-like photosensitive resin composition having such a solid content concentration has good flowability that easily penetrates into a narrow gap and is difficult to cause film breakage because the viscosity is optimized. It becomes.

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

  As described above, the photosensitive resin film may be one obtained by filming the photosensitive resin composition, or may be one obtained by coating the photosensitive resin composition on a carrier film.

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

  Specifically, after a varnish-like photosensitive resin composition is coated on a carrier film using various coater devices, a method of drying this is applied, and a varnish-like photosensitive resin composition is used as a carrier using a spray device. After spraying on a film, the method of drying this, etc. are mentioned. Among these, after applying a varnish-like photosensitive resin composition on a carrier film using various coater apparatuses, such as a bar coater, a die coater, a lip coater, the method of drying this is preferable. Thereby, the photosensitive resin film which does not have a void and has the thickness of a uniform photosensitive resin layer can be manufactured efficiently.

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

  The drying conditions include, for example, 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 viewpoint of handleability, surface cleanliness and the like. At this time, the carrier film may be in the form of a roll that can be wound, or may be in the form of a sheet.

  As a constituent material of a carrier film, a resin material, a metal material, etc. are mentioned, for example. Among these, as the resin material, for example, polyolefins such as polyethylene and polypropylene, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polycarbonates, silicones, fluorine resins, polyimide resins and the like can be mentioned. Moreover, as a metal material, copper or copper alloy, aluminum or aluminum alloy, iron or iron alloy etc. are mentioned, for example.

  Among these, a carrier film containing polyethylene terephthalate which is a kind of polyester is preferably used. Such a carrier film has relatively good peelability while suitably supporting the photosensitive resin film.

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

  The constituent material of the cover film is appropriately selected from those listed as constituent materials of the carrier film, but a cover film containing polyethylene terephthalate, which is a type of polyester, is preferably used from the viewpoints of protection and releasability.

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

  Such a semiconductor device is highly reliable because it has a protective film excellent in chemical resistance. Therefore, high reliability is 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 the electronic device according to the present embodiment includes such a semiconductor device. Equipment, computer for vehicle control, in-vehicle equipment such as a car navigation system, etc. may be mentioned.

  Although the present invention has been described above based on the illustrated embodiments, the present invention is not limited to these.

  For example, the photosensitive resin composition and photosensitive resin film of the present invention can be used for buffer coats for semiconductors, rewiring layers, α-ray preventing films, interlayer insulating films, etc. in addition to the organic insulating layers as in the above embodiment It is applicable. Since all of these are used as permanent films, high mechanical properties possessed by the cured product of the photosensitive resin composition of the present invention act effectively.

  Moreover, the photosensitive resin composition and the photosensitive resin film of the present invention are not only semiconductor devices, but also display devices such as structure forming materials of MEMS (Micro Electro Mechanical Systems) and various sensors, liquid crystal display devices, and organic EL devices. The present invention is also applicable to the structure forming material of

Next, specific examples of the present invention will be described.
1. Preparation of test piece for evaluation of cure shrinkage (Example 1)
First, the raw materials shown in Tables 1 and 2 were dissolved in benzyl alcohol to prepare a solution.

  Next, the prepared solution was filtered with a polypropylene filter having a pore size of 0.2 μm to obtain a varnish-like photosensitive resin composition. The photosensitive resin composition was negative, and the solid content was 50% by mass.

  Next, a 38 μm thick PET (polyethylene terephthalate) film was prepared, and this was used as a carrier film to apply a photosensitive resin composition. A bar coater was used as the coating apparatus. After the application, it was dried at 120 ° C. for 10 minutes to obtain a photosensitive resin film having an average thickness of 150 μm.

  Next, a 38 μm-thick PET film was prepared as a cover film, and this was attached to a photosensitive resin film. Thereby, a laminated film was obtained.

  Next, a test piece in which a silicon chip and a copper pillar were disposed on an organic substrate was prepared. The silicon chip was a 1 cm square and had a thickness of 170 μm. The height of the copper pillar was 190 μm.

  Subsequently, the cover film was peeled off from the laminated film of each example and each comparative example to expose the photosensitive resin film, and the photosensitive resin film was superposed on the silicon chip and the copper pillar.

  Next, the photosensitive resin film and the test piece were pressurized at 100 ° C. and 0.4 MPa for 30 seconds using a vacuum pressure type laminator, and then the carrier film was peeled from the photosensitive resin film. Thereby, the photosensitive resin film was left.

Next, the test piece was subjected to a pre-exposure heat treatment at 70 ° C. for 2 minutes in the atmosphere on a hot plate.
Next, the exposure treatment was applied to the test piece at 300 mJ / cm ² .

