JP7021685B2 - Photosensitive adhesive compositions and semiconductor devices - Google Patents

Description

The present invention relates to photosensitive adhesive compositions and semiconductor devices.

The degree of integration of semiconductor devices has increased year by year according to the prediction called Moore's Law. However, in recent years, the miniaturization of the structure formed in the semiconductor element has approached the physical limit, and the pace of high integration of the semiconductor device has slowed down. Therefore, instead of increasing the density of one semiconductor element, a method has been proposed in which a plurality of semiconductor elements are laminated to increase the apparent degree of integration of the semiconductor device.

The lamination of the plurality of semiconductor elements is performed, for example, by adhering the semiconductor elements (silicon pieces) to each other via a film-like adhesive (see, for example, Patent Document 1).

Recently, with the widespread use of mobile devices, for example, in addition to highly integrated semiconductor devices, it is desired to reduce the size and thickness of semiconductor devices. Therefore, in a semiconductor device having a structure in which a plurality of semiconductor elements are laminated as described above, the thickness of each semiconductor element is becoming thinner.

A thin-walled semiconductor element can be formed by etching a wafer to be a semiconductor element to reduce the thickness. Then, this etching is performed in a state where a film-like adhesive is adhered to the wafer in order to prevent the wafer from being damaged.

Japanese Unexamined Patent Publication No. 2004-051970

However, the present inventor has found that when the etching time is long during etching as described above, 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 bonded to each other via a film-like adhesive after the wafer is separated into individual pieces, the adhesiveness (adhesion) between the semiconductor elements is lowered due to the bubbles. As a result, the reliability of the semiconductor device may decrease.

An object of the present invention is a photosensitive adhesive composition capable of enhancing the adhesiveness (adhesion) between semiconductor elements or the adhesiveness (adhesion) between a semiconductor element and a member to be joined, such a photosensitive adhesive composition. It is an object of the present invention to provide a highly reliable semiconductor device provided with a laminated semiconductor element in which semiconductor elements are bonded to each other by a cured product of the above, and a highly reliable semiconductor device in which a semiconductor element and a member to be joined are bonded.

Such an object is achieved by the present invention of the following (1) to (14).
(1) (A) An alkali-soluble resin composed of a norbornene-based resin, and
(B) Photoacid generator and
(C) An epoxy compound containing two or more glycidyl groups in the molecule (excluding organosilicon compounds having an epoxy structure) and
(D) A phenol compound having a melting point of 50 to 150 ° C., a substituent containing an alkyl chain (-CH _2- ) _n (where n is 1 to 6), and a hydroxyl group equivalent of 150 to 250 g / eq. When,
(X) Phenolic compound A phenol compound having a melting point higher than that of (D),
A photosensitive adhesive composition comprising.
(2) (A) An alkali-soluble resin composed of a norbornene-based resin, and
(B) Photoacid generator and
(C) An epoxy compound containing two or more glycidyl groups in the molecule (excluding organosilicon compounds having an epoxy structure) and
(D) A phenol compound having a melting point of 50 to 150 ° C., a plurality of phenol skeletons, and a hydroxyl group equivalent of 50 to 150 g / eq.
(X) Phenolic compound A phenol compound having a melting point higher than that of (D),
A photosensitive adhesive composition comprising.

(3) The photosensitive adhesive composition according to (2) above, wherein the plurality of phenol skeletons of the (D) phenol compound form a linked polycyclic structure .

(4) The photosensitive adhesive composition according to any one of (1) to (3) above, wherein the (X) phenol compound has a melting point of 151 to 250 ° C.

(5) The photosensitive adhesive composition according to any one of (1) to (4) above, wherein the (X) phenol compound contains a phenol compound having a plurality of phenol skeletons.

(6) The photosensitive adhesive composition according to (5) above, wherein the phenol compound having a plurality of phenol skeletons is a substituent containing a cyclic structure and has at least one substituent bonded to the phenol skeleton. ..

(7) The photosensitive adhesive composition according to any one of (1) to (6) above, wherein the alkali-soluble resin (A) has an acidic group.

(8) (A) An alkali-soluble resin composed of a norbornene-based resin and having a linear substituent having 2 to 30 carbon atoms, and an alkali-soluble resin.
(B) Photoacid generator and
(C) An epoxy compound containing two or more glycidyl groups in the molecule (excluding organosilicon compounds having an epoxy structure) and
(D) It has a melting point of 50 to 150 ° C. and an alkyl chain (-CH). ₂ -) _n A phenol compound having a substituent (where n is 1 to 6) and having a hydroxyl group equivalent of 150 to 250 g / eq.
A photosensitive adhesive composition comprising.
(9) (A) An alkali-soluble resin composed of a norbornene-based resin and having a linear substituent having 2 to 30 carbon atoms, and an alkali-soluble resin.
(B) Photoacid generator and
(C) An epoxy compound containing two or more glycidyl groups in the molecule (excluding organosilicon compounds having an epoxy structure) and
(D) A phenol compound having a melting point of 50 to 150 ° C., a plurality of phenol skeletons, and a hydroxyl group equivalent of 50 to 150 g / eq.
A photosensitive adhesive composition comprising.

(10) The photosensitive adhesive composition according to (8) or (9) above, wherein the linear substituent contains an alkyl ether structure.

(11) The photosensitive adhesive composition according to any one of (8) to (10) above, wherein the linear substituent is a group represented by the following formula (1).

（式（１）中、ｚは、１以上１０以下の整数である。）

(In equation (1), z is an integer of 1 or more and 10 or less.)

(12) The photosensitive adhesive composition according to any one of (8) to (11) above, wherein the alkali-soluble resin (A) contains 20 to 60 mol% of the repeating unit having the linear substituent. ..

(13) A semiconductor device including a laminated semiconductor element.
The laminated semiconductor element is
With multiple semiconductor devices,
The cured product of the photosensitive adhesive composition according to any one of (1) to (12) above, which is provided between the semiconductor elements and joins them.
A semiconductor device characterized by having.
(14) Semiconductor elements and
With the member to be joined,
The cured product of the photosensitive adhesive composition according to any one of (1) to (12) above, which is provided between the semiconductor element and the member to be joined and joins them.
A semiconductor device characterized by having.

By using the cured product of the photosensitive adhesive composition of the present invention as an adhesive layer for adhering semiconductor elements to each other or between a semiconductor element and a member to be bonded, bubbles (voids) are generated at the interface between the semiconductor element and the adhesive layer. It is possible to reduce the amount of air bubbles, and even if air bubbles are generated at the interface, the generated air bubbles can be removed. Therefore, it is possible to improve the adhesiveness (adhesiveness) between the semiconductor elements or the adhesiveness (adhesiveness) between the semiconductor element and the member to be joined.

Further, according to the present invention, a highly reliable semiconductor device including a laminated semiconductor element having high adhesiveness between semiconductor elements can be obtained.
Further, according to the present invention, it is possible to obtain a highly reliable semiconductor device having high adhesiveness between the semiconductor element and the member to be joined.

FIG. 1 is a cross-sectional view showing an example of the semiconductor device of the present invention. FIG. 2 is a diagram for explaining a method of manufacturing the semiconductor device shown in FIG. 1. FIG. 3 is a diagram for explaining a method of manufacturing the semiconductor device shown in FIG. 1. FIG. 4 is a diagram for explaining a method of manufacturing the semiconductor device shown in FIG. 1. FIG. 5 is a diagram 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 the preferred embodiments shown in the accompanying drawings.

<Semiconductor device>
First, an example of the semiconductor device of the present invention will be described.

FIG. 1 is a cross-sectional view showing an example of the semiconductor device of the present invention.
The semiconductor device 10 shown in FIG. 1 is an example having a BGA (Ball Grid Array) type semiconductor package. The semiconductor device 10 includes a plurality of stacked semiconductor chips 20 (semiconductor elements), an adhesive layer 601 for adhering the semiconductor chips 20 to each other, a package substrate 30 for supporting the semiconductor chips 20, a semiconductor chip 20 and a package substrate 30. It has an adhesive layer 101 for adhering the semiconductor chip 20, a mold portion 50 for sealing the semiconductor chip 20, and a solder ball 80 provided below the package substrate 30. Hereinafter, the configuration of each part will be described in detail in order.

The semiconductor chip 20 may be any kind of element, for example, a NAND (Not AND) flash memory, a memory element such as a DRAM (Dynamic Random Access Memory), an IC (Integrated Circuit), or an LSI (Large Scale Integration). Such integrated circuit elements and the like can be mentioned.

