TW201623533A - Photosensitive adhesive composition and semiconductor device - Google Patents

Abstract

A photosensitive adhesive composition of the present invention is used for bonding a semiconductor element and a member to be bonded together. The photosensitive adhesive composition includes an alkali soluble resin (A), a photoacid generator (B), an epoxy compound (C) and a phenol compound (D) having a melting point of 50 to 150 DEG C. By using a cured product of the photosensitive adhesive composition of the present invention as an adhesive layer bonding the semiconductor elements together, it is possible to reduce generation of bubbles (voids) at an interface between the semiconductor element and the adhesive layer. Further, even if the bubbles generate at the interface, it is also possible to remove the generated bubbles. As a result, an adhesive property (adhesion property) between the semiconductor elements can be improved.

Description

Photosensitive adhesive composition and semiconductor device

The present invention relates to a photosensitive adhesive composition and a semiconductor device.

According to a prediction called Moore's Law, the semiconductor device has been increasing year by year. However, in recent years, there has been a case where the structure formed in the semiconductor element is close to the physical limit, and the speed of the high integration of the semiconductor device is continuously slowed down. Therefore, there has been proposed a method of increasing the apparent bulk of a semiconductor device by laminating a plurality of semiconductor elements without increasing the density of one semiconductor element.

The laminate of a plurality of semiconductor elements is carried out, for example, by connecting the semiconductor elements (defects) to each other via a film-like adhesive (for example, see Patent Document 1).

Further, recently, for example, in the spread of mobile devices, in addition to the high integration of semiconductor devices, it is desirable to reduce the size and thickness of semiconductor devices. Therefore, in the semiconductor device in which a plurality of semiconductor elements are stacked as described above, it is possible to promote the thinning of each semiconductor element.

The thin-walled semiconductor element can be formed by etching a wafer to be a semiconductor element to be thinned. Further, in order to prevent breakage of the wafer, the etching is performed in a state where the wafer is followed by a film-like adhesive.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-051970

However, the present inventors have found that when etching is performed as described above, when the etching time is long, bubbles (voids) are generated at the interface between the wafer and the film-like adhesive. When such a problem occurs, when the semiconductor elements are connected to each other via the film-like adhesive after the wafer is singulated, the adhesion (adhesiveness) of the semiconductor elements is lowered by the bubbles. As a result, there is a case where the reliability of the semiconductor device is lowered.

An object of the present invention is to provide a photosensitive adhesive composition capable of improving the adhesion (adhesiveness) of a semiconductor element, and a laminated semiconductor including a cured product of the photosensitive adhesive composition and a semiconductor element. A semiconductor device having high reliability of components.

Such an object is achieved by the present invention of the following (1) to (11).

(1) A photosensitive adhesive composition for bonding a semiconductor element and a member to be joined, comprising: (A) an alkali-soluble resin, (B) a photoacid generator, (C) epoxy The compound and (D) a phenol compound having a melting point of 50 to 150 °C.

(2) The photosensitive adhesive composition according to the above (1), wherein the (D) phenol compound contains at least one of a phenol compound having a substituent containing an aliphatic hydrocarbon group and a phenol compound having a plurality of phenol skeletons. By.

(3) The photosensitive adhesive composition according to the above (2), wherein the phenol compound having a substituent containing an aliphatic hydrocarbon group has a hydroxyl equivalent of from 150 to 250 g/eq.

(4) The photosensitive adhesive composition according to the above (1), wherein the (A) alkali-soluble resin contains a cyclic olefin resin.

(5) The photosensitive adhesive composition according to the above (4), wherein the cyclic olefin resin comprises a lowering An olefinic resin.

(6) The photosensitive adhesive composition according to the above (1), wherein the (A) alkali-soluble resin has a linear substituent having 2 to 30 carbon atoms.

(7) The photosensitive adhesive composition according to the above (6), wherein the linear substituent comprises an alkyl ether structure.

(8) The photosensitive adhesive composition according to the above (6), wherein the linear substituent is a group represented by the following formula (1).

(In the formula (1), z is an integer of 1 or more and 10 or less)

(A) The photosensitive adhesive composition according to the above (6), wherein the (A) alkali-soluble resin contains 20 to 60 mol% of a repeating unit having the linear substituent.

(10) The photosensitive adhesive composition according to the above (1), wherein the (C) epoxy compound has two or more glycidyl groups.

(11) A semiconductor device comprising a laminated semiconductor device, wherein the stacked semiconductor device has a plurality of semiconductor elements, and the (1) is provided between the semiconductor elements and joined to each other (1) The cured product of the photosensitive adhesive composition according to any one of (10).

By using the cured product of the photosensitive adhesive composition of the present invention as an adhesive layer next to the semiconductor elements, bubbles (voids) can be reduced at the interface between the semiconductor element and the adhesive layer, and even if bubbles are generated at the interface, The resulting bubbles can be removed. Therefore, the adhesion (adhesiveness) of the semiconductor elements can be improved.

Moreover, according to the present invention, it is possible to obtain a semiconductor device having a high reliability in a laminated semiconductor device having high adhesion between semiconductor elements.

4‧‧‧ mask

10‧‧‧Semiconductor device

20‧‧‧Semiconductor wafer

21, 22‧‧‧ single film

30‧‧‧Package substrate

31‧‧‧ core substrate

32‧‧‧Insulation

33‧‧‧Solder layer

34‧‧‧Wiring

35‧‧‧through holes

50‧‧‧Mold Department

70‧‧‧bonding line

80‧‧‧ solder balls

90‧‧‧Back grinding film

100‧‧‧Cutting-die film

100a‧‧‧Cut film

100b‧‧‧die film

101, 601‧‧‧Next layer

110‧‧‧Cutting Blade

120‧‧‧Joining device

121‧‧‧ nozzle

200‧‧‧ Wafer laminate

201‧‧‧ wafer

601a‧‧·coating film

601b‧‧‧ openings

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view showing an example of a semiconductor device of the present invention.

2(a) to (e) are views for explaining a method of manufacturing the semiconductor device shown in Fig. 1.

3(f) to (i2) are diagrams for explaining a method of manufacturing the semiconductor device shown in Fig. 1.

4(j1) to (L2) are diagrams for explaining a method of manufacturing the semiconductor device shown in Fig. 1.

5(a) to (d) are views for explaining a method of manufacturing the semiconductor device shown in Fig. 1.

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

<semiconductor device>

First, an example of a semiconductor device of the present invention will be described.

Fig. 1 is a cross-sectional view showing an example of a semiconductor device of the present invention. The semiconductor device 10 shown in FIG. 1 is an example of a ball grid array (BGA) type semiconductor package. The semiconductor device 10 includes a plurality of stacked semiconductor wafers 20 (semiconductor elements), an adhesive layer 601 for bonding the semiconductor wafers 20 to each other, a package substrate 30 for supporting the semiconductor wafers 20, and a subsequent layer 101 of the semiconductor wafers 20 and the package substrates 30. The mold portion 50 of the semiconductor wafer 20 and the solder balls 80 disposed under the package substrate 30 are sealed. Hereinafter, the configuration of each unit will be described in detail.

The semiconductor wafer 20 can be any kind of component, for example, a memory element such as a (NAND, Not AND) flash memory, a DRAM (Dynamic Random Access Memory), such as an integrated circuit. (IC, Integrated Circuit), integrated circuit components such as LSI (Large Scale Integration).

The constituent material of the semiconductor wafer 20 is not particularly limited, and examples thereof include single crystal materials such as ruthenium, ruthenium carbide, and compound semiconductor, polycrystalline materials, and amorphous materials.

The plurality of semiconductor wafers 20 are slightly shifted from each other in the in-plane direction and laminated one by one, thereby constituting the wafer laminate 200 (layered semiconductor device). Again, semi-guided The bulk wafers 20 are followed by each other via the bonding layer 601. Next, a layer 601 is also disposed on the upper surface of the wafer laminate 200. Further, the adhesive layer 601 contains a cured product (a photosensitive adhesive composition after curing) of the photosensitive adhesive composition of the present invention. Further, the photosensitive adhesive composition will be described in detail below.

The package substrate 30 shown in FIG. 1 includes an additional substrate of the core substrate 31, the insulating layer 32, the solder resist layer 33, the wiring 34, and the via holes 35.

The core substrate 31 is a substrate that supports the package substrate 30, and is, for example, a composite material filled with a resin material in a glass cloth.

Further, the insulating layer 32 is an interlayer insulating layer that insulates the wirings 34 from each other or the wiring 34 and the via holes 35, and is made of, for example, a resin material. Further, the solder resist layer 33 is a surface protective layer for protecting the wiring formed on the outermost surface of the package substrate 30, and is made of, for example, a resin material.

Moreover, each of the wiring 34 and the via hole 35 is a transmission path of an electric signal, and includes a metal material such as a single substance or an alloy of Au, Ag, Cu, Al, or Ni.

The solder ball 80 is electrically connected to the wiring 34, and is fused to an external circuit to function as an electrode for connecting the wiring 34 to another circuit.

The wafer laminate 200 in which a plurality of semiconductor wafers 20 are laminated is placed on the upper surface of the package substrate 30. The wafer laminate 200 and the package substrate 30 are followed by the adhesion layer 101.

Further, a part of the wiring 34 of the package substrate 30 is exposed on the upper surface of the package substrate 30 to constitute an exposed portion. The exposed portion and the electrode portion of each semiconductor wafer 20 are connected by a bonding wire 70.

The mold portion 50 shown in FIG. 1 is configured to cover the side surface and the upper surface of the wafer laminate 200 and cover the entire upper surface of the package substrate 30. borrow Thus, the wafer laminate 200 can be protected from the external environment. The mold portion 50 includes various resin materials such as an epoxy resin and a phenol resin.

<Method of Manufacturing Semiconductor Device>

Next, a method of manufacturing the semiconductor device 10 will be described.

2 to 5 are views for explaining a method of manufacturing the semiconductor device shown in Fig. 1, respectively. In the following description, for convenience of explanation, the upper side of FIGS. 2 to 5 will be referred to as "upper" and the lower side will be referred to as "lower".

The manufacturing method of the semiconductor device 10 includes a coating step of applying a liquid containing a photosensitive adhesive composition onto a wafer (semiconductor substrate) to obtain a coating film; and an exposure step obtained by the alignment The coating film is exposed; the developing step is to pattern the coating film by development; the processing step is to perform etching treatment and ashing treatment on the wafer provided with the coating film; and the back grinding step is performed on the wafer Grinding on the back side; cutting step of dicing the wafer into a plurality of semiconductor wafers; and mounting step of picking up the semiconductor wafer and mounting it on the package substrate, picking up another semiconductor wafer and crimping it Previously mounted semiconductor wafer (joined member). Hereinafter, each step will be described in order.

[1] Coating step

First, a wafer 201 for cutting out the semiconductor wafer 20 (see FIG. 2(a)) is prepared, and a liquid containing a photosensitive adhesive composition is applied thereon (on one side). Thereby, as shown in FIG. 2(b), the coating film 601a is formed on the wafer 201. Further, on the wafer 201, a semiconductor circuit, an electrode pad, or the like is formed in advance in correspondence with each of the semiconductor wafers 20. That is, the wafer 201 is provided to a so-called pre-step of the semiconductor fabrication step. Therefore, by wafer 201 is cut and singulated in the later-described steps, and a plurality of semiconductor wafers 20 can be cut out from the wafer 201.

The coating method is not particularly limited, and examples thereof include a spin coating method, a spray coating method, an inkjet method, a roll coating method, and a printing method.

The liquid (liquid film) containing the photosensitive adhesive composition to be applied may be heated and dried as needed. In this case, the heating temperature is preferably from 70 to 160 ° C, more preferably from 80 to 150 ° C. Further, the heating time is appropriately set depending on the heating temperature, and is preferably from 5 seconds to 30 minutes, more preferably from 10 seconds to 15 minutes.