Next, the exposed test piece was subjected to a post-exposure heat treatment at 70 ° C. for 5 minutes in the atmosphere on a hot plate.
Next, the test piece was subjected to development for 90 seconds using PGMEA (propylene glycol monomethyl ether acetate) as a developer in a spray developing device.
Next, the film was heated at 200 ° C. for 90 minutes to obtain a cured film.

  As described above, a test piece for curing shrinkage evaluation provided with an organic substrate, a silicon chip, and a cured film (resin film) was obtained. In addition, FIG. 7 is a longitudinal cross-sectional view which shows typically the structure of the test piece for hardening shrinkage evaluation. The test piece 7 for curing shrinkage evaluation shown in FIG. 7 has an organic substrate 71, a silicon chip 72, a copper pillar 73 and a cured film 74. The silicon chip 72 and the copper pillar 73 are embedded in the cured film 74.

(Examples 2 to 9)
A test piece for evaluation of curing shrinkage was obtained in the same manner as in Experimental Example 1 except that the configuration of the photosensitive resin film was changed as shown in Tables 1 to 3. In addition, in the change of molecular weight distribution, the molecular weight fractionation method by GPC was used.

(Comparative Examples 1 to 5)
A test piece for evaluation of curing shrinkage was obtained in the same manner as in Experimental Example 1 except that the configuration of the photosensitive resin film was changed as shown in Tables 1 to 3. In addition, in the change of molecular weight distribution, the molecular weight fractionation method by GPC was used.

2. Evaluation of Molecular Weight Distribution of Photosensitive Resin Composition First, the photosensitive resin compositions of Examples and Comparative Examples were subjected to molecular weight distribution measurement by gel permeation chromatography (GPC).

  Then, the content of the dimer and the weight average molecular weight were calculated. The calculation results are shown in Tables 2 and 3.

3. Evaluation of Test Pieces for Evaluation of Curing Shrinkage First, the test pieces for evaluating curing shrinkage obtained in the respective Examples and Comparative Examples were cut, and the cross section was observed with an electron microscope.

  Next, a distance t1 from the surface of the organic substrate to the surface of the cured film 74 in the portion where the copper pillar 73 exists and a distance t2 from the surface of the organic substrate 71 to the surface of the cured film 74 in the portion where neither the silicon chip 72 nor the copper pillar 73 exists And were measured.

  Next, the difference in distance (t1−t2), that is, the height of the step on the surface of the cured film 74 was calculated. The calculation results are shown in Tables 2 and 3.

4. Evaluation of Cured Product of Photosensitive Resin Composition First, with respect to the cured product of the photosensitive resin composition of each example and each comparative example, the glass transition temperature was measured using a thermal mechanical analyzer (TMA).
The measurement results are shown in Tables 2 and 3.

  As apparent from Tables 2 and 3, it was found that the height of the step formed on the surface of the cured film was sufficiently low in the test pieces obtained in each example. That is, it was recognized that the test piece obtained in each example had high surface flatness of the cured film.

DESCRIPTION OF SYMBOLS 1 semiconductor device 2 through electrode substrate 3 semiconductor package 7 test piece 20 for curing shrinkage evaluation photosensitive resin film 21 organic insulating layer 22 through wiring 23 semiconductor chip 24 lower layer wiring layer 25 upper layer wiring layer 26 solder bump 31 package substrate 32 semiconductor chip 33 Bonding wire 34 sealing layer 35 solder bump 41 mask 42 opening 71 organic substrate 72 silicon chip 73 copper pillar 74 cured film 202 substrate 210 photosensitive resin layer

Claims (8)

Thermosetting resin,
A phenolic resin capable of reacting with the thermosetting resin;
A photosensitizer,
Including
The photosensitive resin composition characterized in that the content of the dimer in the phenolic resin is 3% by mass or less.   The photosensitive resin composition according to claim 1, further comprising an adhesion promoter.   The photosensitive resin composition according to claim 1, wherein the thermosetting resin is an epoxy resin.   A photosensitive resin film comprising the photosensitive resin composition according to any one of claims 1 to 3.   The photosensitive resin film according to claim 4 having a thickness of 100 to 1000 μm. A semiconductor chip,
The resin film containing the hardened | cured material of the photosensitive resin composition of any one of the Claims 1 thru | or 3 provided at least on the surface of the said semiconductor chip,
A semiconductor device comprising:   The semiconductor device according to claim 6, wherein the resin film is provided to embed the semiconductor chip.   An electronic apparatus comprising the semiconductor device according to claim 6.

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