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

The plurality of semiconductor chips 20 are laminated so as to be slightly offset from each other in the in-plane direction, thereby forming a chip laminate 200 (laminated semiconductor element). Further, the semiconductor chips 20 are bonded to each other via the adhesive layer 601. The adhesive layer 601 is also provided on the upper surface of the chip laminate 200. Further, the adhesive layer 601 is composed of a cured product (photosensitive adhesive composition after curing) of the photosensitive adhesive composition of the present invention. The photosensitive adhesive composition will be described in detail later.

The package substrate 30 shown in FIG. 1 is a build-up substrate including a core substrate 31, an insulating layer 32, a solder resist layer 33, a wiring 34, and a conduction via 35.

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

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

Further, the wiring 34 and the conduction via 35 are transmission lines for electric signals, respectively, and are made of a metal material such as a simple substance or an alloy of Au, Ag, Cu, Al, and Ni, respectively.

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

The chip laminate 200 formed by laminating a plurality of semiconductor chips 20 is placed on the upper surface of the package substrate 30. The chip laminate 200 and the package substrate 30 are adhered to each other by an adhesive 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 and constitutes an exposed portion. The exposed portion and the electrode portion of each semiconductor chip 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 chip laminate 200 and also cover the entire upper surface of the package substrate 30. Thereby, the chip laminate 200 can be protected from the external environment. Such a mold portion 50 is made of various resin materials such as an epoxy resin and a phenol resin, for example.

<Manufacturing method of semiconductor devices>
Next, a method for manufacturing the semiconductor device 10 will be described.

2 to 5 are diagrams for explaining the manufacturing method of the semiconductor device shown in FIG. 1, respectively. In the following description, for convenience of explanation, the upper part of FIGS. 2 to 5 is referred to as "upper" and the lower part is referred to as "lower".

The method for manufacturing the semiconductor device 10 includes a coating step of applying a liquid containing a photosensitive adhesive composition on a wafer (semiconductor substrate) to obtain a coating film, an exposure step of exposing the obtained coating film, and development. A development process for patterning a coating film, a processing process for etching and ashing a wafer provided with a coating film, a back grind process for grinding the back surface of the wafer, and dying the wafer into multiple semiconductor chips. It has a dicing process for unifying, and a mounting process for picking up a semiconductor chip and mounting it on a package substrate, and then picking up another semiconductor chip and crimping it onto the previously mounted semiconductor chip (bonded member). .. Hereinafter, each step will be described in sequence.

[1] Coating Step First, a wafer 201 (see FIG. 2A) for cutting out the semiconductor chip 20 is prepared, and a liquid containing a photosensitive adhesive composition is coated on the wafer 201 (on one side). As a result, as shown in FIG. 2B, the coating film 601a is formed on the wafer 201. A semiconductor circuit, an electrode pad, or the like is formed in advance on the wafer 201 corresponding to each semiconductor chip 20. That is, the wafer 201 is used in the so-called pre-process of the semiconductor manufacturing process. Therefore, a plurality of semiconductor chips 20 can be cut out from the wafer 201 by cutting the wafer 201 in a step described later and disassembling the wafer 201 into individual pieces.

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.

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

The liquid containing the photosensitive adhesive composition is prepared by appropriately adding a solvent or the like capable of dissolving the photosensitive adhesive composition of the present invention to the photosensitive adhesive composition. Further, it is preferable that the solvent to be used can be removed by volatilization when heated in the step described later. Specifically, such solvents include toluene, xylene, benzene, dimethylformamide, tetrahydrofuran, ethyl cellosolve, ethyl acetate, N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, dimethylsulfoxide, and diethylene glycol. Dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl lactate, ethyl lactate, butyl lactate, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, methyl-1,3-butylene glycol Examples thereof include acetate, 1,3-butylene glycol-3-monomethyl ether, methyl pyruvate, ethyl pyruvate, methyl-3-methoxypropionate, etc., and one or a combination of two or more of these may be used. can. Among these, a solvent containing any one of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, γ-butyrolactone and cyclohexanone is particularly preferable because of its high solubility and easy removal by volatilization.

[2] Exposure Step Next, a mask 4 is provided so as to be in contact with the coating film 601a formed on the wafer 201, and an exposure treatment is performed on a desired region (exposure region) of the coating film 601a (see FIG. 2C). As a result, a photoreaction occurs in the coating film 601a in the exposed region, and patterning is potentially performed (a latent image is formed).

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

In this exposure step, a mask provided away from the coating film 601a may be used instead of the mask 4 provided in contact with the coating film 601a. When X-rays or electron beams with high directivity are used for the exposure process, the use of the mask can be omitted.

The exposure amount in the exposure process is appropriately set according to the thickness of the coating film 601a, the sensitivity of the photosensitive adhesive composition, and the like, but is preferably about 30 to 3000 mJ / cm ² as an example.

[3] Development Step Next, the coating film 601a that has been exposed is subjected to a development treatment. As a result, the exposed portion (exposed area of the coating film 601a) is removed, and the desired patterning is applied as shown in FIG. 2 (d). By such a development process, for example, an electrode pad for connecting the bonding wire 70 to the semiconductor chip 20 can be exposed. In addition, the coating film 601a on the dicing line that becomes a cutting margin in the dicing step described later can be removed.

In the developing process, the developer is brought into contact with the exposed coating film 601a. As a result, the coating film 601a in the exposed portion is dissolved in the developing solution and removed. As a result, the opening 601b is formed in the coating film 601a. Examples of the developer include alkali metal carbonates, alkali metal hydroxides, alkaline developers such as tetraammonium hydroxide, and organic developers such as dimethylformamide and N-methyl-2-pyrrolidone. Can be mentioned. Among these, an alkaline developer is particularly preferably used as the developer. The alkaline developer has the characteristics that the load on the environment is small and the residue is unlikely to be generated.

Moreover, as a method of supplying a developer, for example, a method such as a spray, a paddle, a dipping, an ultrasonic wave and the like can be mentioned.

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

[4] Treatment Step Next, the wafer 201 provided with the coating film 601a is subjected to an etching treatment. At this time, the coating film 601a provided with the opening 601b functions as an etching mask. As a result, the surface (upper surface) of the wafer 201 in the region corresponding to the opening 601b is selectively etched. As a result, if a passivation film is formed on the surface of the wafer 201, it can be removed and the electrode pad for connecting the bonding wire 70 can be exposed.

Examples of the etching process include a plasma etching process (dry etching process) by supplying plasma to the wafer 201, various wet etching processes, and the like, as shown in FIG. 3 (f). The plasma etching treatment can be performed under generally known conditions, and for example, the treatment gases are fluorine compound gas (CF ₄ , CHF ₃ ), fluorine compound gas (CF ₄ , CHF ₃ ) and oxygen gas (O). Using a mixture gas with ₂ ) or a mixture gas of fluorine compound gas (CF ₄ , CHF ₃ ) and argon gas (Ar), the output is 200 to 2000 W, the time is 0.2 to 15 minutes, and the gas flow rate is 50. It can be performed under the condition of ~ 1000 sccm.

Then, if necessary, the wafer 201 provided with the coating film 601a is subjected to an ashing treatment. As a result, the treatment residue and the like generated by the etching treatment can be removed, and the surface of the coating film 601a and the surface of the electrode pad can be cleaned. As a result, it is possible to increase the adhesive force of the adhesive layer 601 described later and increase the bonding force of the bonding wire 70 to the electrode pad.

Examples of the ashing treatment include plasma treatment, wet treatment using a chemical, and the like. For the plasma treatment, for example, oxygen gas (O ₂ ), a mixed gas of oxygen gas (O ₂ ) and argon gas (Ar) or the like is used as the treatment gas, the output is 200 to 2000 W, and the treatment time is 0.2 to 15. The gas flow rate can be 50 to 1000 sccm.

[5] Backgrinding Step Next, as shown in FIG. 3 (g), the backgrinding film 90 is attached onto the coating film 601a. The back grind film 90 supports the wafer 201 during the back grind treatment, and suppresses the occurrence of defects such as chipping and cracking in the wafer 201.

Next, the back surface (the other surface side) of the wafer 201 is ground (back grind processing). As a result, the broken line portion in FIG. 3 (h) is removed, and the thickness of the wafer 201 can be reduced. By backgrinding, the thickness of the wafer 201 can be reduced to about 20 to 100 μm, although it depends on the thickness of the original wafer 201.
For the back grind processing, for example, a device called a back grinding wheel is used.

By cutting the coating film 601a obtained from the photosensitive adhesive composition of the present invention, it is possible to cut out the adhesive layer 601 that exhibits sufficient adhesive force with the semiconductor chip 20. In addition, the coating film 601a obtained from the photosensitive adhesive composition of the present invention exhibits sufficient adhesive strength to the backgrinding film 90. Therefore, by attaching the back grind film 90 on the coating film 601a, the back grind film 90 can surely support the coating film 601a and the wafer 201. As a result, the position of the wafer 201 with respect to the back grind film 90 does not shift during the back grind processing, so that the back grind processing with high accuracy can be performed on the wafer 201. Therefore, it is possible to suppress the variation in the thickness of the wafer 201. As a result, it is possible to obtain a semiconductor chip 20 in which tilting or the like is unlikely to occur when laminated.