The liquid system containing the photosensitive adhesive composition is prepared by appropriately adding a solvent or the like which can be dissolved in the photosensitive adhesive composition of the present invention. Further, the solvent to be used is preferably one which can be removed by volatilization when heated in the later-described step. Specifically, examples of the solvent include toluene, xylene, benzene, dimethylformamide, tetrahydrofuran, ethyl stilbene, ethyl acetate, N-methyl-2-pyrrolidone, and γ- Butyrolactone, N,N-dimethylacetamide, dimethyl hydrazine, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, two Propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl ethyl ketone, cyclohexanone, methyl-1,3-butanediol acetate, 1 Further, 3-butanediol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, and methyl 3-methoxypropionate may be used alone or in combination of two or more. Among these, in terms of high solubility and easy removal by volatilization, it is particularly preferable to contain propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, γ-butyrolactone, and cyclohexanone. Solvent for either.

[2] Exposure step

Then, the mask is set in contact with the coating film 601a formed on the wafer 201. The cover 4 exposes a desired region (exposure region) of the coating film 601a (see Fig. 2(c)). Thereby, a photoreaction occurs in the coating film 601a in the exposure region, and patterning (forming a latent image) is potentially performed.

Examples of the light used for the exposure treatment include electromagnetic waves or particle beams of various wavelengths, and examples thereof include ultraviolet rays such as i-rays, visible rays, lasers, X-rays, and electron beams. Among them, ultraviolet rays or visible rays having a wavelength of about 200 to 700 μm are preferably used. Further, the exposure treatment can be carried out, for example, in an air atmosphere, an inert gas atmosphere, or a reduced pressure atmosphere.

In the exposure step, a mask provided separately from the coating film 601a may be used instead of the mask 4 provided in contact with the coating film 601a. Further, in the case where an X-ray or an electron beam having a high directivity is used for the exposure processing, the use of the mask can be omitted.

The exposure amount in the exposure treatment is appropriately set depending on the thickness of the coating film 601a or the sensitivity of the photosensitive adhesive composition, and is preferably about 30 to 3,000 mJ/cm ² as an example.

[3] Development step

Then, the coating film 601a subjected to the exposure treatment is subjected to development processing. Thereby, the exposed portion (the exposed region of the coating film 601a) is removed, and the desired patterning is performed as shown in Fig. 2(d). By such development processing, for example, the electrode pads for connecting the bonding wires 70 can be exposed to the semiconductor wafer 20. Moreover, the coating film 601a on the cutting line which becomes the cutting edge can be removed in the cutting step described later.

In the development processing, the developer is brought into contact with the coating film 601a subjected to the exposure treatment. Thereby, the coating film 601a of the exposure portion is dissolved in the developer to be removed. Thereby, the opening portion 601b is formed in the coating film 601a. As the developer, for example, a base can be mentioned An alkali developer such as a metal carbonate, an alkali metal hydroxide or tetraammonium hydroxide, or an organic developer such as dimethylformamide or N-methyl-2-pyrrolidone . Among these, it is more preferable to use an alkaline developer as the developer. Further, the alkaline developer has a feature that the load on the environment is small and residue is less likely to occur.

Further, examples of the method of supplying the developer include spraying, liquid coating, dipping, and ultrasonic.

Further, in the present embodiment, the coating film 601a has a so-called positive photosensitive property, but the coating film 601a may have a so-called negative photosensitive property.

[4] Processing steps

Then, the wafer 201 on which the coating film 601a is provided is subjected to an etching treatment. At this time, the coating film 601a having the opening 601b functions as an etching mask. Thereby, the etching process is selectively performed on the surface (upper surface) of the wafer 201 in the region corresponding to the opening 601b. As a result, when a passivation film is formed on the surface of the wafer 201, it can be removed to expose the electrode pads for connecting the bonding wires 70.

As the etching treatment, for example, plasma etching treatment (dry etching treatment), various wet etching treatments, and the like are performed by supplying plasma to the wafer 201 as shown in FIG. 3(f). The plasma etching treatment can be carried out under generally known conditions, for example, a fluorine compound gas (CF ₄ , CHF ₃ ), a mixture gas of a fluorine compound gas (CF ₄ , CHF ₃ ) and oxygen (O ₂ ), or a fluorine compound can be used. A gas mixture of a gas (CF ₄ , CHF ₃ ) and argon (Ar) is used as a processing gas, and the output is 200 to 2000 W, the time is 0.2 to 15 minutes, and the gas flow rate is 50 to 1000 sccm.

Thereafter, the wafer 201 provided with the coating film 601a is subjected to ashing treatment as needed. Thereby, the treatment residue or the like generated by the etching treatment is removed to form the coating film 601a. The surface or electrode pad surface becomes clean. As a result, the adhesion of the bonding layer 601 to be described later or the bonding force of the bonding pad 70 to the electrode pad can be improved.

Examples of the ashing treatment include plasma treatment, wet treatment using a chemical, and the like. For example, using an oxygen plasma treatment (O _2), oxygen (O ₂₎ and argon (Ar) gas as the processing gas mixture, the output is 200 ~ 2000W, the treatment time is 0.2 to 15 minutes, gas flow rate was 50 It is carried out under conditions of ~1000 sccm.

[5] Back grinding step

Then, as shown in FIG. 3(g), the back surface polishing film 90 is attached to the coating film 601a. The back surface polishing film 90 supports the wafer 201 during the back surface polishing process, and suppresses defects such as defects or cracks in the wafer 201.

Then, the back surface (the other surface side) of the wafer 201 is ground (back surface polishing treatment). Thereby, the broken line portion of FIG. 3(h) can be removed to make the thickness of the wafer 201 thin. By the back grinding process, the thickness of the wafer 201 is different from the thickness of the original wafer 201, and can be reduced to about 20 to 100 μm. The back grinding treatment uses, for example, a device called a back grinding wheel.

Further, by cutting the coating film 601a obtained from the photosensitive adhesive composition of the present invention, the adhesive layer 601 exhibiting a sufficient adhesion force with the semiconductor wafer 20 can be cut out. Further, the coating film 601a obtained from the photosensitive adhesive composition of the present invention also exhibits a sufficient adhesion to the back surface polishing film 90. Therefore, the back surface polishing film 90 can reliably support the coating film 601a and the wafer 201 by attaching the back surface polishing film 90 to the coating film 601a. As a result, since the positional deviation of the wafer 201 with respect to the back surface polishing film 90 does not occur at the time of the back surface polishing process, the wafer 201 can be subjected to high-precision back surface polishing. Therefore, thickness unevenness of the wafer 201 can be suppressed. The result is that The semiconductor wafer 20 having a tilt or the like is less likely to be formed during lamination.

Further, in the case of the present embodiment, the wafer 201 to be subjected to the back surface polishing step is formed into a film by the coating film 601a, and the back surface polishing treatment is performed in this state. As described above, the coating film 601a is provided with the mechanical properties of the semiconductor wafers 20 that can be reliably followed. Therefore, the coating film 601a also functions to mechanically support the wafer 201 by interposing between the wafer 201 and the back surface polishing film 90. Further, since the coating film 601a is slightly cured after being formed on the wafer 201 in a liquid phase state, the adhesion to the wafer 201 is good. Therefore, by performing the back grinding process on the wafer 201 provided with the coating film 601a, a more uniform process can be realized.

As the back surface polishing film 90, an ultraviolet (UV) ultraviolet peeling type back surface polishing film can be used. By using such a back surface polishing film 90, when the back surface polishing film 90 is peeled off from the coating film 601a after the back surface polishing treatment, the back surface polishing can be greatly reduced by performing UV irradiation treatment on the coating film 601a only by interposing the back surface polishing film 90. The adhesion between the film 90 and the coating film 601a. As a result, the back surface polishing film 90 can be smoothly peeled off from the coating film 601a without causing a large load on the coating film 601a.

[6] Cutting step

Then, the wafer 201 is subjected to a dicing process. Thereby, the wafer 201 is singulated (divided) into a plurality of semiconductor wafers 20.

The dicing process is performed in a state where the wafer 201 is attached to the dicing die adhesion film or the dicing film. The dicing-die adhesion film or dicing film is used to fix the wafer 201 during the dicing process.

3(i1) and 3(i2) are views showing an example in which the dicing film 100a is attached to the back side of the wafer 201 ground in the back grinding step. Furthermore, Figure 3 (i1) A wafer 201 or the like for cutting out the semiconductor wafer 20 used in the lowermost layer of the wafer laminate 200 (the layer closest to the package substrate 30) is shown. On the other hand, Fig. 3 (i2) shows a wafer 201 or the like for cutting out the semiconductor wafer 20 used for the layer other than the lowermost layer of the wafer laminate 200.

In Fig. 3 (i1), the dicing die-bonding film 100, which is a laminate of the dicing film 100a and the die attach film 100b, is attached to the back surface of the wafer 201. On the other hand, in FIG. 3 (i2), the dicing film 100a is attached to the back surface of the wafer 201.

Then, as shown in FIG. 4 (j1) and FIG. 4 (j2), the back surface polishing film 90 is peeled off from the coating film 601a.

Then, the wafer 201 on which the coating film 601a is provided is subjected to a dicing process. As shown in FIG. 4 (k1) and FIG. 4 (k2), the cutting process is performed in such a manner that the cutting blade 110 reaches the dicing film 100a. As a result, the coating film 601a, the wafer 201, and the die attach film 100b are each singulated, and as shown in FIG. 4 (k1), the bonding layer 601, the semiconductor wafer 20 (first semiconductor element), and the bonding layer 101 are laminated. The single piece 21 is cut out. Similarly, the coating film 601a and the wafer 201 are each singulated, and as shown in FIG. 4 (k2), the single piece 22 in which the adhesive layer 601 and the semiconductor wafer 20 (second semiconductor element) are laminated is cut out.

Furthermore, in the present embodiment, a plurality of semiconductor wafers 20 are cut out by performing a dicing process on one wafer 201 (a bonded body of a plurality of semiconductor wafers 20). However, the present invention is not limited thereto, and for example, a plurality of semiconductor wafers 20 which are singulated in advance may be used. In this case, the cutting step can be omitted. Moreover, the back grinding step can be omitted in the case where the wafer 201 or the semiconductor wafer 20 is initially thin.

Further, the order of the steps of the back grinding step and the cutting step is not limited to the above order, and the order may be exchanged. That is, the back surface polishing process may be performed after performing the dicing process on the wafer 201.

[7] Installation steps

4(L1) and 4(L2) are views showing an example in which the cut piece 21 and the single piece 22 are picked up by the suction nozzle 121 of the joining device 120, respectively.

First, the single piece 21 is picked up by the suction nozzle 121 of the bonding device 120, and is crimped (mounted) on the package substrate 30 as shown in Fig. 5(a). At this time, the back surface of the semiconductor wafer 20 and the package substrate 30 are next via the adhesion layer 101. Further, the adhesive layer 101 is formed by singulating the die attach film 100b. However, the adhesive layer 101 may be formed of, for example, an uncured or semi-cured material (a photosensitive adhesive composition that does not reach complete curing) of the photosensitive adhesive composition of the present invention. In this case, the package substrate 30 also corresponds to a non-joining member joined to the semiconductor element 20. That is, the photosensitive adhesive composition of the present invention can be used not only for bonding the semiconductor element 20 and the semiconductor element (joined member) 20 but also for bonding the semiconductor element 20 to the package substrate (joined member) 30. Furthermore, the member to be joined is not limited to these.

Then, the single piece 22 is crimped onto the previously mounted single piece 21. Thereby, as shown in FIG. 5(b), two semiconductor wafers 20 can be laminated via the bonding layer 601. Thereafter, by repeating this step, as shown in FIG. 5(c), the wafer laminate 200 in which a plurality of semiconductor wafers 20 are laminated can be obtained. At this time, by laminating the positions of the semiconductor wafers 20 while being shifted from each other, the semiconductor wafer 20 can secure a region (a region corresponding to the opening portion 601b of the coating film 601a) to which the bonding wires 70 are connected. That is, the electrode portions of the semiconductor wafer 20 can be exposed by laminating the positions of the semiconductor wafers 20 while being shifted.

Further, when the semiconductor wafer 20 is mounted, the layer 601 is heated while being heated. Thereby, the layer 601 exhibits sufficient adhesion, and the semiconductor crystal The sheets 20 are firmly followed to each other. The heating temperature in this case is preferably about 30 to 150 °C. Further, it is preferable that the crimping load at the time of mounting is about 0.1 to 100 N, and the crimping time is about 0.1 to 10 seconds.