Further, in the case of the present embodiment, the coating film 601a is formed on the wafer 201 to be subjected to the back grind step, and the back grind treatment is performed in that state. As described above, the coating film 601a has mechanical properties that can reliably bond the semiconductor chips 20 to each other. Therefore, the coating film 601a also has a function of mechanically supporting the wafer 201 by interposing between the wafer 201 and the back grind 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 applying the back grind treatment to the wafer 201 provided with the coating film 601a, more uniform treatment becomes possible.

As the back grind film 90, a UV peeling type back grind film can be used. By using such a backgrinding film 90, when the backgrinding film 90 is peeled off from the coating film 601a after the backgrinding treatment, the backgrinding film is simply subjected to UV irradiation treatment on the coating film 601a via the backgrinding film 90. The adhesive force between the 90 and the coating film 601a can be significantly reduced. As a result, the backgrind film 90 can be smoothly peeled off from the coating film 601a without imposing a large burden on the coating film 601a.

[6] Dicing Step Next, the wafer 201 is subjected to a dicing process. As a result, the wafer 201 is separated (separated) into a plurality of semiconductor chips 20.

The dicing process is performed in a state where the wafer 201 is attached to a dicing die attach film or a dicing film. This dicing die attach 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 surface side of the wafer 201 ground in the back grind step, respectively. Note that FIG. 3 (i1) illustrates a wafer 201 or the like for cutting out a semiconductor chip 20 used for the lowermost layer (the layer closest to the package substrate 30) of the chip laminate 200. On the other hand, FIG. 3 (i2) illustrates a wafer 201 or the like for cutting out a semiconductor chip 20 used for a layer other than the bottom layer of the chip laminate 200.

In FIG. 3 (i1), the dicing die attach film 100, which is a laminate of the dicing film 100a and the dicing 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 FIGS. 4 (j1) and 4 (j2), the back grind film 90 is peeled off from the coating film 601a.

Next, the wafer 201 provided with the coating film 601a is subjected to a dicing process. The dicing process is performed so that the dicing blade 110 reaches the dicing film 100a as shown in FIGS. 4 (k1) and 4 (k2). As a result, the coating film 601a, the wafer 201, and the die attach film 100b are individually separated, and as shown in FIG. 4 (k1), the adhesive layer 601, the semiconductor chip 20 (first semiconductor element), and the adhesive layer 101 are laminated. The piece 21 is cut out. Similarly, the coating film 601a and the wafer 201 are individually separated, and as shown in FIG. 4 (k2), the individual pieces 22 formed by laminating the adhesive layer 601 and the semiconductor chip 20 (second semiconductor element) are cut out. ..

In this embodiment, one wafer 201 (a junction of a plurality of semiconductor chips 20) is subjected to a dicing process to cut out a plurality of semiconductor chips 20. However, the present invention is not limited to this, and for example, a plurality of semiconductor chips 20 that have been individually separated may be used. In this case, the dicing step can be omitted. Further, when the wafer 201 or the semiconductor chip 20 is thin from the beginning, the back grind step can be omitted.

Further, the process order of the back grind process and the dicing process is not limited to the above-mentioned order, and the order may be interchanged. That is, the wafer 201 may be subjected to a dicing process and then a back grind process.

[7] Mounting Process FIGS. 4 (L1) and 4 (L2) are diagrams showing an example in which the cut pieces 21 and the pieces 22 are picked up by the collet 121 of the bonding device 120, respectively.

First, the individual pieces 21 are picked up by the collet 121 of the bonding device 120 and crimped (mounted) on the package substrate 30 as shown in FIG. 5A. At this time, the back surface of the semiconductor chip 20 and the package substrate 30 are adhered to each other via the adhesive layer 101. The adhesive layer 101 is formed by individualizing the die attach film 100b. However, the adhesive layer 101 may be formed of, for example, an uncured or semi-cured product of the photosensitive adhesive composition of the present invention (a photosensitive adhesive composition that has not been completely cured). In this case, the package substrate 30 also corresponds to a non-bonded member bonded to the semiconductor element 20. That is, the photosensitive adhesive composition of the present invention is used not only for bonding the semiconductor element 20 and the semiconductor element (bonded member) 20, but also for bonding the semiconductor element 20 and the package substrate (bonded member) 30. be able to. The members to be joined are not limited to these.

Subsequently, the individual piece 22 is crimped onto the previously mounted individual piece 21. As a result, as shown in FIG. 5B, two semiconductor chips 20 can be laminated via the adhesive layer 601. After that, by repeating this step, as shown in FIG. 5C, a chip laminate 200 formed by laminating a large number of semiconductor chips 20 can be obtained. At this time, by stacking the semiconductor chips 20 while shifting their positions from each other, it is possible to secure a region (a region corresponding to the opening 601b of the coating film 601a) in which the bonding wire 70 is connected in the semiconductor chip 20. That is, the electrode portion of the semiconductor chip 20 can be exposed by laminating the semiconductor chips 20 while shifting the positions of the semiconductor chips 20 from each other.

Further, when mounting the semiconductor chip 20, the adhesive layer 601 is heated. As a result, the adhesive layer 601 exhibits sufficient adhesive force, and the semiconductor chips 20 can be firmly adhered 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.

After that, the electrode portion of each semiconductor chip 20 and the exposed portion of the wiring 34 of the package substrate 30 are connected by a bonding wire 70 as shown in FIG. 5D.

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

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

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

The method for manufacturing a semiconductor device of the present invention may include a heating step between the above-mentioned [3] developing step and [4] processing step. In this heating step, the developed coating film 601a is heated (see FIG. 2E). As a result, a predetermined curing reaction (thermosetting reaction) occurs in the photosensitive adhesive composition constituting the coating film 601a. As a result, the photosensitive adhesive composition is slightly cured (semi-cured), and the adhesiveness 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. The heating time is appropriately set according to the heating temperature, but is preferably 35 to 120 minutes, more preferably 40 to 100 minutes. This optimizes the mechanical properties such as the elastic modulus of the coating film 601a, and imparts sufficient resistance to the etching treatment and the ashing treatment to the coating film 601a.

Further, the coating film 601a is formed of the photosensitive adhesive composition of the present invention, and the adhesive layer 601 formed from such a coating film 601a exhibits relatively high solubility in an organic solvent. Therefore, for example, even when it becomes necessary to remove the coating film 601a after forming the coating film 601a on the wafer 201, the coating film 601a is efficiently dissolved while suppressing the generation of residues (residues). , Can be removed. Therefore, the wafer 201 can be used (reworked) again in the bonding process without wasting it. As a result, the process yield of the semiconductor device 10 can be improved.

The method for manufacturing a semiconductor device may include a step of irradiating the entire surface of the coating film with light (light irradiation step) in addition to the heating step or instead of the heating step.

<Photosensitive adhesive composition>
Next, the 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 that serves as a base material for the adhesive layer 601. Further, the photosensitive adhesive composition contains (A) an alkali-soluble resin, so that the adhesive force (adhesive force) of the adhesive layer 601 to the semiconductor chip 20 can be enhanced. Therefore, the adhesive layer 601 can bond the semiconductor chips 20 to each other more firmly. Further, when the photosensitive adhesive composition contains (A) an alkali-soluble resin, the coating film 601a can be imparted with solubility in an alkali developer. Therefore, an alkaline developing solution having a small environmental load can be used, and the environmental load in the developing process can be reduced.

Specific examples of the (A) alkali-soluble resin include phenol-based resins, acrylic-based resins, cyclic olefin-based resins, polyamide-based resins, polyimide-based resins, polyvinylphenol-based resins, and the like, and one of these is mentioned. Species or a combination of two or more can be used. Among these, the (A) alkali-soluble resin is particularly preferably a cyclic olefin resin. Examples of the cyclic olefin-based resin include norbornene-based resins and benzocyclobutene-based resins. Among these, the norbornene-based resin is preferable as the cyclic olefin-based resin. By using a photosensitive adhesive composition containing a cyclic olefin resin, it is possible to obtain an adhesive layer 601 having particularly excellent adhesive force to the semiconductor chip 20. In particular, by using a photosensitive adhesive composition containing a norbornene-based resin, the adhesive force of the adhesive layer 601 to the semiconductor chip 20 can be further enhanced. Further, since the norbornene-based resin has high hydrophobicity, it is possible to form an adhesive layer 601 that is unlikely to cause dimensional changes due to water absorption by using a photosensitive adhesive composition containing the norbornene-based resin.

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

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

Structures derived from cyclic olefins include monocyclics such as cyclohexene and cyclooctene, norbornene, norbornadiene, dicyclopentadiene, dihydrodicyclopentadiene, tetracyclopentadiene, tricyclopentadiene, dihydrotricyclopentadiene, and tetracyclopentadiene. Examples thereof include structures derived from polycyclic bodies such as dihydrotetracyclopentadiene. Among these, as the structure derived from the cyclic olefin, the structure derived from norbornene is particularly preferable. The structure derived from norbornene contributes to the improvement of the adhesive force of the adhesive layer 601 to the semiconductor chip 20. The structure derived from norbornene also contributes to improving the heat resistance of the photosensitive adhesive composition and the flexibility of the photosensitive adhesive composition after curing.

Examples of the substituent having an acidic group include a carboxyl group, a phenolic hydroxyl group, a substituent having -C (OH)-(CF ₃ ) ₂ , -N (H) -S (O) ₂ -CF ₃ and the like. Among these, a substituent having any one of a carboxyl group and -C (OH)-(CF ₃ ) ₂ is particularly preferable. When the cyclic olefin resin contains a substituent having such an acidic group, the solubility of the photosensitive adhesive composition in an alkaline developer can be increased. Therefore, in the manufacture of the semiconductor device, it is possible to reduce the undissolved residue of the photosensitive adhesive composition after development, and it is possible to further improve the patterning property at the time of development.

For this reason, the first repeating unit is particularly preferably at least one of the following formula (2) and the following formula (3). When the cyclic olefin resin contains such a first repeating unit, the adhesiveness of the adhesive layer 601 to the semiconductor chip 20 and the solubility of the photosensitive adhesive composition in an alkaline developer can be further improved.

In the above formula (2) and the above formula (3), x and y are preferably integers of 0 or more and 10 or less, respectively, and more preferably 1 or more and 5 or less. As a result, it is possible to obtain an adhesive layer 601 capable of more firmly adhering the semiconductor chips 20 to each other.

The cyclic olefin resin may have at least one kind of first repeating unit, but preferably has two or more different kinds of first repeating units, and the above formula (2) and the above formula (3). It is more preferred to have both first repeat units. This makes it possible to further improve the adhesiveness of the adhesive layer 601 to the semiconductor chip 20 and the solubility of the photosensitive adhesive composition in an alkaline developer.

The optimum value of the content of the first repeating unit in the cyclic olefin resin can be determined in consideration of the solubility of the photosensitive adhesive composition in an alkaline developer, and is, for example, 10 to 80 mol%. It is preferably present, and more preferably 20 to 70 mol%. If the content of the first repeating unit is less than the lower limit, it may be difficult to sufficiently develop the solubility of the photosensitive adhesive composition in an alkaline developer. Further, when the content of the first repeating unit exceeds the upper limit value, the characteristics of the cyclic olefin resin other than the first repeating unit are sufficiently exhibited depending on the type of the first repeating unit. It may not be possible.

The acidic group in the cyclic olefin resin is preferably 0.001 to 0.01 mol per 1 g of the polymer. More preferably, it is 0.0015 to 0.006 mol. This makes it possible to particularly increase the solubility of the photosensitive adhesive composition in an alkaline developer.

Further, it is preferable that the cyclic olefin resin also has a second repeating unit different from the above-mentioned first repeating unit.

The second repeating unit comprises a structure derived from a cyclic olefin as a main skeleton and a substituent bonded to this structure and different from the substituent possessed by the first repeating unit.

As the main skeleton of the second repeating unit, the structure mentioned in the first repeating unit described above can be used. Among these, the main skeleton of the second repeating unit is a structure derived from norbornene from the viewpoint of heat resistance of the photosensitive adhesive composition and flexibility of the photosensitive adhesive composition after curing. Is particularly preferable. Further, the main skeletons of the first and second repeating units may be different from each other, but are preferably the same. In particular, it is preferable that the main skeletons of the first and second repeating units are both structures derived from norbornene. As a result, the adhesive force of the adhesive layer 601 to the semiconductor chip 20 can be further increased, and the elastic modulus of the adhesive layer 601 can be appropriately lowered. Therefore, the adhesive layer 601 can bond the semiconductor chips 20 to each other more firmly, and by appropriately increasing the flexibility of the adhesive layer 601, the stress concentration generated at the bonding interface between the semiconductor chips 20 can be alleviated. Can be done.

The substituent contained in the second repeating unit preferably has 2 to 30 carbon atoms, and more preferably 4 to 15 carbon atoms. When the number of carbon atoms is within 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 increased. As a result, cracks generated in the semiconductor chip 20 and the adhesive layer 601 due to stress concentration at the bonding interface between the semiconductor chips 20 and peeling between the semiconductor chip 20 and the adhesive layer 601 can be further suppressed. Further, it is possible to suppress the occurrence of damage to the semiconductor chip 20 and the adhesive layer 601 due to an impact from the outside.

The substituent of the second repeating unit may have a cyclic structure, a branched structure, or the like, but a linear structure is preferable. Thereby, the elastic modulus of the photosensitive adhesive composition after curing can be further lowered, and the flexibility of the adhesive layer 601 can be further increased.

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 curing can have excellent flexibility.

As the group having an alkyl ether structure, a group represented by the following formula (1) is particularly preferable. Thereby, the flexibility of the adhesive layer 601 can be further increased.

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

Therefore, 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, so that the photosensitive adhesive composition with respect to the alkaline developer by the first repeating unit It is possible to suitably achieve both the function of sufficiently increasing the solubility of the substance and the function of setting the elastic coefficient of the photosensitive adhesive composition after curing by the second repeating unit to an appropriate value.

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

When the cyclic olefin resin contains a second repeating unit, the content of the second repeating unit in the cyclic olefin resin is, for example, preferably 20 to 60 mol%, preferably 25 to 50 mol%. Is more preferable. If the content of the second repeating unit is less than the 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 some cases. Further, when the content of the second repeating unit exceeds the upper limit value, the characteristics of the cyclic olefin resin other than the second repeating unit are sufficiently exhibited depending on the type of the second repeating unit. It may not be possible.

From the above, the cyclic olefin resin represented by the following formula (5) is preferably used. By containing the cyclic olefin resin represented by the formula (5), the photosensitive adhesive composition imparts the mechanical strength required for the adhesive layer 601 and more appropriate flexibility (stress relaxation property). be able to. Further, the photosensitive adhesive composition can exhibit particularly excellent solubility in an alkaline developer. In addition, it is possible to obtain an adhesive layer 601 having particularly excellent adhesive strength to the semiconductor chip 20.

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

In the formula (5), the degree of polymerization of the second repeating unit (that is, n / (l + m)) with respect to the degree of polymerization of the first repeating unit is preferably 0.3 to 2.0, and is 0. It is more preferably .4 to 1.5. As a result, the stress concentration generated at the bonding interface between the semiconductor chips 20 can be particularly relaxed, and the adhesive layer 601 capable of more firmly adhering the semiconductor chips 20 to each other can be obtained.

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, and more preferably 8,000 to 100,000. Is even more preferable. As a result, it is possible to obtain an adhesive layer 601 having particularly excellent adhesive strength to the semiconductor chip 20.

The weight average molecular weight (Mw) of the cyclic olefin resin can be measured by gel permeation chromatography (GPC) using a standard cyclic olefin resin in accordance with ASMDS3536-91. ..

The glass transition temperature of the cyclic olefin resin is preferably 100 to 250 ° C. By using such a cyclic olefin 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 as a temperature at which an exothermic reaction occurs when the temperature is raised from room temperature at a temperature rising rate of 5 ° C./min, for example, by a differential scanning calorimetry method.
The alkali-soluble resin (A) other than the cyclic olefin resin can also have the same effect as described above by synthesizing the alkali-soluble resin so as to satisfy the same conditions as described for the cyclic olefin resin.

<(B) Photoacid generator>
(B) The photoacid generator is a positive type light capable of generating an acid by a light reaction during exposure by irradiation with energy rays and increasing the solubility of the photosensitive adhesive composition in the alkaline developer of the exposed portion. It has a function as an acid generator. Thereby, in the manufacture of the semiconductor device, it is possible to further reduce the occurrence of undissolved residue after development in the exposed portion which is the exposed portion of the photosensitive adhesive composition (coating film 601a). Therefore, the patterning property at the time of development can be improved. In addition, the photosensitive adhesive composition contains (B) a photoacid generator, and in the production of a semiconductor device, a reaction of cross-linking (A) an alkali-soluble resin with (C) an epoxy compound described later by irradiation with energy rays. It may have a function as a negative type photoacid generator capable of promoting the above.