Thereafter, as shown in FIG. 5(d), the electrode portions of the semiconductor wafers 20 are connected to the exposed portions of the wirings 34 of the package substrate 30 by the bonding wires 70.

Then, by molding the mold portion 50 so as to cover the wafer laminate 200 and the package substrate 30, the semiconductor device 10 shown in FIG. 1 can be obtained.

The molding of the mold portion 50 can be performed by injecting a sealing material into the molding die using, for example, a transfer molding machine. In this case, it is preferable to set the temperature of the molding die to about 130 to 250 ° C, the injection pressure to about 3 to 10 MPa, and the holding time after the injection to about 10 to 10 minutes.

After the mold release, the mold portion 50 and the adhesive layer 601 are finally cured (completely hardened) by heating the molded body as necessary. In this case, the heating temperature is preferably about 130 to 250 ° C, and the heating time is preferably about 10 minutes to 10 hours.

Furthermore, the method of fabricating the semiconductor device of the present invention may have a heating step between the above [3] development step and [4] treatment step. In this heating step, the coating film 601a subjected to the development treatment is heated (see FIG. 2(e)). Thereby, a predetermined hardening reaction (thermosetting reaction) is generated in the photosensitive adhesive composition constituting the coating film 601a. As a result, the photosensitive adhesive composition is slightly cured (semi-hardened), and the adhesion of the coating film 601a is increased.

The heating temperature of the coating film 601a is not particularly limited, but is preferably 80 to 170 ° C, more preferably 120 to 160 ° C. Further, the heating time is appropriately set depending on the heating temperature, and is preferably 35 to 120 minutes, more preferably 40 to 100 minutes. Thereby, the mechanical properties such as the elastic modulus of the coating film 601a are optimized, and the coating film 601a is given to the etching place. Rational or ashing treatment is adequately tolerated.

Further, the coating film 601a is formed of the photosensitive adhesive composition of the present invention, and the adhesive layer 601 formed of such a coating film 601a exhibits relatively high solubility to an organic solvent. Therefore, even if the coating film 601a needs to be removed after the film 201 is formed by the coating film 601a, for example, generation of residue (residue) can be suppressed, and the coating film 601a can be efficiently dissolved and removed. Therefore, the wafer 201 is not wasted and can be re-applied to the subsequent process (for secondary processing). As a result, the improvement in the step yield of the semiconductor device 10 can be achieved.

Further, the method of manufacturing the semiconductor device may have a step of irradiating light to the entire surface of the coating film (light irradiation step) in addition to or in place of the heating step.

<Photosensitive adhesive composition>

Next, a photosensitive adhesive composition (the photosensitive adhesive composition of the present invention) constituting the adhesive layer 601 will be described.

"composition"

The photosensitive adhesive composition contains (A) an alkali-soluble resin, (B) a photoacid generator, (C) an epoxy compound, and (D) a phenol compound.

Hereinafter, each material constituting the photosensitive adhesive composition will be described in detail.

<(A) alkali soluble resin>

(A) The alkali-soluble resin is a material which becomes a base material of the adhesive layer 601. Further, by including the (A) alkali-soluble resin in the photosensitive adhesive composition, the adhesion (adhesion force) of the adhesive layer 601 to the semiconductor wafer 20 can be improved. Therefore, it can be half by the layer 601 The conductor wafers 20 are more firmly connected to each other. Further, by including the (A) alkali-soluble resin in the photosensitive adhesive composition, the coating film 601a can be made soluble in the alkaline developing solution. Therefore, it is possible to use an alkaline developer having a small environmental load, and it is possible to reduce the environmental load in the development step.

Specific examples of the (A) alkali-soluble resin include a phenol resin, an acrylic resin, a cyclic olefin resin, a polyamide resin, a polyimide resin, and a polyvinylphenol resin. One type or a combination of two or more types can be used. Among these, as the (A) alkali-soluble resin, a cyclic olefin-based resin is particularly preferable. Examples of the cyclic olefin-based resin include a drop. An olefin resin, a benzocyclobutene resin, or the like. Among these, as the cyclic olefin resin, it is preferred to lower An olefinic resin. By using a photosensitive adhesive composition containing a cyclic olefin resin, an adhesive layer 601 which is particularly excellent in adhesion to the semiconductor wafer 20 can be obtained. Especially by using inclusion The photosensitive adhesive composition of the olefinic resin can further improve the adhesion of the adhesive layer 601 to the semiconductor wafer 20. Again, due to the drop The olefinic resin has a higher hydrophobicity, so by using the inclusion The photosensitive adhesive composition of the olefinic resin can form the adhesive layer 601 which is less likely to cause dimensional change due to water absorption.

Hereinafter, a case where (A) the alkali-soluble resin is a cyclic olefin-based resin will be described as a representative. The cyclic olefin resin preferably has an acidic group (a substituent showing an acidity). Specifically, the cyclic olefin resin preferably contains at least one repeating unit (first repeating unit) having an acidic group.

The first repeating unit has a structure derived from a cyclic olefin (cyclic olefin monomer) as a main skeleton, and a substituent bonded to the structure and having an acidic group.

Examples of the structure derived from a cyclic olefin include a monocyclic ring derived from cyclohexene or cyclooctene. Alkene Diene, dicyclopentadiene, dihydrodicyclopentadiene, tetracyclododecene, tricyclopentadiene, dihydrotricyclopentadiene, tetracyclopentadiene, dihydrotetracyclopentadiene Structures such as polycyclic bodies. In these, as a structure derived from a cyclic olefin, it is particularly preferred to The structure of the olefin. From descending The configuration of the olefin helps to increase the adhesion of the bonding layer 601 to the semiconductor wafer 20. Again, from the drop The structure of the olefin also contributes to the improvement of the heat resistance of the photosensitive adhesive composition and the softness of the photosensitive adhesive composition after curing.

Examples of the substituent having an acidic group include a substituent having a carboxyl group, a phenolic hydroxyl group, -C(OH)-(CF ₃ ) ₂ , -N(H)-S(O) ₂ -CF _{3 ,} or the like. In particular, a substituent having any one of a carboxyl group and -C(OH)-(CF ₃ ) ₂ is preferred. When the cyclic olefin-based resin contains such a substituent having an acidic group, the solubility of the photosensitive adhesive composition to the alkaline developer can be improved. Therefore, in the manufacture of the semiconductor device, the undissolved residue of the photosensitive adhesive composition after development can be reduced, and the patterning property at the time of development can be further improved.

According to the above, the first repeating unit is preferably at least one of the following formula (2) and the following formula (3). By including such a first repeating unit in the cyclic olefin resin, the adhesion of the adhesive layer 601 to the semiconductor wafer 20 and the solubility of the photosensitive adhesive composition to the alkaline developing solution can be further improved.

[Chemical 3]

In the above formula (2) and the above formula (3), x and y are each preferably an integer of 0 or more and 10 or less, more preferably an integer of 1 or more and 5 or less. Thereby, an adhesive layer 601 capable of adhering the semiconductor wafers 20 to each other more firmly can be obtained.

The cyclic olefin resin may have at least one first repeating unit, preferably two or more different first repeating units, and more preferably both of the above formula (2) and the above formula (3). The first repeat unit. Thereby, the adhesion of the adhesive layer 601 to the semiconductor wafer 20 and the solubility of the photosensitive adhesive composition to the alkaline developing solution can be further improved.

The content ratio of the first repeating unit in the cyclic olefin resin can be determined in consideration of the solubility of the photosensitive adhesive composition to the alkaline developing solution, and is preferably, for example, 10 to 80 mol%, more preferably 20%. 70 mol%. When the content rate of the first repeating unit is less than the above lower limit value, it may be difficult to sufficiently express the solubility of the photosensitive adhesive composition to the alkaline developing solution. In addition, when the content of the first repeating unit is more than the above-mentioned upper limit, the characteristics of the configuration other than the first repeating unit in the cyclic olefin resin cannot be sufficiently exhibited depending on the type of the first repeating unit. .

The acidic group in the cyclic olefin resin is preferably 0.001 to 0.01 mol per 1 g of the polymer. More preferably 0.0015~0.006 moles. Thereby, the solubility of the photosensitive adhesive composition to the alkaline developing solution can be particularly improved.

Further, the cyclic olefin resin preferably has a second repeating unit different from the first repeating unit.

The second repeating unit has a structure derived from a cyclic olefin as a main skeleton and a substituent bonded to the structure and different from the substituent of the first repeating unit.

As the main skeleton of the second repeating unit, the structure exemplified in the above first repeating unit can be used. In the above, the main skeleton of the second repeating unit is particularly preferably derived from the viewpoint of the heat resistance of the photosensitive adhesive composition or the flexibility of the photosensitive adhesive composition after curing. The structure of the olefin. Further, the main skeletons of the first and second repeating units may be different from each other, but are preferably the same. In particular, the main skeletons of the first and second repeating units are derived from the descending The structure of the alkene is preferred. Thereby, the adhesion of the bonding layer 601 to the semiconductor wafer 20 can be further improved, and the elastic modulus of the bonding layer 601 can be appropriately reduced. Therefore, by the bonding layer 601, the semiconductor wafers 20 can be more firmly adhered to each other, and by appropriately increasing the flexibility of the bonding layer 601, the stress concentration generated at the bonding interface between the semiconductor wafers 20 can be alleviated.

The number of carbon atoms of the substituent in the second repeating unit is preferably from 2 to 30, more preferably from 4 to 15. When the carbon number is in the above range, the elastic modulus of the photosensitive adhesive composition after curing is lowered, and the flexibility of the adhesive layer 601 can be improved. Thereby, the crack generated in the semiconductor wafer 20 or the subsequent layer 601 or the peeling of the semiconductor wafer 20 and the adhesion layer 601 accompanying the stress concentration at the joint interface between the semiconductor wafers 20 can be further suppressed. Further, it is possible to suppress breakage of the semiconductor wafer 20 or the subsequent layer 601 due to an external impact.

Further, the substituent of the second repeating unit may be a cyclic structure or a branched structure, and is preferably a linear structure. Thereby, the elastic modulus of the photosensitive adhesive composition after curing can be further reduced, and the flexibility of the adhesive layer 601 can be further improved.

Examples of the linear substituent having 2 to 30 carbon atoms include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, and a group having an alkyl ether structure. Among these, as the linear substituent having 2 to 30 carbon atoms, a group having an alkyl ether structure is particularly preferable. Thereby, the photosensitive adhesive composition after hardening can have excellent flexibility.

The group having a structure of an alkyl ether is preferably a group represented by the following formula (1). Thereby, the flexibility of the adhesive layer 601 can be further improved.

In the above formula (1), z is preferably an integer of 1 or more and 10 or less, more preferably an integer of 2 or more and 6 or less. Thereby, the adhesive layer 601 having better flexibility can be obtained.

According to the above, the second repeating unit is particularly preferably the following formula (4). (A) The alkali-soluble resin has a second repeating unit represented by the following formula (4) in addition to the above-mentioned first repeating unit, whereby it is preferably achieved at the same time that the first repeating unit can be sufficiently improved. The function of the solubility of the photosensitive adhesive composition to the alkaline developer and the function of the elastic modulus of the photosensitive adhesive composition obtained by the second repeating unit after curing are moderate.

In particular, in the above formula (4), z is preferably 1 or more and 10 or less. An integer is more preferably an integer of 2 or more and 5 or less. Thereby, the elastic modulus of the photosensitive adhesive composition after hardening can be made a better value.

In addition, when the cyclic olefin resin contains the second repeating unit, the content of the second repeating unit in the cyclic olefin resin is, for example, preferably 20 to 60 mol%, more preferably 25 to 50 mol%. When the content rate of the second repeating unit is less than the above lower limit, it is difficult to adjust the elastic modulus of the photosensitive adhesive composition after curing to a desired value depending on the type of the second repeating unit. In addition, when the content rate of the second repeating unit is more than the above-mentioned upper limit, the characteristics of the configuration other than the second repeating unit in the cyclic olefin resin cannot be sufficiently exhibited depending on the type of the second repeating unit. Hey.