Specific examples of the (B) photoacid generator include onium salts, halogenated organic compounds, quinonediazide compounds, α, α-bis (sulfonyl) diazomethane compounds, and α-carbonyl-α-sulfonyl-diazomethane compounds. , Sulphonic compound, organic acid ester compound, organic acid amide compound, organic acid imide compound and the like, and one or a combination of two or more of these can be used. Among these, it is particularly preferable to use a quinonediazide compound as the (B) photoacid generator. Examples of the quinone diazide compound include compounds having a 1,2-benzoquinone diazide or a 1,2-naphthoquinone diazide structure. More specifically, (B) the photoacid generator is an ester of 1,2-naphthoquinone-2-diazide-5-sulfonic acid or 1,2-naphthoquinone-2-diazide-4-sulfonic acid and a phenol compound. It preferably contains a compound. Since these generate a carboxyl group by a photoreaction during exposure by energy ray irradiation (particularly irradiation), the solubility of the exposed portion in an alkaline developer can be further increased. Therefore, the photosensitive adhesive composition can exhibit higher solubility in an alkaline developer even with a particularly small exposure amount. As a result, the patterning property at the time of development can be further improved.

The content of the (B) photoacid generator is not particularly limited, but is preferably 1 to 50 parts by mass, more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin. preferable. If the content of the (B) photoacid generator is less than the lower limit, the exposure and development characteristics of the (B) photosensitive adhesive composition may deteriorate depending on the type of the photoacid generator and the like. .. Further, even if the content of (B) the photoacid generator exceeds the above upper limit value, no further increase in the effect can be expected, and (B) depending on the type of the photoacid generator, in the photosensitive adhesive composition. (B) There is a possibility that the characteristics of the material other than the photoacid generator cannot be fully exhibited.

<(C) Epoxy compound>
The (C) epoxy compound has a function of cross-linking (A) an alkali-soluble resin (particularly, a cyclic olefin resin).

The (C) epoxy compound may be either an aromatic epoxy compound having an aromatic ring in the molecule or an aliphatic epoxy compound having no aromatic ring in the molecule. However, as the (C) epoxy compound, an aliphatic epoxy compound is more preferable. As a result, the crosslink density of the alkali-soluble resin (A) in the photosensitive adhesive composition can be set to an appropriate value, and the flexibility of the adhesive layer 601 can be appropriately increased.

Further, the epoxy compound (C) preferably has a branched structure or a linear structure, and more preferably has a branched structure. By containing the (C) epoxy compound having a branched structure in the photosensitive adhesive composition, the crosslink density of the (A) alkali-soluble resin in the photosensitive adhesive composition can be set to an appropriate value. , The flexibility of the adhesive layer 601 can be appropriately increased. As a result, the adhesive layer 601 having the necessary mechanical strength and having excellent stress relaxation property for relaxing the stress concentration generated at the bonding interface between the semiconductor chips 20 can be obtained.

Further, the epoxy compound (C) 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. As a result, the crosslink density of the alkali-soluble resin (A) in the photosensitive adhesive composition can be set to an appropriate value, and an adhesive layer 601 having the required mechanical strength and excellent stress relaxation property can be obtained. Can be done.

Examples of such (C) epoxy compound include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, and trimethylol ethanetriglycidyl 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 Co., Ltd.), YH-300, YH-301, YD-8125G, YDF-8170G, YD-825GS, YD-825GS, YD-870GS, ZX-1059, ZX-1542, PG-207GS, ZX-1658GS (manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd.), YL980, YL983U, YL6810, YL7410, YX7700, YX8000, YX8034, YED216D, jER152, jER157S Mitsubishi Chemical Co., Ltd.), EP-3300S, EP-3950L, EP-4000L, EP-4010L, EP-4088L (ADEKA Co., Ltd.), Celoxide 2021P, Celoxide 2081 (Dycel Co., Ltd.), EPPN-201-L, EPPN -501H, EPPN-501HY, EPPN-502H, XD-1000 (Nippon Kayaku), LX-01 (Daiso Co., Ltd.), PG-100, EG-200, EG-280, CG-400, CG-500 (Osaka) Gas Chemical Co., Ltd.), EX-211L, EX-212L, EX-214L, EX-216L, EX-321L, EX-850L, EX-946L (Nagase Chemtech Co., Ltd.), VG3101L (Printec Co., Ltd.), SR -14BJ, SR-16H, SR-TMPL, SR-PG, SR-PTMG, SR-8EGS (Sakamoto Yakuhin Kogyo Co., Ltd.), cyclohexene oxide type epoxy resin, etc. may be mentioned, and one or more of these may be used. Can be used in combination. Among these, as the (C) epoxy compound, trimethylolpropan triglycidyl ether, 1,6-hexanediol diglycidyl ether, polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, hydrogenated. Bisphenol A diglycidyl ether is particularly preferred. Thereby, the cross-linking reaction of the alkali-soluble resin (A) in the photosensitive adhesive composition can be promoted, and the adhesive layer 601 having more excellent stress relaxation property can be obtained more easily and more reliably.

The content of the (C) epoxy compound is not particularly limited, but is preferably 1 to 100 parts by mass, more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin. If the content of the (C) epoxy compound is less than the lower limit, the stress relaxation property of the adhesive layer 601 may decrease depending on the type of the (C) epoxy compound or the like. On the other hand, if the content of the (C) epoxy compound exceeds the upper limit, the viscosity of the photosensitive adhesive composition may become too high.

<(D) Phenolic compound having a melting point of 50 to 150 ° C.>
The photosensitive adhesive composition comprises, for example, a coating film 601a by containing (D) a phenol compound having a melting point of 50 to 150 ° C. (hereinafter, may be simply referred to as “(D) phenol compound”). It is possible to suppress the generation of bubbles between the adhesive layer 601 and the semiconductor chip 20 when etching the wafer 201 or when the semiconductor chips 20 are crimped to each other via the adhesive layer 601. Further, even when bubbles are generated between the adhesive layer 601 and the semiconductor chip 20, the generated bubbles can be removed. By making it difficult for air bubbles to be left behind at the interface between the adhesive layer 601 and the semiconductor chip 20, the adhesive force of the adhesive layer 601 to the semiconductor chip 20 can be enhanced, and thus the semiconductor chips 20 are firmly adhered to each other. be able to. Therefore, a highly reliable chip laminate 200 can be finally obtained.

Further, by using the photosensitive adhesive composition containing (D) a phenol compound, an adhesive layer 601 showing relatively high solubility in an organic solvent can be obtained. Therefore, for example, even when it becomes necessary to remove the coating film 601a obtained by applying the photosensitive adhesive composition to the wafer 201, the coating film 601a is efficiently used while suppressing the generation of residues (residues). It can be well dissolved and removed. As a result, the wafer 201 can be subjected to (reworking) the bonding process again without wasting it. Therefore, it is possible to improve the process yield of the semiconductor device 10.

The phenol compound (D) has a melting point of 50 to 150 ° C., preferably a melting point of 60 to 130 ° C., and more preferably 70 to 120 ° C. Thereby, the above-mentioned effect due to the photosensitive adhesive composition containing the (D) phenol compound can be more remarkably exhibited. Such (D) phenol compound preferably 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.

Further, the phenol compound (D) (particularly, a phenol compound having a substituent containing an aliphatic hydrocarbon group) preferably has a hydroxyl group equivalent of 150 to 250 g / eq, and has a hydroxyl group equivalent of 160 to 240 g / eq. It is more preferable that the hydroxyl group equivalent is 180 to 220 g / eq. When the hydroxyl group equivalent is within the above range, a photosensitive adhesive composition having more optimum solubility in an alkaline developer can be obtained. On the other hand, if the hydroxyl group equivalent is less than the lower limit, the water absorption rate of the photosensitive adhesive composition may increase and its reliability may decrease depending on the type and amount of the (D) phenol compound added. There is sex. If the hydroxyl equivalent exceeds the upper limit, the solubility of the photosensitive adhesive composition in an alkaline developer is significantly reduced, and there is a possibility that undissolved residue of the photosensitive adhesive composition may occur after development.

The hydroxyl equivalent of the (D) phenol compound can be measured by a method of titrating a solution obtained by mixing the (D) phenol compound in a standard alkaline solution.

(D) When the phenol compound contains a phenol compound having a substituent containing an aliphatic hydrocarbon group (a substituent having an alkyl chain ( _-CH2- ) n), the solubility of the adhesive layer 601 in an organic solvent is further increased. Can be enhanced. Therefore, even when it becomes necessary to remove the coating film 601a, the coating film 601a can be more efficiently dissolved and removed, so that the reworkability can be improved.

The alkyl chain (-CH _2- ) n preferably has a value of n of 1 to 6, and more preferably 2 to 4. Thereby, the solubility of the adhesive layer 601 in the organic solvent can be further enhanced.