From the above, it is preferred to use a cyclic olefin-based resin represented by the following formula (5). The photosensitive adhesive composition can impart desired mechanical strength and more appropriate flexibility (stress relaxation property) to the adhesive layer 601 by including the cyclic olefin resin represented by the formula (5). Further, the photosensitive adhesive composition can exhibit particularly excellent solubility to an alkaline developer. Further, the adhesion layer 601 which is particularly excellent in adhesion to the semiconductor wafer 20 can be obtained.

In the above formula (5), l, m, and n are integers of 1 or more and 100 or less. Further, as described above, x is preferably an integer of 0 or more and 10 or less, and y is preferably an integer of 0 or more and 10 or less, and z is preferably an integer of 1 or more and 10 or less.

In the formula (5), the degree of polymerization (i.e., n/(l+m)) of the second repeating unit with respect to the degree of polymerization of the first repeating unit is preferably from 0.3 to 2.0, more preferably from 0.4 to 1.5. Thereby, it is possible to obtain a bonding layer 601 in which the stress concentration generated at the bonding interface between the semiconductor wafers 20 can be moderated and the semiconductor wafers 20 can be more firmly adhered to each other.

Further, the weight average molecular weight (Mw) of the cyclic olefin resin is preferably 5,000 to 500,000, more preferably 7,000 to 200,000, still more preferably 8,000 to 100,000. Thereby, the adhesive layer 601 which is particularly excellent in the adhesion force to the semiconductor wafer 20 can be obtained.

Further, the weight average molecular weight (Mw) of the cyclic olefin resin can be measured by gel permeation chromatography (GPC) using ASTM DMS 3536-91 as a standard cyclic olefin resin.

Further, the glass transition temperature of the cyclic olefin resin is preferably from 100 to 250 °C. By using such a cyclic olefin-based resin having a glass transition temperature, the heat resistance of the photosensitive adhesive composition becomes higher, and the reliability of the semiconductor device 10 at a high temperature can be further improved.

The glass transition temperature of the cyclic olefin resin can be determined by, for example, a differential scanning calorimetry method, as a temperature at which an exothermic reaction occurs at a temperature increase rate of 5° C./min from a normal temperature. In addition, the (A) alkali-soluble resin other than the cyclic olefin-based resin is synthesized so as to satisfy the same conditions as those described for the cyclic olefin-based resin, whereby the same effects as described above can be obtained.

<(B) Photoacid generator>

(B) The photoacid generator has a function as a positive photoacid generator, which is capable of utilizing energy The acid generated in the photoreaction at the time of exposure by the ray irradiation can increase the solubility of the photosensitive adhesive composition of the exposed portion to the alkaline developing solution. As a result, in the production of the semiconductor device, the undissolved residue after development in the exposed portion which is the exposed portion of the photosensitive adhesive composition (coating film 601a) can be further reduced. Therefore, the patterning property at the time of development can be improved. Further, the photosensitive adhesive composition may have a function as a negative photoacid generator which can be used in the manufacture of a semiconductor device by irradiating an energy ray by including a (B) photoacid generator. The reaction of crosslinking (A) an alkali-soluble resin by (C) epoxy compound mentioned later is promoted.

Specific examples of the (B) photoacid generator include an onium salt, a halogenated organic compound, a quinonediazide compound, an α,α-bis(sulfonyl)diazomethane compound, and α-carbonyl-α. A sulfonyl-diazomethane-based compound, an anthracene compound, an organic acid ester compound, an organic acid decylamine compound, an organic acid quinone imine compound, or the like may be used alone or in combination of two or more. Among these, as the (B) photoacid generator, it is particularly preferable to use a quinonediazide compound. Examples of the quinonediazide compound include a compound having a 1,2-benzoquinonediazide or a 1,2-naphthoquinonediazide structure. More specifically, the (B) photoacid generator preferably comprises 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonate. An ester compound of an acid and a phenol compound. Since these carboxyl groups are generated in the photoreaction during exposure by energy ray irradiation (especially radiation irradiation), the solubility of the exposed portion to the alkaline developing solution can be further increased. Therefore, the photosensitive adhesive composition can exhibit higher solubility to an alkaline developer even at a particularly small exposure amount. As a result, the patterning property at the time of development can be further improved.

The content of the photo-acid generator (B) is not particularly limited, and is preferably from 1 to 50 parts by mass, more preferably from 5 to 30 parts by mass, per 100 parts by mass of the (A) alkali-soluble resin. If the content of the (B) photoacid generator is less than the above lower limit, according to (B) photoacid generator There is a possibility that the exposure and development characteristics of the photosensitive adhesive composition are lowered depending on the type and the like. In addition, even if the content of the (B) photoacid generator exceeds the above upper limit, an increase in the above effect cannot be expected, and depending on the type of the photoacid generator (B), the photosensitive adhesive cannot be sufficiently exhibited. The characteristic of the material other than the (B) photoacid generator in the composition.

<(C) epoxy compound>

(C) The epoxy compound has a function of crosslinking (A) an alkali-soluble resin (especially a cyclic olefin-based resin).

The (C) epoxy compound may be any of an aromatic epoxy compound containing an aromatic ring in the molecule or an aliphatic epoxy compound containing no aromatic ring in the molecule. However, as the (C) epoxy compound, an aliphatic epoxy compound is more preferable. Thereby, the crosslinking density of the (A) alkali-soluble resin in the photosensitive adhesive composition can be made moderate, and the flexibility of the adhesive layer 601 can be appropriately improved.

Further, the (C) epoxy compound is preferably a branched structure or a linear structure, and more preferably has a branched structure. By the photosensitive adhesive composition comprising the (C) epoxy compound having a branched structure, the crosslinking density of the (A) alkali-soluble resin in the photosensitive adhesive composition can be made moderate, and The softness of layer 601 is then moderately increased. Thereby, the adhesion layer 601 which has the required mechanical strength and the stress concentration which the stress concentration generate|occur|produces by the junction interface of the semiconductor wafer 20 is moderated is more excellent.

Further, the (C) epoxy compound preferably contains two or more glycidyl groups in the molecule, and more preferably contains three or more and nine or less glycidyl groups in the molecule. Thereby, the cross-linking of the (A) alkali-soluble resin in the photosensitive adhesive composition can be achieved. The density becomes a moderate value, and the adhesive layer 601 having the required mechanical strength and superior stress relaxation property can be obtained.

Examples of such an (C) epoxy compound include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and trimethylolpropane three. Glycidyl ether, trimethylolethane triglycidyl ether, sorbitol polyglycidyl ether, pentaerythritol polyglycidyl ether, EXA-830CRP, EXA-830VLP, EXA-835LV, EXA-850CRP, EPICLON-830-S , EPICLON-840-S, EPICLON-850-S, EPICLON-850-CRP, EPICLON-850-LC, HP-7200, HP-7200L, HP-7200H (manufactured by DIC Corporation), YH-300, YH- 301, YD-8125G, YDF-8170G, YD-825GS, YD-825GSH, YD-870GS, ZX-1059, ZX-1542, PG-207GS, ZX-1658GS (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.), YL980 , YL983U, YL6810, YL7410, YX7700, YX8000, YX8034, YED216D, jER152, jER157S70, jER1032H60 (manufactured by Mitsubishi Chemical Corporation), EP3300S, EP3950L, EP-4000L, EP4010L, EP4088L (ADEKA Co., Ltd.), Celloxide 2021P, Celloxide 2081 (DAICEL Co., Ltd.), EPPN-201-L, EPPN-501H, EPPN-501HY, EPPN-502H, XD-1000 (Nippon Chemical), LX-01 (DAISO Co., Ltd.), PG-100, EG-200, EG-280, CG-400, CG-500 (Osaka Gas Chemicals Co., Ltd.) , EX-211L, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L, EX-946L (Nagase chemteX Co., Ltd.), VG3101L (Printec Co., Ltd.), SR-14BJ, SR- 16H, SR-TMPL, SR-PG, SR-PTMG, SR-8EGS (Sakamoto Pharmaceutical Co., Ltd.), epoxycyclohexane type epoxy resin, etc., one of these or a combination of 2 can be used. Use more than one species. Among these, as the (C) epoxy compound, trimethylolpropane triglycidyl ether, 1,6-hexanediol diglycidyl ether, polypropylene glycol diglycidyl ether, polyethylene glycol II are particularly preferable. Glycidyl ether, polytetramethylene glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether. Thereby, the crosslinking reaction of the (A) alkali-soluble resin in the photosensitive adhesive composition can be promoted, and the adhesion layer 601 which is more excellent in stress relaxation property can be obtained more easily and surely.

The content of the (C) epoxy compound is not particularly limited, and is preferably from 1 to 100 parts by mass, more preferably from 5 to 50 parts by mass, per 100 parts by mass of the (A) alkali-soluble resin. When the content of the (C) epoxy compound is less than the above lower limit, the stress relaxation property of the adhesive layer 601 may be lowered depending on the type of the epoxy compound (C) or the like. On the other hand, when the content of the (C) epoxy compound exceeds the above upper limit, the viscosity of the photosensitive adhesive composition may become excessively high.

<(D) Phenolic compound having a melting point of 50 to 150 ° C >

The photosensitive adhesive composition contains (D) a phenol compound having a melting point of 50 to 150 ° C (hereinafter sometimes simply referred to as "(D) phenol compound"), for example, etching the wafer 201 having the coating film 601a. When the semiconductor wafers 20 are bonded to each other via the bonding layer 601, generation of bubbles between the bonding layer 601 and the semiconductor wafer 20 can be suppressed. Further, even in the case where bubbles are generated between the adhesion layer 601 and the semiconductor wafer 20, the generated bubbles can be removed. As a result, air bubbles are less likely to remain at the interface between the bonding layer 601 and the semiconductor wafer 20, whereby the adhesion of the bonding layer 601 to the semiconductor wafer 20 can be improved, so that the semiconductor wafers 20 can be firmly adhered to each other. Therefore, the wafer laminate 200 having higher reliability can be finally obtained.

Further, by using a photosensitive adhesive group containing the (D) phenol compound As the product, an adhesive layer 601 which exhibits a relatively high solubility to an organic solvent can be obtained. Therefore, even when the coating film 601a obtained by applying the photosensitive adhesive composition to the wafer 201 is removed, for example, generation of residue (residue) can be suppressed and the coating film 601a can be efficiently dissolved and removed. . Thereby, the wafer 201 is not wasted and can be re-supplied to the subsequent process (secondary processing). Therefore, the improvement of the step yield of the semiconductor device 10 can be achieved.

Further, the (D) phenol compound has a melting point of 50 to 150 ° C, preferably a melting point of 60 to 130 ° C, and more preferably a melting point of 70 to 120 ° C. Thereby, the above effects obtained by including the (D) phenol compound in the photosensitive adhesive composition can be more clearly exhibited. The (D) phenol compound is preferably at least one of a phenol compound having a substituent having an aliphatic hydrocarbon group and a phenol compound having a plurality of phenol skeletons.

Further, the (D) phenol compound (especially a phenol compound having a substituent containing an aliphatic hydrocarbon group) preferably has a hydroxyl equivalent of from 150 to 250 g/eq, more preferably a hydroxyl equivalent of from 160 to 240 g/eq, and further preferably a hydroxyl equivalent of 180~220g/eq. When the hydroxyl equivalent is within the above range, a photosensitive adhesive composition which is further optimized for solubility in an alkaline developer can be obtained. On the other hand, when the hydroxyl group equivalent is less than the above-mentioned lower limit, the water absorption rate of the photosensitive adhesive composition becomes high depending on the type or addition amount of the phenol compound (D), and the reliability thereof may be lowered. Further, when the hydroxyl group equivalent exceeds the above upper limit value, the solubility of the photosensitive adhesive composition to the alkaline developer is remarkably lowered, and the undissolved residue of the photosensitive adhesive composition is generated after development.

Further, the hydroxyl equivalent of the (D) phenol compound can be determined by titrating a solution of the (D) phenol compound in a standard alkaline solution.

In the case where the (D) phenol compound contains a phenol compound having a substituent containing an aliphatic hydrocarbon group (a substituent having an alkyl chain (-CH ₂ -) n), the solubility of the adhesion layer 601 in an organic solvent can be further improved. . Therefore, even when the coating film 601a has to be removed, the coating film 601a can be dissolved and removed more efficiently, so that the secondary workability can be improved.

The value of n of the alkyl chain (-CH ₂ -) n is preferably from 1 to 6, more preferably from 2 to 4. Thereby, the solubility of the adhesive layer 601 in an organic solvent can be further improved.

Examples of the substituent containing the aliphatic hydrocarbon group include a methylene group, an ethylidene group, a trimethylene group, a butyl group, and a 2,2-dimethylbutyl group.

Further, the (D) phenol compound preferably has a structure derived from benzoic acid. Specifically, it preferably has a structure derived from monohydroxybenzoic acid such as benzoic acid, 2-hydroxybenzoic acid or 3-hydroxybenzoic acid, or dihydroxybenzoic acid such as 2,4-hydroxybenzoic acid.

Specific examples of such a (D) phenol compound include 4-(1,1-dimethylpropyl)phenol, 4-cyclohexylphenol, and 4-(1,1,3,3-tetra Methyl butyl) phenol, 4-(4-hydroxyphenyl)-2-butanone, 4'-hydroxybutanone, 4'-hydroxyphenylpentanone, 4'-hydroxybenzophenone, 3-(4 -hydroxyphenyl)propionic acid, methyl 3-hydroxybenzoate, ethyl 3-hydroxybenzoate, methyl 4-hydroxybenzoate, ethyl 4-hydroxybenzoate, propyl 4-hydroxybenzoate, 4- Isopropyl hydroxybenzoate, butyl 4-hydroxybenzoate, isobutyl 4-hydroxybenzoate, hexyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 1,3-double [2-(4) - hydroxyphenyl)-2-propyl]benzene, BisP-DED (manufactured by Honshu Chemical Industry Co., Ltd.), etc., may be used alone or in combination of two or more. Among these, as the (D) phenol compound, propyl 4-hydroxybenzoate, methyl 4-hydroxybenzoate, butyl 4-hydroxybenzoate, and hexyl 4-hydroxybenzoate are particularly preferable. Thereby, the adhesion layer 601 which is especially excellent in the adhesive force of the semiconductor wafer 20 and the solubility with respect to an organic solvent is obtained.

Further, in the case where the (D) phenol compound contains a phenol compound having a plurality of phenol skeletons, the hydroxyl equivalent thereof is preferably from 50 to 150 g/eq, more preferably from 70 to 130. g/eq, especially preferably 90~110g/eq. Further, a plurality of phenol skeletons may be a condensed type (fusion type) in which a phenol skeleton is bonded to each other by a single bond and is not directly bonded to each other, or a phenol skeleton is directly bonded to each other without a single bond. Any of the multi-ring structures is preferably a connected multi-ring structure. Thereby, the adhesion layer 601 which is especially excellent in the adhesive force of the semiconductor wafer 20 and the solubility with respect to an organic solvent is obtained.

The content of the (D) phenol compound is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the (A) alkali-soluble resin. When the content of the (D) phenol compound is less than the above lower limit, the solubility of the photosensitive adhesive composition in the organic solvent may be lowered depending on the type of the (D) phenol compound or the like. Even if the content of the (D) phenol compound exceeds the above upper limit, an increase in the above effect cannot be expected. In this case, depending on the type of the (D) phenol compound, the properties of the material other than the phenol compound in the photosensitive adhesive composition (D) cannot be sufficiently exhibited.

Further, the photosensitive adhesive composition preferably contains two or more kinds of (D) phenol compounds as described above. Specifically, it is preferred to contain two or more kinds of (D) phenol compounds having mutually different melting points, and more preferably two (D) phenol compounds having mutually different melting points. Thereby, the adhesion of the photosensitive adhesive composition (adjacent layer 601), the stress relaxation property, and the solubility in an organic solvent can be further improved.

In addition, when two or more (D) phenol compounds are contained, the total content of these is preferably in the above range.

The photosensitive adhesive composition contains the above (A) alkali-soluble resin, (B) photoacid generator, (C) epoxy compound, and (D) phenol compound, and is manufactured, for example, in the manufacture of a semiconductor device. When the wafer 201 of the coating film 601a is etched or when the semiconductor wafer 20 is bonded to each other via the bonding layer 601, it is not easy to leave bubbles at the interface between the layer 601 and the semiconductor wafer 20. Therefore, the semiconductor crystal can be formed by the bonding layer 601 The sheets 20 are firmly adhered to each other, so that the wafer laminate 200 having higher reliability can be obtained. Further, although the subsequent layer 601 has a single-layer structure, it has stress relaxation properties in addition to sufficient adhesion. Therefore, it is not necessary to provide two layers of the layer excellent in adhesion and excellent in stress relaxation between the semiconductor wafers 20, and therefore it is possible to prevent the entire thickness of the wafer laminate 200 from becoming significantly thick. As a result, the semiconductor device 10 having high reliability with low back, adhesion, and stress relaxation property can be obtained. Such a semiconductor device 10 is particularly useful in electronic devices such as mobile devices that are actively small and portable. In other words, the semiconductor device 10 is useful for miniaturization, thinning, and weight reduction of an electronic device, and is less likely to damage the semiconductor device 10 even when the electronic device is dropped or rotated. Features.

Further, the solubility and secondary processing of the cured product of the (A) alkali-soluble resin, (B) photoacid generator, (C) epoxy compound, and (D) phenol compound photosensitive adhesive composition to an organic solvent Excellent sex.

Further, such a photosensitive adhesive composition preferably further comprises (X) a phenol compound having a melting point higher than that of the (D) phenol compound. Thereby, the adhesion of the adhesive layer 601 can be particularly improved. Further, the melting point of the (X) phenol compound is preferably from 151 to 250 ° C, more preferably from 181 to 230 ° C. Further, the (X) phenol compound preferably contains a phenol compound having a plurality of phenol skeletons. The phenol compound having a plurality of phenol skeletons preferably has a substituent having a cyclic structure and bonded to at least one of the above phenol skeletons. Thereby, the above effects can be more clearly exerted.

Further, the content of the (X) phenol compound is preferably 0.2 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass of the (A) alkali-soluble resin. When the content of the (X) phenol compound is within the above range, the above effects can be more clearly exhibited.

Further, the photosensitive adhesive composition is particularly preferably composed of two kinds of (D) phenol compounds. And further comprising (X) a phenol compound. Thereby, the adhesive layer 601 which is especially excellent in adhesiveness, stress relaxation property, and solubility in an organic solvent can be obtained.

Further, the photosensitive adhesive composition may further contain (D) a phenol compound and a phenol compound other than the phenol compound, a leveling agent, a flame retardant, a plasticizer, a hardening accelerator, an antioxidant, and a adhesion aid, as needed. Wait.

For example, a phenolic antioxidant, an amine-based antioxidant, a phosphorus-based antioxidant, and a thioether-based antioxidant can be used, and one type or a combination of two or more types can be used. Among these, as the antioxidant, it is preferred to use a combination of a phenol-based antioxidant and an amine-based antioxidant.

By including such an antioxidant, oxidation of the photosensitive adhesive composition (coating film 601a) in the oxidation at the time of curing of the photosensitive adhesive composition and the subsequent process can be suppressed.

Examples of the phenolic antioxidant include pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], and 3,9-bis{2-[3-( 3-tert-butyl-4-hydroxy-5-methylphenyl)propanoxy]-1,1-dimethylethyl}2,4,8,10-tetraoxaspiro[5,5 Undecane, octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 1,6-hexanediol-bis[3-(3,5- Di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl) Benzene, 2,6-di-t-butyl-4-methylphenol, 2,6-di-t-butyl-4-ethylphenol, 2,6-diphenyl-4-octadecyloxy Phenol, 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol, stearyl (3,5-di-t-butyl-4-hydroxyphenyl) Propionate, distearyl (3,5-di-t-butyl-4-hydroxybenzyl)phosphonate, thiodiethylene glycol bis[(3,5-di-t-butyl-4- Hydroxyphenyl)propionate], 4,4'-thiobis(6-tert-butyl-m-cresol), 2-octylthio-4,6-di(3,5-di-3rd 4-hydroxyphenoxy)-all three , 2,2'-methylenebis(4-methyl-6-tert-butyl-6-butylphenol), 2,2'-methylenebis(4-ethyl-6-tributyl) Phenol), bis[3,3-bis(4-hydroxy-3-t-butylphenyl)butanoic acid]diol, 4,4'-butylene bis(6-t-butyl-m-group Phenol), 2,2'-ethylenebis(4,6-di-t-butylphenol), 2,2'-ethylenebis(4-secondbutyl-6-tert-butylphenol) 1,1,3-Tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, bis[2-t-butyl-4-methyl-6-(2-hydroxyl) 3-tert-butyl-5-methylbenzyl)phenyl]terephthalate, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tributyl) Benzyl)isocyanurate, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,3, 5-tris[(3,5-di-t-butyl-4-hydroxyphenyl)propanyloxyethyl]isocyanurate, tetrakis[methylene-3-(3,5-di-third) Butyl-4-hydroxyphenyl)propionate]methane, 2-tert-butyl-4-methyl-6-(2-propenyloxy-3-tert-butyl-5-methylbenzyl Phenol, 3,9-bis(1,1-dimethyl-2-hydroxyethyl)-2,4-8,10-tetraoxaspiro[5,5]undecane-bis[β-( 3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], triethyl Alcohol bis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], 1,1'-bis(4-hydroxyphenyl)cyclohexane, 2,2' -methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-Asia Methyl bis(6-(1-methylcyclohexyl)-4-methylphenol), 4,4'-butylene bis(3-methyl-6-tert-butylphenol), 3,9-double (2-(3-Tertibutyl-4-hydroxy-5-methylphenylpropanoxy) 1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro ( 5,5) undecane, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-bis(3,5-di-t-butyl-4- Hydroxybenzyl) sulfide, 4,4'-thiobis(6-tert-butyl-2-methylphenol), 2,5-di-t-butylhydroquinone, 2,5-di-third Hydroquinone, 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2,4-dimethyl- 6-(1-Methylcyclohexyl)styrene phenol, 2,4-bis((octylthio)methyl)-5-methylphenol, and the like. Among these, a phenolic antioxidant such as 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol is preferred.

As the amine-based antioxidant, N, N'-di-second butyl-p-benzoic acid can be cited. Amine, 4,4'-dimethoxydiphenylamine, 4-isopropoxydiphenylamine, N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3 -Dimethylbutyl)-N'-phenyl-p-phenylenediamine, 4,4'-bis(?,?-dimethylbenzyl)diphenylamine, and the like. Among these, as the amine-based antioxidant, 4,4'-dimethoxydiphenylamine, 4-isopropoxydiphenylamine, 4,4'-di(?, ?- is preferable. A diphenylamine compound such as dimethylbenzyl)diphenylamine.

Examples of the phosphorus-based antioxidant include bis-(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite and tris(2,4-di-t-butylphenylene). Phosphate), tetrakis(2,4-di-t-butyl-5-methylphenyl)-4,4'-extended biphenyldiphosphinate, 3,5-di-t-butyl-4 -hydroxybenzylphosphonate-diethyl ester, bis-(2,6-di Phenyl) pentaerythritol diphosphite, 2,2-methylenebis(4,6-di-t-butylphenyl)octyl phosphite, tris (mixed mono- and di-decylphenyl phosphite) , bis(2,4-di-t-butylphenyl)pentaerythritol-diphosphite, bis(2,6-di-t-butyl-4-methoxycarbonylethyl-phenyl)pentaerythritol II Phosphite, bis(2,6-di-t-butyl-4-octadecyloxycarbonylethyl-phenyl)pentaerythritol diphosphite, and the like. Among these, a phosphorus-based antioxidant is preferably a phosphite or a phosphate.

Examples of the thioether-based antioxidant include dilauryl 3,3′-thiodipropionate and bis(2-methyl-4-(3-n-dodecyl)thiopropoxycarbonyl)- 5-t-butylphenyl) sulfide, distearyl 3,3'-thiodipropionate, pentaerythritol-tetrakis(3-lauryl)thiopropionate, and the like.