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

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

Specific examples of such (D) phenol compound include 4- (1,1-dimethylpropyl) phenol, 4-cyclohexylphenol, and 4- (1,1,3,3-tetramethylbutyl). Pharmon, 4- (4-Hydroxyphenyl) -2-butanone, 4'-hydroxybutyrophenone, 4'-hydroxyvalerophenone, 4'-hydroxyhexanophenone, 3- (4-hydroxyphenyl) propionic acid, 3-hydroxy Methyl benzoate, ethyl 3-hydroxybenzoate, methyl 4-hydroxybenzoate, ethyl 4-hydroxybenzoate, propyl 4-hydroxybenzoate, isopropyl 4-hydroxybenzoate, butyl 4-hydroxybenzoate, 4-hydroxybenzoate Isobutyl acid acid, hexyl 4-hydroxybenzoate, benzyl 4-hydroxybenzoate, 1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene, BisP-DED (manufactured by Honshu Chemical Industry Co., Ltd.), etc. , And one or a combination of two or more of these can be used. Among these, as the phenol compound (D), propyl 4-hydroxybenzoate, methyl 4-hydroxybenzoate, butyl 4-hydroxybenzoate, and hexyl 4-hydroxybenzoate are particularly preferable. As a result, it is possible to obtain an adhesive layer 601 having a particularly high adhesive force to the semiconductor chip 20 and more excellent solubility in an organic solvent.

When the phenol compound (D) contains a phenol compound having a plurality of phenol skeletons, the hydroxyl group equivalent thereof is preferably 50 to 150 g / eq, more preferably 70 to 130 g / eq, and 90 to 90 to eq. It is particularly preferably 110 g / eq. In addition, a plurality of phenolic skeletons are a linked polycyclic structure in which phenolic skeletons are connected by a single bond and are not directly bonded to each other, or a condensed type (fusion) in which phenolic skeletons are directly bonded to each other without a single bond. Any of the polycyclic structures of the type) may be used, but a articulated polycyclic structure is preferable. As a result, it is possible to obtain an adhesive layer 601 having a particularly high adhesive force to the semiconductor chip 20 and more excellent solubility in an organic solvent.

The content of the (D) phenol compound is preferably 0.5 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 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 value, the solubility of the photosensitive adhesive composition in an organic solvent may decrease depending on the type of the (D) phenol compound and the like. (D) Even if the content of the phenol compound exceeds the upper limit, no further increase in the effect can be expected. Further, in this case, depending on the type of the (D) phenol compound, the characteristics of the material other than the (D) phenol compound in the photosensitive adhesive composition may not be sufficiently exhibited.

Further, it is preferable that the photosensitive adhesive composition contains two or more kinds of the (D) phenol compound as described above. Specifically, it is preferable to contain two or more kinds of (D) phenol compounds having different melting points from each other, and it is more preferable to contain two kinds of (D) phenol compounds having different melting points from each other. Thereby, the adhesiveness, stress relaxation property, and solubility in the organic solvent of the photosensitive adhesive composition (adhesive layer 601) can be further enhanced.

When two or more kinds of (D) phenol compounds are contained, the total content thereof is preferably within the above-mentioned range.

A semiconductor device is manufactured by including (A) an alkali-soluble resin, (B) a photoacid generator, (C) an epoxy compound, and (D) a phenol compound as described above in a photosensitive adhesive composition. In, for example, when the wafer 201 provided with the coating film 601a is etched or when the semiconductor chips 20 are crimped to each other via the adhesive layer 601, air bubbles are less likely to be left at the interface between the adhesive layer 601 and the semiconductor chip 20. Become. Therefore, the semiconductor chips 20 can be firmly adhered to each other by the adhesive layer 601, and thus a highly reliable chip laminate 200 can be obtained. Further, although the adhesive layer 601 has a one-layer structure, it has sufficient adhesiveness and stress relaxation property. Therefore, it is not necessary to provide two layers, a layer having excellent adhesiveness and a layer having excellent stress relaxation property, between the semiconductor chips 20, so that the overall thickness of the chip laminate 200 is remarkably thick. It can be prevented from becoming. As a result, it is possible to obtain a highly reliable semiconductor device 10 having a low profile and excellent adhesiveness and stress relaxation property. Such a semiconductor device 10 is particularly useful in an electronic device having an extremely small internal volume and used while being carried, such as a mobile device. That is, such a semiconductor device 10 is useful in that it contributes to miniaturization, thinning, and weight reduction of the electronic device, and the function of the semiconductor device 10 is not easily impaired even when the electronic device is dropped or swung around. Is.

Further, the cured product of the photosensitive adhesive composition containing (A) an alkali-soluble resin, (B) a photoacid generator, (C) an epoxy compound, and (D) a phenol compound is soluble in an organic solvent. , And excellent reworkability.

Further, it is preferable that such a photosensitive adhesive composition further contains an (X) phenol compound having a melting point higher than that of the (D) phenol compound. Thereby, the adhesiveness of the adhesive layer 601 can be particularly improved. The melting point of the (X) phenol compound is preferably 151 to 250 ° C, more preferably 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 is a substituent containing a cyclic structure, and preferably has a substituent bonded to at least one of the phenol skeletons. This makes it possible to exert the above effect more remarkably.

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 with respect to 100 parts by mass of the (A) alkali-soluble resin. .. When the content of the phenol compound (X) is within the above range, the above-mentioned effect can be more remarkably exhibited.

Further, it is particularly preferable that the photosensitive adhesive composition contains two kinds of the (D) phenol compound and further contains the (X) phenol compound. This makes it possible to obtain an adhesive layer 601 having particularly excellent adhesiveness, stress relaxation property, and solubility in an organic solvent.

Further, the photosensitive adhesive composition may contain, if necessary, a phenol compound other than (D) phenol compound and (X) phenol compound, a leveling agent, a flame retardant, a plasticizer, a curing accelerator, an antioxidant, and an adhesion aid. It may further contain an agent or the like.

Examples of the antioxidant include phenol-based antioxidants, amine-based antioxidants, phosphorus-based antioxidants and thioether-based antioxidants, and one or a combination of two or more of these may be used. can. However, among these, as the antioxidant, it is preferable to use a phenol-based antioxidant and an amine-based antioxidant in combination.

By including such an antioxidant, it is possible to suppress the oxidation of the photosensitive adhesive composition during curing and the oxidation of the photosensitive adhesive composition (coating film 601a) in the subsequent process or the like.

Examples of the phenolic antioxidant include pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,9-bis {2- [3- (3-t). -Butyl-4-hydroxy-5-methylphenyl) propionyloxy] -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-t-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-octadesiloxyphenol, 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 glycolbis [(3,5-di-t-butyl-4-hydroxy) Phenyl) propionate], 4,4'-thiobis (6-t-butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-t-butyl-4-hydroxyphenoxy) -s -Triazine, 2,2'-methylenebis (4-methyl-6-t-butyl-6-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), bis [3,3-bis (4-Hydroxy-3-t-butylphenyl) butyric acid] glycol ester, 4,4'-butylidenebis (6-t-butyl-m-cresol), 2,2'-ethylidenebis (4,6-di) -T-Butylphenol), 2,2'-Etilidenebis (4-s-Butyl-6-t-Butylphenol), 1,1,3-Tris (2-Methyl-4-hydroxy-5-t-Butylphenyl) Butan, bis [2-t-butyl-4-methyl-6- (2-hydroxy-3-t-butyl-5-methylbenzyl) phenyl] terephthalate, 1.3.5-tris (2,6-dimethyl- 3-Hydroxy-4-t-butylbenzyl) 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) propionyloxyethyl] isocyanurate, tetrakis [ Methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, 2-t-butyl-4-methyl-6- (2-acryloyloxy-3-t-butyl-5-) Methylbenzyl) phenol, 3,9-bis (1,1-dimethyl-2-hydroxyethyl) -2,4-8,10-tetraoxaspiro [5,5] undecane-bis [β- (3-t-) Butyl-4-hydroxy-5-methylphenyl) propionate], triethylene glycol bis [β- (3-t-butyl-4-hydroxy-5-methylphenyl) propionate], 1,1'-bis (4-hydroxy) Phenyl) cyclohexane, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 2,2'-methylenebis (6- (1- (1-) Methylcyclohexyl) -4-methylphenol), 4,4'-butylidenebis (3-methyl-6-t-butylphenol), 3,9-bis (2- (3-t-butyl-4-hydroxy-5-methylphenylpropionyloxy) ) 1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, 4,4'-thiobis (3-methyl-6-t-butylphenol), 4,4'-bis (3,5-G-t-butyl-4-hydroxybenzyl) Sulfide, 4,4'-thiobis (6-t-butyl-2-methylphenol), 2,5-G-t-butylhydroquinone, 2,5-G-t -Amilhydroquinone, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate, 2,4-dimethyl-6- (1-methylcyclohexyl, sintered phenol,) Examples thereof include 2,4-bis ((octylthio) methyl) -5-methylphenol. Among these, phenolic antioxidants such as 2,6-bis [(2-hydroxy-5-methylphenyl) methyl] -4-methylphenol are preferable.