In the case where the photosensitive adhesive composition contains an antioxidant, the content of the antioxidant is preferably 0.1 to 50 parts by mass, more preferably 0.5 to 30 parts by mass, per 100 parts by mass of the (A) alkali-soluble resin.

Further, examples of the adhesion aid include vinyl trimethoxy decane, vinyl triethoxy decane, 3-glycidoxy propyl trimethoxy decane, and 3-glycidoxy propyl methyl di Oxydecane, 3-glycidoxypropyltriethoxydecane, 5,6-epoxyhexyltriethoxydecane, p-styryltrimethoxydecane, 3-methylpropenyloxypropane Methyldimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-methylpropenyloxypropylmethyldiethoxydecane, 3-methylpropenyloxy Propyltriethoxydecane, 3-propenyloxypropyltrimethoxydecane, bis[3-(triethoxydecyl)propyl]tetrasulfide, bis[3-(triethoxydecane) , propyl] disulfide, 3-isocyanate propyl triethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, benzyl methoxy propyl trimethoxy decane, benzoic acid醯oxypropyl triethoxy decane, 1,6-bis(trimethoxydecyl)hexane, lower Alkenyl trimethoxy decane Alkenyl triethoxy decane, 3-(triethoxydecyl)propyl succinic anhydride, 6-azidosulfonylhexyl triethoxy decane, 2-(3,4-epoxycyclohexyl) Ethyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltriethoxydecane, tris(3-trimethoxydecylpropyl)isocyanurate, [2-(3) -cyclohexenyl)ethyl]trimethoxydecane, [2-(3-cyclohexenyl)ethyl]triethoxydecane, (3-cyclopentadienylpropyl)triethoxydecane , pentyltrimethoxydecane, pentyltriethoxydecane, n-hexyltrimethoxydecane, n-hexyltriethoxydecane, n-octyltrimethoxydecane, n-octyltriethoxydecane,decyl Trimethoxydecane, decyltriethoxydecane, dodecyltrimethoxydecane, dodecyltriethoxydecane, bis(triethoxydecyl)methane, bis(trimethoxydecylalkyl) Ethane, bis(triethoxydecyl)ethane, bis(trimethoxydecyl)hexane, bis(triethoxydecyl)hexane, bis(trimethoxydecyl)octane, Bis(triethoxydecyl)octane, bis(trimethoxydecyl)benzene, bis[(3-methyldi) Oxyalkylene)propyl]polypropylene oxide, polymethoxymethoxyalkyl methacrylate, polyethoxylated methacrylate, trifluoropropyltrimethoxydecane, 1,3-two Methyltetramethoxydioxane, and the like. However, the adhesion aid is not limited to these. These may be used singly or in combination of two or more. By including such a adhesion aid in the photosensitive adhesive composition, the adhesion (adhesion force) of the bonding layer 601 to the semiconductor wafer 20 can be further improved.

In the case where the photosensitive adhesive composition contains the adhesion aid, the content of the adhesion aid is preferably 0.1 to 30 parts by mass, more preferably 0.2 to 20 parts by mass, per 100 parts by mass of the (A) alkali-soluble resin.

Materiality

Next, the physical properties of the photosensitive adhesive composition (physical properties of the subsequent layer 601) will be described in detail.

The elastic modulus of the photosensitive adhesive composition after curing, that is, the adhesive layer 601 at 25 ° C is preferably 2.0 to 3.5 GPa. Further, the elastic modulus of the photosensitive adhesive composition before curing at 25 ° C is preferably 70 to 120% of the elastic modulus of the photosensitive adhesive composition after curing at 25 ° C. Further, the adhesion of the photosensitive adhesive composition before curing to the etching treatment and the ashing treatment to the semiconductor wafer 20 at 25 ° C is preferably 20.0 to 200.0 N. In other words, using a photosensitive adhesive composition, a film is formed on the semiconductor wafer 20 having a size of 4 mm × 4 mm in plan view, without hardening the film (completely hardening), and for a film having an uncured or semi-hardened state (before hardening) When the semiconductor wafer 20 of the photosensitive adhesive composition is subjected to etching treatment and ashing treatment, the adhesion of the film to the semiconductor wafer 20 at 25 ° C is preferably 20.0 to 200.0 N. When the adhesive force is converted into a unit area of the semiconductor wafer 20 in a plan view, it is 1.25 to 12.5 MPa (N/mm ² ).

The elastic modulus at 25 ° C of the photosensitive adhesive composition before curing is compared with that of the photosensitive adhesive composition after curing at 25 ° C The modulus is within a predetermined range, such as a significant deformation of the photosensitive adhesive composition prior to hardening or a decrease in enthalpy flow from the wafer 201. Therefore, the accuracy of the positional overlap of the semiconductor wafer 20 can be improved. Further, since the amount of change in the modulus of elasticity before and after curing is relatively small, the amount of shrinkage accompanying the light is also reduced. As a result, the stress generated at the interface between the adhesion layer 601 and the semiconductor wafer 20 due to the hardening shrinkage can be reduced. From this point of view, it also contributes to improving the reliability of the wafer laminate 200.

On the other hand, the photosensitive adhesive composition before curing which is subjected to the etching treatment and the ashing treatment has sufficient adhesion to the semiconductor wafer 20 for wafer bonding. Therefore, the bonding layer 601 fixes the semiconductor wafers 20 to each other more firmly, contributing to improvement in the reliability of the wafer laminate 200.

By using the photosensitive adhesive composition satisfying the above conditions, the adhesive layer 601 which simultaneously achieves sufficient adhesion and stress relaxation can be easily obtained. In other words, the subsequent layer 601 has a layer protective function (buffer coating function) of the buffer coating film and a subsequent function (wafer bonding function) of the wafer bonding film. Therefore, the wafer laminate 200 can be formed without lowering the reliability of the wafer laminate 200, and the wafer laminate 200 can be thinned compared to the conventional technique using two layers. Further, as the thickness of the wafer laminate 200 is reduced, the volume of the mold portion 50 can be reduced, or the bonding wire 70 can be shortened. This contributes to the reduction in weight and cost.

Further, the photosensitive adhesive composition after curing has a modulus of elasticity at 25 ° C of preferably 2.2 to 3.2 GPa, more preferably 2.4 to 3.0 GPa. In addition, when the elastic modulus of the photosensitive adhesive composition after curing is less than the above lower limit, the adhesion of the adhesive layer 601 is slightly lowered depending on the composition of the photosensitive adhesive composition. Further, when the mold portion 50 contains a filler, the filler may penetrate the adhesive layer 601 to adversely affect the semiconductor wafer 20. On the other hand, if it feels hardened When the elastic modulus of the optical adhesive composition exceeds the above upper limit, the flexibility of the adhesive layer 601 is lowered depending on the composition of the photosensitive adhesive composition, so that the stress relaxation property is lowered. Therefore, for example, it is not possible to alleviate the residual stress caused by the lamination of the semiconductor wafer 20 or the local concentration of the thermal stress accompanying the difference in thermal expansion between the semiconductor wafer 20 and the adhesion layer 601, and the semiconductor wafer 20 may be cracked.

In addition, the elastic modulus of the photosensitive adhesive composition after curing can be obtained, for example, by using an ultra-micro hardness tester ENT-1000 (manufactured by ELIONIX Co., Ltd.), and measuring temperature 25 °C, load 2mN, hold time 1 second, using a Bercovitch indenter (triangular cone, 115° angle) and measured according to ISO14577.

Further, the elastic modulus of the photosensitive adhesive composition after curing can be obtained as the elastic modulus of the coating film 601a after the mounting step.

Further, the elastic modulus of the photosensitive adhesive composition before curing at 25 ° C is more preferably 75 to 115% with respect to the elastic modulus of the photosensitive adhesive composition after curing at 25 ° C, and further Good is set to 80~110%. In addition, when the elastic modulus of the photosensitive adhesive composition before curing is less than the above lower limit value, the adhesiveness of the photosensitive adhesive composition becomes large, but the film of the photosensitive adhesive composition is easily deformed. . As a result, for example, when the semiconductor wafer 20 is temporarily placed in the film, the position of the semiconductor wafer 20 is likely to be shifted, or the photosensitive adhesive composition is discharged from the wafer 201. On the other hand, when the elastic modulus of the photosensitive adhesive composition before curing exceeds the above upper limit value, the adhesiveness is lowered, and it is difficult to temporarily arrange the semiconductor wafer 20. Further, the elastic modulus of the photosensitive adhesive composition before curing can also be measured in the same manner as the elastic modulus of the photosensitive adhesive composition after curing.

Moreover, the elastic modulus of the photosensitive adhesive composition before curing can be used as The elastic modulus of the coating film 601a after the processing step and before the mounting step was determined.

On the other hand, the photosensitive adhesive composition before curing which is subjected to the etching treatment and the ashing treatment has an adhesion force at 25 ° C of the semiconductor wafer 20 of preferably 30 to 180 N (1.875 to 11.25 MPa), and more preferably 40~160N (2.5~10MPa). Further, when the bonding force is lower than the lower limit value, bubbles may easily enter the interface between the bonding layer 601 and the semiconductor wafer 20. On the other hand, when the adhesion force exceeds the above upper limit value, when bubbles enter at the interface between the adhesion layer 601 and the semiconductor wafer 20, it is difficult to eliminate the bubbles.

Further, the adhesion of the photosensitive adhesive composition before curing to the etching treatment and the ashing treatment to the semiconductor wafer 20 can be measured as follows. First, the semiconductor wafers 20 are bonded to each other via the photosensitive adhesive composition of the present invention before the curing by the etching treatment and the ashing treatment to obtain a semiconductor wafer adherend. Thereafter, a wafer adhesive strength of the semiconductor wafer was determined as a bonding force to the semiconductor wafer 20 using a universal adhesive strength tester Dage 4000 (manufactured by Dage Japan Co., Ltd.). The wafer shear strength is such that a semiconductor wafer 20 is pressed from the side (side surface) of the semiconductor wafer via body in the horizontal direction (in the in-plane direction of the semiconductor wafer 20) by a shearing tool, and the joint between the semiconductor wafers 20 is broken. Determined by the intensity of time.

Further, the adhesion of the photosensitive adhesive composition before the curing by the etching treatment and the ashing treatment to the semiconductor wafer 20 can be obtained as the adhesion force of the coating film 601a to the semiconductor wafer 20 after the processing step and before the mounting step. .

In addition, the above-mentioned etching treatment refers to, for example, a process of removing the passivation film on the surface of the semiconductor wafer 20 so that the electrode pads for connecting the bonding wires 70 are exposed. Specifically, a mixed gas of a fluorine compound gas (CF ₄ ), argon (Ar), and oxygen (O ₂ ) is used as a gas, and the output is 2500 W, the time is 6 minutes, and the CF ₄ flow rate/Ar flow rate is used. The etching treatment was carried out under the conditions of /SO ₂ flow rate of 200 sccm /200 sccm /50 sccm.

In addition, the above-mentioned ashing treatment is, for example, a process of removing the treatment residue or the like generated by the etching treatment to purify the surface of the back layer 601 or the surface of the electrode pad. Specifically, a plasma treatment using oxygen (O ₂ ) under the conditions of an output of 600 W, a time of 12 minutes, and an O ₂ flow rate of 200 sccm is used.

Further, such etching treatment and ashing treatment may promote deterioration of the organic material. Therefore, in the case of a coating film (adhesive layer) having low etching resistance and ashing resistance, the semiconductor wafers 20 cannot be sufficiently adhered to each other. On the other hand, the coating film 601a (adhesion layer 601) formed using the photosensitive adhesive composition has sufficient etching resistance and ashing resistance. Therefore, even after such etching treatment and ashing treatment, the adhesion of the coating film 601a can be suppressed from being lowered, and as a result, the adhesion force as described above is exhibited. Therefore, such a photosensitive adhesive composition can be easily used in various processes in the subsequent process without considering the decrease in the adhesiveness. Therefore, the manufacturing process of the semiconductor device 10 can be easily simplified and reduced in cost, which is useful in the above aspects.

Further, the rate of change before and after the treatment step of the elastic modulus of the photosensitive adhesive composition is preferably within a certain range. Therefore, it is preferable to appropriately set the heating conditions in the heating step which are considered to have an influence on the resistance (etching resistance and ashing resistance) of the processing step so that the rate of change is within a certain range.

Specifically, the elastic modulus at 25 ° C after the heating step of the photosensitive adhesive composition and before the treatment step is set to X [GPa], and the elastic modulus at 25 ° C after the treatment step is set to Y [ In the case of GPa], X and Y preferably satisfy the relationship of 0.7≦X/Y≦1.5, and more preferably satisfy the relationship of 0.8≦X/Y≦1.3. The film containing the photosensitive adhesive composition is satisfied by the above-described relationship by the rate of change of the elastic modulus before and after the treatment step 601a has sufficient mechanical properties for maintaining the patterned shape and has sufficient adhesion to the semiconductor wafer 20 for each other. That is, in the processing step of performing the etching treatment and the ashing treatment, the deterioration of the coating film 601a is promoted, but in the case where the rate of change of the elastic modulus before and after the processing step satisfies the above relationship, the coating film 601a sufficiently maintains the pattern. The shape after the formation is fully functioned as the adhesive layer 601 in the mounting step. Therefore, when the rate of change of the elastic modulus before and after the treatment step satisfies the above relationship, the coating film 601a containing the photosensitive adhesive composition can simultaneously function as an etching mask and a function as the adhesive layer 601.

Further, in the above-described processing steps, an etching process and an ashing process which satisfy the above processing conditions are performed.

Further, the minimum melt viscosity of the photosensitive adhesive composition before curing at 100 to 200 ° C is preferably 20 to 500 Pa ‧ . Since such a photosensitive adhesive composition is excellent in wettability to the semiconductor wafer 20, it is not easy to generate voids or the like in the adhesion layer 601. Therefore, a uniform adhesive layer 601 having less unevenness in physical properties can be formed. As a result, when the semiconductor wafer 20 is bonded to each other via the bonding layer 601, local concentration of stress is less likely to occur, and generation of cracks in the semiconductor wafer 20 or occurrence of peeling between the semiconductor wafer 20 and the adhesion layer 601 can be further suppressed. Further, the minimum melt viscosity of the photosensitive adhesive composition before curing can be measured by a rheometer, and can be obtained as the minimum melt viscosity of the coating film 601a after the treatment step and before the mounting step.

Further, the minimum melt viscosity of the photosensitive adhesive composition before curing is preferably from 25 to 400 Pa s, and more preferably from 30 to 300 Pa s.

Further, the photosensitive adhesive composition before curing has a certain adhesiveness, and on the other hand, by performing UV irradiation treatment, the adhesiveness can be lowered. Therefore, the photosensitive adhesive composition before curing can be controlled by the presence or absence of UV irradiation treatment Adhesion (adhesion).

Specifically, the adhesion of the back surface polishing film 90 of the photosensitive adhesive composition before curing will be described. First, a coating film 601a is formed on the wafer 201 using a photosensitive adhesive composition. Next, the coating film 601a is cured (completely cured), and the etching process and the ashing treatment are performed on the wafer 201 having the uncured or semi-hardened coating film 601a (photosensitive adhesive composition before curing). Thereafter, a UV-peeled back surface polishing film 90 was attached to the coating film 601a, and the adhesion of the back surface polishing film 90 to the coating film 601a at 25 ° C was measured. The adhesive force is preferably 3.0 N/25 mm or more. Such a photosensitive adhesive composition can exhibit sufficient adhesion to the back surface polishing film 90 even after being subjected to a treatment for promoting deterioration of the organic material such as etching treatment or ashing treatment. Therefore, for example, when the wafer 201 formed of the coating film 601a having the photosensitive adhesive composition is subjected to the back surface polishing treatment, the wafer 201 can be surely fixed, and the precision of the back surface polishing treatment can be further improved.

Further, the adhesion is more preferably 3.5 N/25 mm or more and 10.0 N/25 mm or less.

Further, the above adhesive force can be measured as follows. First, the back surface polishing film 90 (width: 25 mm, length: 75 mm) of the UV peeling type was bonded so as to be in contact with the coating film 601a of the photosensitive adhesive composition. Next, the measurement temperature was set to 25° C., the peeling speed was set to 10.0±0.2 mm/s, and the peeling angle was 180°, and one end of the longitudinal direction of the back surface polishing film 90 was stretched, and the photosensitive adhesive composition was used. The coating film 601a peels off the back surface polishing film 90. The above adhesion can be obtained by measuring the average value of the load required for the peeling at this time (180° peeling force, unit: N/25 mm, in accordance with JIS Z 0237).

On the other hand, the photosensitive connection before hardening after UV irradiation treatment The adhesion of the primer composition to the back surface polishing film 90 at 50 ° C is preferably 0.5 N / 25 mm or less. Thereby, the adhesion of the photosensitive adhesive composition before curing after the UV irradiation treatment to the back surface polishing film 90 can be sufficiently reduced. Therefore, for example, when the back surface polishing film 90 is peeled off from the coating film 601a of the photosensitive adhesive composition after the back surface polishing treatment, the back surface polishing film 90 can be smoothly peeled off without causing a large load on the coating film 601a. Further, the back surface polishing film 90 can be peeled off under the adhesion of the non-destructive coating film 601a and the semiconductor wafer 20. As a result, for example, when the individual sheets 21 and 22 are picked up after the dicing process, it is possible to prevent defects such as defects in the semiconductor wafer 20.

Further, by reducing the above-described adhesive force after the UV irradiation treatment, it is possible to suppress adhesion of the photosensitive adhesive composition to the dicing blade 110, for example, in the dicing step, or adhesion of the photosensitive adhesive composition to the suction nozzle 121 in the mounting step. . As a result, it is possible to suppress the occurrence of dicing failure or pickup failure.

Further, the adhesion after the UV irradiation treatment is more preferably 0.05 N/25 mm or more and 0.40 N/25 mm or less.

In the UV irradiation treatment, the coating film 601a is irradiated with light having a wavelength of 365 nm through the back surface polishing film 90 so that the integrated light amount is 600 mJ/cm ² .

Further, the UV-peelable back surface polishing film 90 is made of an acrylic resin.

Further, the adhesion force after the UV irradiation treatment can be measured by the photosensitive adhesive composition before the curing treatment and the ashing treatment, and the adhesion of the back surface polishing film 90 to the above-mentioned adhesion at 25 ° C. The measurement method was carried out in the same manner.

The present invention has been described above, but the present invention is not limited thereto. For example, any component may be added to the photosensitive adhesive composition. Further, any structure may be added to the semiconductor device.

[Examples]

Next, a specific embodiment of the present invention will be described.

(Example 1) [1] (A) Synthesis of alkali-soluble resin (cyclic olefin resin A-1)

Several glasswares were prepared and dried at 60 ° C and 0.1 Torr for 18 hours. Thereafter, all glassware was placed in the glove box.

Next, toluene (992 g), dimethoxyethane (116 g), and 1,1-bistrifluoromethyl-2-(bicyclo[2.2.1]heptane were added to one glassware (glassware X). 2-en-5-yl)ethyl alcohol (hereinafter, HFANB) (148 g, 0.54 mol), 3-bicyclo[2.2.1]hept-2-en-2-yl)propionic acid ethyl ester (hereinafter, EPEsNB) (20.7 g, 0.107 mol), 5-((2-(2-methoxyethoxy)ethoxy)methyl)bicyclo[2.2.1]hept-2-ene (hereinafter, NBTON) (61.9 g , 0.274 mol), a mixture containing each monomer was obtained. Thereafter, the mixture was subjected to rinsing (nitrogen flushing) by flowing nitrogen gas while heating at 45 ° C for 30 minutes.

Further, EPEsNB (14.2 g, 0.073 mol) and NBTON (46.7 g, 0.159 mol) were mixed in another glassware (glassware Y), and nitrogen purge was performed. After the completion of the nitrogen purge, bis(toluene)bis(perfluorophenyl)nickel (5.82 g, 0.012 mol) dissolved in 60.5 ml of toluene was placed in the glassware Y. At the same time, it took 3 hours to add the mixture in the above glassware X to the glassware Y at a rate at which the polymerization reaction was carried out to obtain a reaction solution.

Next, the unreacted monomer in the reaction solution was removed by dissolving the reaction solution in a solution of about 1 L of methanol/tetrahydrofuran (THF) (= 4 mol/5 mol). Next, the ester in the reaction solution was hydrolyzed by sodium hydroxide/sodium acetate (=4.8 mol/1 mol) sodium hydroxide solution at 60 ° C for 4 hours to obtain a solution A. Thereafter, methanol (405 g), THF (87 g), acetic acid (67 g), formic acid (67 g), deionized water (21 g) It was added to the solution A and stirred at 50 ° C for 15 minutes. If the stirring is stopped, the solution A will be separated into an aqueous layer and an organic layer, so the aqueous layer of the upper layer is removed, and the organic layer is washed with a solution of methanol/deionized water (=390 g/2376 g) at 60 ° C for 15 minutes. 3 times. Then, the obtained polymer was diluted into propylene glycol methyl ether acetate, and solvent replacement was performed so that the concentration of the polymer became 40%. Thus, a polymer (cyclic olefin resin A-1) in a solution state represented by the formula (7) was obtained.

The yield of the cyclic olefin resin A-1 was 93.1%. The weight average molecular weight (Mw) of the cyclic olefin resin A-1 was 85,900. The molecular weight polydispersity index (PD) of the cyclic olefin resin A-1 was 2.52.

Further, the composition of the cyclic olefin resin A-1 was ¹ H-NMR, and the HFANB was 45.0 mol%, and 2-(bicyclo[2.2.1]hept-2-en-5-yl)propionic acid (hereinafter referred to as EPENB) is 15.0 mol% and NBTON is 40.0 mol%.

(in equation (7), l:m:n=45:15:40)

[2] Production of photosensitive adhesive composition

The cyclic olefin-based resin A-1 (22.0 parts by mass based on the solid content) of the (A) alkali-soluble resin obtained in the above [1], and the photoacid generator B as the photo-acid generator (B) -1 (4.0 parts by mass), epoxy compound C-1 as (C) epoxy compound (5.0 mass) The phenol compound D-1 (3.0 parts by mass) as the (D) phenol compound, the antioxidant E-1 (2.0 parts by mass), the antioxidant E-2 (3.0 parts by mass), and the solvent (solvent) Propylene glycol methyl ether acetate (61.0 parts by mass including propylene glycol methyl ether acetate contained in the solution of the cyclic olefin resin A-1) was mixed to obtain a uniform photosensitive adhesive composition. The material used for the photosensitive adhesive composition of Example 1 is shown below.

<Photoacid generator B-1>

As the photoacid generator B-1, a compound represented by the following formula (8) is prepared.

<epoxy compound C-1>

As the epoxy compound C-1, a compound represented by the following formula (9) is prepared.

<phenol compound D-1>

As the phenol compound D-1, a compound (butyl 4-hydroxybenzoate) represented by the following formula (10) is prepared.

The melting point of the phenol compound D-1 was 70 °C. The weight average molecular weight (Mw) of the phenol compound D-1 was 194. The hydroxyl equivalent of the phenol compound D-1 was 194 g/eq.

<Antioxidant E-1>

As the antioxidant E-1, a compound represented by the following formula (11) (4,4'-bis(?,?-dimethylbenzyl)diphenylamine) is prepared.

<Antioxidant E-2>

As the antioxidant E-2, a compound represented by the following formula (12) (2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol) was prepared.

[化12]

(Examples 2 to 18, Comparative Examples 1 to 4)

The materials constituting the photosensitive adhesive composition were changed as shown in Tables 1 and 2, and the contents of the respective materials were set as shown in Tables 1 and 2, except that the same manner as in Example 1 was carried out. A photosensitive adhesive composition was obtained. In addition, the materials used for the photosensitive adhesive composition of each Example and each comparative example are shown below.

<Cyclic olefin resin A-2>

The compound represented by the following formula (13) is prepared as the cyclic olefin resin A-2 ((A) alkali-soluble resin).

(in equation (13), l:m:n=25:15:60)

<Cyclic olefin resin A-3>

The compound represented by the following formula (14) is prepared as the cyclic olefin resin A-3 ((A) alkali-soluble resin).