Examples of amine-based antioxidants include N, N'-di-sec-butyl-p-phenylenediamine, 4,4'-dimethoxydiphenylamine, 4-isoporoxydiphenylamine, and N-isopropyl-N'-phenyl-p-phenylene. Examples thereof include diamine, N- (1,3-dimethylbutyl) -N'-phenyl-p-phenylenediamine, 4,4'-di (α, α-dimethylbenzyl) diphenylamine and the like. Among these, as the amine-based antioxidant, diphenylamine-based compounds such as 4,4'-dimethoxydiphenylamine, 4-isopoloxydiphenylamine, and 4,4'-di (α, α-dimethylbenzyl) diphenylamine are preferable.

Phosphorus antioxidants include bis- (2,6-di-t-butyl-4-methylphenyl) pentapentaerythritol diphosphite, tris (2,4-di-t-butylphenylphosphite), and tetrakis. (2,4-G-t-butyl-5-methylphenyl) -4,4'-biphenylenediphosphonite, 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, bis- (2,6) -Dicumylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite, tris (mixed monoand di-nonylphenylphosphite), bis (2, 4-Di-t-Butylphenyl) pentaerythritol-di-phosphite, bis (2,6-di-t-butyl-4-methoxycarbonylethyl-phenyl) pentaerythritol diphosphite, bis (2,6- Di-t-butyl-4-octadecyloxycarbonylethyl-phenyl) pentaerythritol diphosphite and the like can be mentioned. Among these, phosphite and phosphate are preferable as phosphorus-based antioxidants.

Thioether-based antioxidants include dilauryl 3,3'-thiodipropionate, bis (2-methyl-4- (3-n-dodecyl) thiopropionyloxy) -5-t-butylphenyl) sulfide, and distearyl-. Examples thereof include 3,3'-thiodipropionate and pentaerythritol-tetrakis (3-lauryl) thiopropionate.

When the photosensitive adhesive composition contains an antioxidant, the content of the antioxidant is preferably 0.1 to 50 parts by mass, preferably 0.5 parts by mass, based on 100 parts by mass of the (A) alkali-soluble resin. It is more preferably to 30 parts by mass.

As the adhesion aid, vinyltrimethoxysilane, vinyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 5 , 6-Epoxyhexyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltri Ethoxysilane, 3-acryloxypropyltrimethoxysilane, bis [3- (triethoxysilyl) propyl] tetrasulfide, bis [3- (triethoxysilyl) propyl] disulfide, 3-isopropylpropyltriethoxysilane, phenyltrimethoxy Silane, phenyltriethoxysilane, benzoyroxypropyltrimethoxysilane, benzyloxypropyltriethoxysilane, 1,6-bis (trimethoxysilyl) hexane, norbornenyltrimethoxysilane, norbornenyltriethoxysilane, 3 -(Triethoxysilyl) propylsuccinic acid anhydride, 6-azidosulfonylhexyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane Silane, tris (3-trimethoxysilylpropyl) isocyanurate, [2- (3-cyclohexenyl) ethyl] trimethoxysilane, [2- (3-cyclohexenyl) ethyl] triethoxysilane, (3-cyclopentadi) Enilpropyl) triethoxysilane, pentilt remethoxysilane, pentilt reethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, decyltrimethoxysilane, Decyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, bis (triethoxysilyl) methane, bis (trimethoxysilyl) ethane, bis (triethoxysilyl) ethane, bis (trimethoxysilyl) hexane, bis (tri) Ethoxysilyl) hexane, bis (trimethoxysilyl) octane, bis (triethoxysilyl) octane, bis (trimethoxysilyl) benzene, bis [(3-methyldimethoxy) Cyril) Propyl] Polypropylene oxide, polymethacrylate trimethoxysilyl ester, polymethacrylate triethoxysilyl ester, trifluoropropyltrimethoxysilane, 1,3-dimethyltetramethoxydisiloxane and the like can be mentioned. However, the adhesion aid is not limited to these. These may be used alone or in combination of two or more. By including such an adhesion aid in the photosensitive adhesive composition, the adhesive force (adhesive force) of the adhesive layer 601 to the semiconductor chip 20 can be further enhanced.

When the photosensitive adhesive composition contains an adhesion aid, the content of the adhesion aid is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the (A) alkali-soluble resin, 0.2. It is more preferably to 20 parts by mass.

≪Physical characteristics≫
Next, the physical characteristics of the photosensitive adhesive composition (physical characteristics of the adhesive layer 601) will be described in detail.

The elastic modulus of the cured photosensitive adhesive composition, that is, the adhesive layer 601 at 25 ° C. is preferably 2.0 to 3.5 GPa. 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 adhesive force of the photosensitive adhesive composition before curing, which has been subjected to the etching treatment and the ashing treatment, to the semiconductor chip 20 at 25 ° C. is preferably 20.0 to 200.0N. In other words, the photosensitive adhesive composition is used to form a film on a semiconductor chip 20 having a size of 4 mm × 4 mm in a plan view, and the film is uncured or semi-cured without being cured (completely cured). When the semiconductor chip 20 provided with the film (photosensitive adhesive composition before curing) is subjected to an etching treatment and an ashing treatment, the adhesive force of the film to the semiconductor chip 20 at 25 ° C. is 20.0 to 200.0N. Is preferable. When this adhesive force is converted into the unit area of the size of the semiconductor chip 20 in a plan view, it is 1.25 to 12.5 MPa (N / mm ² ).

The elastic modulus of the photosensitive adhesive composition before curing at 25 ° C. is within a predetermined range with respect to the elastic modulus of the photosensitive adhesive composition after curing at 25 ° C., for example, curing. The risk of the previous photosensitive adhesive composition being significantly deformed or flowing out of the wafer 201 is reduced. Therefore, the accuracy of alignment when stacking the semiconductor chips 20 can be improved. Furthermore, since the amount of change in elastic modulus before and after curing is relatively small, the amount of shrinkage due to photosensitization can also be reduced. As a result, the stress generated at the interface between the adhesive layer 601 and the semiconductor chip 20 due to the curing shrinkage can be reduced. From this point of view, it also contributes to improving the reliability of the chip laminate 200.

On the other hand, the pre-cured photosensitive adhesive composition subjected to the etching treatment and the ashing treatment has sufficient adhesion to the semiconductor chip 20 required for die bonding. Therefore, the adhesive layer 601 firmly fixes the semiconductor chips 20 to each other and contributes to the improvement of the reliability of the chip laminate 200.

By using a photosensitive adhesive composition satisfying the above conditions, it is possible to easily obtain an adhesive layer 601 having both sufficient adhesiveness and stress relaxation property. In other words, the adhesive layer 601 has an element protection function (buffer coat function) of the buffer coat film and an adhesive function (die bonding function) of the die bonding film by itself. Therefore, the chip laminate 200 can be formed without lowering the reliability of the chip laminate 200, and the chip laminate 200 can be made thinner than the conventional one using two layers. Further, as the thickness of the chip laminate 200 is reduced, the volume of the mold portion 50 can be reduced and the bonding wire 70 can be shortened, which contributes to weight reduction and cost reduction.

The elastic modulus of the photosensitive adhesive composition after curing at 25 ° C. is more preferably 2.2 to 3.2 GPa, and further preferably 2.4 to 3.0 GPa. If the elastic modulus of the photosensitive adhesive composition after curing is less than the lower limit, the adhesive strength of the adhesive layer 601 may be slightly lowered depending on the composition of the photosensitive adhesive composition. Further, when the filler is contained in the mold portion 50, the filler may penetrate the adhesive layer 601 and adversely affect the semiconductor chip 20. On the other hand, when the elastic modulus of the photosensitive adhesive composition after curing exceeds the upper limit value, 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 local concentration of the residual stress caused by the lamination of the semiconductor chips 20 and the thermal stress caused by the difference in thermal expansion between the semiconductor chip 20 and the adhesive layer 601 and crack the semiconductor chip 20. May cause.

The elastic modulus of the photosensitive adhesive composition after curing was set to a measurement temperature of 25 ° C., a load of 2 mN, and a holding time of 1 second using, for example, an ultrafine hardness tester ENT-1000 (manufactured by Elionix Inc.). It can be determined by measuring according to ISO14577 using a Berkovich indenter (triangular pyramid, anti-ridge angle 115 °).