(in equation (14), l:m:n=25:35:40)

<phenol compound D-2>

As the phenol compound D-2 ((D) phenol compound), a compound (hexyl hydroxybenzoate) represented by the following formula (15) is prepared.

The melting point of the phenol compound D-2 was 53 °C. The weight average molecular weight (Mw) of the phenol compound D-2 was 222. The hydroxyl equivalent of the phenol compound D-2 was 222 g/eq.

<phenol compound D-3>

As the phenol compound D-3 ((D) phenol compound), a compound (methyl 4-hydroxybenzoate) represented by the following formula (16) is prepared.

The melting point of the phenol compound D-3 was 127 °C. The weight average molecular weight (Mw) of the phenol compound D-3 was 152. The phenolic compound D-3 had a hydroxyl equivalent of 152 g/eq.

<phenol compound D-4>

As the phenol compound D-4 ((D) phenol compound), a compound (2-dodecylphenol) represented by the following formula (17) is prepared.

The melting point of the phenol compound D-4 was 42 °C. The weight average molecular weight (Mw) of the phenol compound D-4 was 262. The hydroxyl equivalent of the phenol compound D-4 was 262 g/eq.

<phenol compound D-5>

As the phenol compound D-5 ((D) phenol compound), a compound (1,8,9-trihydroxyindole) represented by the following formula (18) is prepared.

The melting point of the phenol compound D-5 was 181 °C. The weight average molecular weight (Mw) of the phenol compound D-5 was 226. The hydroxyl equivalent of the phenol compound D-5 was 113 g/eq.

<phenol compound D-6>

As the phenol compound D-6 ((D) phenol compound), a compound (2,2'-dihydroxydiphenylmethane) represented by the following formula (19) is prepared.

The melting point of the phenol compound D-6 was 120 °C. The weight average molecular weight (Mw) of the phenol compound D-6 was 200. The hydroxyl equivalent of the phenol compound D-6 was 100 g/eq.

<phenol compound X-1>

As the phenol compound X-1 ((X) phenol compound), a compound represented by the following formula (20) (4,4'-[(2-hydroxyphenyl)methylene] bis[2-cyclohexyl-) is prepared. 5-methylphenyl]).

The melting point of the phenol compound X-1 was 222 °C. The weight average molecular weight (Mw) of the phenol compound X-1 was 484. The hydroxyl equivalent of the phenol compound X-1 was 161 g/eq.

[Chemistry 20]

<epoxy compound C-2>

An aromatic epoxy compound represented by the following formula (21) is prepared as the epoxy compound C-2.

[3] Production of evaluation test pieces

First, the photosensitive adhesive composition used in each of the examples and the comparative examples was applied onto a tantalum semiconductor wafer, and prebaked at 120 ° C for 5 minutes. Thereby, a coating film was obtained.

Then, the obtained coating film was subjected to heat treatment at 150 ° C for 40 minutes to obtain a semi-cured (before hardening) coating film. Then, the semiconductor wafer having the coating film is sequentially subjected to etching treatment and ashing treatment. The etching treatment uses a mixed gas of a fluorine compound gas (CF ₄ ), argon (Ar), and oxygen (O ₂ ) at an output of 2500 W for 6 minutes, and a CF ₄ flow rate/Ar flow rate/O ₂ flow rate of 200 sccm/ It was carried out under the conditions of 200 sccm / 50 sccm. Further, the ashing treatment was carried out using a mixed gas of O ₂ and Ar at an output of 600 W, a time of 12 minutes, and an O ₂ flow rate of 200 sccm.

Then, another semiconductor wafer is superposed on the coating film, and the temperature is on one side. The film was pressed at a load of 10 N for 5 seconds while heating at 150 °C.

In this manner, test pieces for evaluation in which two semiconductor wafers were formed via an adhesive layer were produced.

[4] Evaluation of photosensitive adhesive composition and evaluation test piece [4.1] Evaluation of the follow-up [4.1.1] Evaluation of adhesion during development

First, the photosensitive adhesive composition used in each of the examples and the comparative examples was applied onto a tantalum semiconductor wafer, and prebaked at 120 ° C for 5 minutes. Thereby, a coating film having a thickness of 10 μm was obtained.

Then, the obtained coating film was subjected to exposure treatment through a mask having a line width of 100 μm and a gap pattern. This exposure treatment was carried out by irradiating light having a wavelength of 365 nm and a light intensity of 5 mW/cm ² in air for each portion of one coating film at different times.

Then, the coating film subjected to the exposure treatment was developed with an alkaline developer (2.38% aqueous solution of tetramethylammonium hydroxide) at 23 ° C for 40 seconds, and then rinsed with pure water for 20 seconds. The coating film (adhesive layer) having an opening having a width of 100 μm after development was observed by an optical microscope, and the degree of peeling of the coating film from the semiconductor wafer (whether or not the pattern was peeled off) was evaluated based on the following evaluation criteria.

<Evaluation criteria>

A: The entire coating film was not peeled off from the semiconductor wafer.

B: Less than 30% of the coating film was peeled off from the semiconductor wafer.

C: 30% or more of the coating film and less than 50% were peeled off from the semiconductor wafer.

D: 50% or more of the coating film was peeled off from the semiconductor wafer.

Further, in Comparative Examples 1, 2, and 4, since the pattern having a width of 100 μm could not be opened, the evaluation of the adhesion could not be performed at the time of development. Further, in Comparative Example 3, 50% or more of the coating film was peeled off from the semiconductor wafer, and the desired pattern could not be opened.

[4.1.2] Evaluation of strength

With respect to the obtained test piece for evaluation, a semiconductor wafer was pressed in the horizontal direction from the side (side surface) of the semiconductor wafer by using a Dage 4000 (manufactured by Dage Japan Co., Ltd.), and the joint surface fracture between the wafers was measured. The wafer shear strength around the wafer. The wafer size is 4 mm x 4 mm. Then, the measured wafer shear strength was evaluated based on the following evaluation criteria.

<Evaluation criteria>

A: The wafer shear strength is very high.

B: The wafer shear strength is high.

C: The wafer shear strength is low.

D: The wafer shear strength is very low.

Further, in Comparative Example 4, the coating film (adhesive layer) was peeled off from the semiconductor wafer, and the evaluation of the adhesion strength could not be performed.

[4.2] Evaluation of secondary processability

First, the photosensitive adhesive composition used in each of the examples and the comparative examples was applied onto a tantalum semiconductor wafer, and prebaked at 120 ° C for 5 minutes. With this, A coating film was obtained.

Then, the obtained coating film was subjected to heat treatment at 150 ° C for 40 minutes. Then, the semiconductor wafer on which the coating film was formed after the heat treatment was immersed in propylene glycol-1-monomethyl ether-2-acetate, and left for 20 hours.

Then, the semiconductor wafer was taken out from propylene glycol-1-monomethyl ether-2-acetate, and the presence or absence of the coating film residue was visually observed, and the secondary workability was evaluated based on the following evaluation criteria.

<Evaluation criteria>

A: No residue of the coating film was found at all.

B: The residue of the coating film was slightly found.

C: More residue of the coating film was found.

D: The coating film was hardly removed.

[4.3] Evaluation of the photosensitivity of photosensitive adhesive compositions

First, the photosensitive adhesive composition used in each of the examples and the comparative examples was applied onto a tantalum semiconductor wafer, and prebaked at 120 ° C for 5 minutes. Thereby, a coating film having a thickness of 10 μm was obtained.

Then, the obtained coating film was subjected to exposure treatment through a mask having a line width of 100 μm and a gap pattern. This exposure treatment was carried out by irradiating light having a wavelength of 365 nm and a light intensity of 5 mW/cm ² in air for each coating film while changing the time.

Then, the coating film subjected to the exposure treatment is subjected to development processing. Then, the minimum exposure amount (unit: mJ/cm ² ) when the residual film ratio of the unexposed portion defined as follows is 90% or more and the residual film ratio of the exposed portion is 0% is obtained.

Residual film rate of unexposed part = 100 × film thickness after development of unexposed part / film thickness after prebaking

Residual film rate of exposed portion = 100 × film thickness after development of exposed portion / film thickness after prebaking

The obtained exposure amount is shown in Table 1.

Further, the coating film of each of the comparative examples did not cause a photoreaction at the time of exposure, and the coating film could not be removed by the development treatment. Therefore, regarding the coating film of each comparative example, the evaluation of the photosensitivity (measurement of the exposure amount) could not be performed.

[4.4] Evaluation of Residual Film Rate (Residual Rate) of Photosensitive Adhesive Composition

First, in the same manner as in [4.3], the coating film subjected to the exposure treatment was prepared for each of the examples and the comparative examples. Then, the coating film subjected to the exposure treatment was subjected to development treatment, and then heat treatment was performed at 150 ° C for 40 minutes. Then, the residual film ratio of the unexposed portion defined as follows was determined.

Residual film rate = 100 × film thickness after development of unexposed portion / film thickness after prebaking

The residual film ratios obtained are shown in Table 1.

Further, the coating film of each of the comparative examples did not cause a photoreaction at the time of exposure, and the coating film could not be removed by the development treatment. Therefore, the evaluation of the residual film ratio of the coating film of each comparative example was impossible.

As is apparent from Tables 1 and 2, in the photosensitive adhesive composition and the test piece for evaluation of each of the examples, bubbles remaining on the interface with the semiconductor wafer were suppressed, and it was confirmed that there was sufficient between the semiconductor wafer and the adhesive layer. Then force (close contact force). Further, the coating film (adhesive layer) used in each of the examples after the heat treatment has sufficient solubility to the organic solvent, that is, the so-called secondary workability is good. Further, it was confirmed that the test piece for evaluation of each of the examples had a high residual ratio of the unexposed portion. Further, the semiconductor device including the laminated semiconductor device in which the semiconductor elements are bonded to each other by the cured material of the photosensitive adhesive composition of each of the examples has high reliability. On the other hand, as described in the above [4.3], the coating film formed using the photosensitive adhesive composition of each comparative example cannot be removed by the development treatment. Therefore, a semiconductor device having a laminated semiconductor element cannot be obtained.

(industrial availability)

By using the cured product of the photosensitive adhesive composition of the present invention as an adhesive layer next to the semiconductor elements, bubbles (voids) can be reduced at the interface between the semiconductor element and the adhesive layer, and even if bubbles are generated at the interface, The resulting bubbles can be removed. As a result, the adhesion (adhesiveness) of the semiconductor elements can be improved. Therefore, the present invention has industrial applicability.

Claims (11)

A photosensitive adhesive composition for bonding a semiconductor element and a member to be joined, comprising: (A) an alkali-soluble resin, (B) a photoacid generator, (C) an epoxy compound, and (D) A phenolic compound having a melting point of 50 to 150 °C. The photosensitive adhesive composition of claim 1, wherein the (D) phenol compound comprises at least one of a phenol compound having a substituent containing an aliphatic hydrocarbon group and a phenol compound having a plurality of phenol skeletons. The photosensitive adhesive composition of claim 2, wherein the phenol compound having a substituent containing an aliphatic hydrocarbon group has a hydroxyl equivalent of from 150 to 250 g/eq. The photosensitive adhesive composition of claim 1, wherein the (A) alkali-soluble resin contains a cyclic olefin resin. The photosensitive adhesive composition of claim 4, wherein the cyclic olefin resin comprises a lowering An olefinic resin. The photosensitive adhesive composition of claim 1, wherein the (A) alkali-soluble resin has a linear substituent having 2 to 30 carbon atoms. The photosensitive adhesive composition of claim 6, wherein the linear substituent comprises an alkyl ether structure. The photosensitive adhesive composition according to claim 6, wherein the linear substituent is a group represented by the following formula (1), [Chem. 21] (In the formula (1), z is an integer of 1 or more and 10 or less). The photosensitive adhesive composition according to claim 6, wherein the (A) alkali-soluble resin contains 20 to 60 mol% of a repeating unit having the linear substituent. The photosensitive adhesive composition of claim 1, wherein the (C) epoxy compound has two or more glycidyl groups. A semiconductor device including a laminated semiconductor device, wherein the stacked semiconductor device includes a plurality of semiconductor elements, and any of claims 1 to 10 which are provided between the semiconductor elements and are bonded thereto A cured product of a photosensitive adhesive composition.