The elastic modulus of the photosensitive adhesive composition after curing can be determined 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. More preferably, it is 80 to 110%. When the elastic modulus of the photosensitive adhesive composition before curing is lower than the lower limit, the adhesiveness of the photosensitive adhesive composition is increased, but the film of the photosensitive adhesive composition is easily deformed. As a result, for example, when the semiconductor chip 20 is temporarily arranged via this coating film, the position of the semiconductor chip 20 may be easily displaced, or the photosensitive adhesive composition may flow out from the wafer 201. On the other hand, if the elastic modulus of the photosensitive adhesive composition before curing exceeds the upper limit value, the adhesiveness may decrease and it may be difficult to temporarily arrange the semiconductor chip 20.
The elastic modulus of the photosensitive adhesive composition before curing can be measured in the same manner as the elastic modulus of the photosensitive adhesive composition after curing.

The elastic modulus of the photosensitive adhesive composition before curing can be determined as the elastic modulus of the coating film 601a after the treatment step and before the mounting step.

On the other hand, the adhesive force of the photosensitive adhesive composition before curing to the semiconductor chip 20 subjected to the etching treatment and the ashing treatment at 25 ° C. is more preferably 30 to 180 N (1.875 to 11.25 MPa). , More preferably 40 to 160 N (2.5 to 10 MPa). If the adhesive force is less than the lower limit, air bubbles may easily enter the interface between the adhesive layer 601 and the semiconductor chip 20. On the other hand, when the adhesive force exceeds the upper limit value, if air bubbles enter the interface between the adhesive layer 601 and the semiconductor chip 20, it may be difficult to remove them.

The adhesive force of the photosensitive adhesive composition before curing, which has been subjected to the etching treatment and the ashing treatment, to the semiconductor chip 20 can be measured as follows. First, the semiconductor chips 20 are bonded to each other via the photosensitive adhesive composition of the present invention before curing, which has been subjected to an etching treatment and an ashing treatment to obtain a semiconductor chip adhesive. After that, a universal bond tester Dage4000 (manufactured by Daige Japan Co., Ltd.) is used, and the die share strength of the semiconductor chip adhesive is determined as the adhesive strength to the semiconductor chip 20. The die-share strength is when one of the semiconductor chips 20 is pushed horizontally (in-plane direction of the semiconductor chip 20) with a share tool from the side (side surface) of the semiconductor chip adhesive, and the joint surface between the semiconductor chips 20 is broken. Required as strength.

Further, the adhesive force of the photosensitive adhesive composition before curing, which has been subjected to the etching treatment and the ashing treatment, to the semiconductor chip 20 is determined as the adhesive force of the coating film 601a to the semiconductor chip 20 after the treatment step and before the mounting step. be able to.

The etching process is, for example, a process of removing the passivation film on the surface of the semiconductor chip 20 and exposing the electrode pad for connecting the bonding wire 70. Specifically, a mixed gas of a fluorine compound gas (CF ₄ ), an argon gas (Ar) and an oxygen gas (O ₂ ) is used as the gas, the output is 2500 W, the time is 6 minutes, and the CF ₄ flow rate / Ar flow rate / O. ₂ Examples of the etching process are performed under the condition that the flow rate is 200 sccm / 200 sccm / 50 sccm.

Further, the ashing treatment is, for example, a treatment of removing treatment residues and the like generated by the etching treatment to clean the surface of the adhesive layer 601 and the surface of the electrode pad. Specific examples thereof include plasma treatment using oxygen gas (O ₂ ) under the conditions that the output is 600 W, the time is 12 minutes, and the O ₂ flow rate is 200 sccm.

It should be noted that such an etching treatment and an ashing treatment may accelerate the deterioration of the organic material. Therefore, in the case of a coating film (adhesive layer) having low etching resistance and ashing resistance, there is a possibility that the semiconductor chips 20 cannot be sufficiently adhered to each other. On the other hand, the coating film 601a (adhesive layer 601) formed by using the photosensitive adhesive composition has sufficient etching resistance and ashing resistance. Therefore, even after such an etching treatment and an ashing treatment, a decrease in the adhesive strength of the coating film 601a is suppressed, and as a result, the adhesive strength as described above is exhibited. Therefore, such a photosensitive adhesive composition does not need to consider a decrease in adhesiveness in various treatments in the adhesive process, so that the manufacturing process of the semiconductor device 10 can be easily simplified and the cost can be reduced easily. It is useful in that it can be done.

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

Specifically, the elastic modulus at 25 ° C. after the heating step and before the treatment step of the photosensitive adhesive composition is defined as X [GPa], and the elastic modulus at 25 ° C. after the treatment step is defined as Y [GPa]. Then, it is preferable that X and Y satisfy the relationship of 0.7 ≦ X / Y ≦ 1.5, and more preferably satisfy the relationship of 0.8 ≦ X / Y ≦ 1.3. When the rate of change in elastic modulus before and after the treatment step satisfies the above relationship, the coating film 601a composed of the photosensitive adhesive composition has sufficient mechanical properties to maintain the patterned shape. At the same time, it has sufficient adhesiveness to bond the semiconductor chips 20 to each other. That is, in the treatment step in which the etching treatment and the ashing treatment are performed, the deterioration of the coating film 601a is promoted, but when the rate of change in elastic modulus before and after the treatment step satisfies the above relationship, the coating film 601a is used. , While sufficiently retaining the patterned shape, it sufficiently functions as an adhesive layer 601 in the mounting process. Therefore, when the rate of change in elastic modulus before and after the treatment step satisfies the above relationship, the coating film 601a composed of such a photosensitive adhesive composition has a function as an etching mask and as an adhesive layer 601. It can be compatible with the function.

In the processing step, an etching process and an ashing process that satisfy the above-mentioned processing conditions are performed.

The minimum melt viscosity of the photosensitive adhesive composition before curing at 100 to 200 ° C. is preferably 20 to 500 Pa · s. Since such a photosensitive adhesive composition has excellent wettability with respect to the semiconductor chip 20, voids and the like are less likely to occur in the adhesive layer 601. Therefore, it is possible to form a homogeneous adhesive layer 601 with little variation in physical properties. As a result, when the semiconductor chips 20 are bonded to each other via the adhesive layer 601, it is difficult to cause local concentration of stress, cracks occur in the semiconductor chip 20, and peeling occurs between the semiconductor chip 20 and the adhesive layer 601. Can be further suppressed. The minimum melt viscosity of the photosensitive adhesive composition before curing can be measured by a reometer, and can be determined as the minimum melt viscosity of the coating film 601a after the treatment step and before the mounting step.

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

Further, while the photosensitive adhesive composition before curing has a certain adhesiveness, the adhesiveness can be reduced by subjecting it to UV irradiation treatment. Therefore, the adhesiveness (adhesive strength) of the photosensitive adhesive composition before curing can be controlled by the presence or absence of the UV irradiation treatment.

Specifically, the adhesive force of the photosensitive adhesive composition before curing to the backgrinding film 90 will be described. First, the photosensitive adhesive composition is used to form a coating film 601a on the wafer 201. Next, the etching treatment and the ashing treatment described above are performed on the wafer 201 provided with the uncured or semi-cured coating film 601a (photosensitive adhesive composition before curing) without curing (completely curing) the coating film 601a. Apply. Then, a UV peeling type back grind film 90 is attached onto the coating film 601a, and the adhesive force of the back grind film 90 to the coating film 601a at 25 ° C. is measured. The adhesive strength is preferably 3.0 N / 25 mm or more. Such a photosensitive adhesive composition can exhibit sufficient adhesive strength to the backgrinding film 90 even after being subjected to a treatment such as an etching treatment or an ashing treatment that accelerates the deterioration of the organic material. Therefore, for example, when the wafer 201 on which the coating film 601a of the photosensitive adhesive composition is formed is subjected to the backgrinding treatment, the wafer 201 can be reliably fixed and the accuracy of the backgrinding treatment can be further improved. ..

The adhesive strength is more preferably 3.5 N / 25 mm or more and 10.0 N / 25 mm or less.

Further, the adhesive strength can be measured as follows. First, a UV peeling type backgrind film 90 (width 25 mm, length 75 mm) is attached so that the adhesive surface is 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 one end of the backgrinding film 90 in the longitudinal direction was pulled so that the peeling angle was 180 °. The backgrind film 90 is peeled off from the coating film 601a of the photosensitive adhesive composition. The adhesive force can be obtained by measuring the average value of the load required for peeling at this time (180 ° peeling adhesive force, unit: N / 25 mm, JIS Z 0237 compliant).

On the other hand, the adhesive force of the photosensitive adhesive composition before curing after being subjected to UV irradiation treatment to the backgrinding film 90 at 50 ° C. is preferably 0.5 N / 25 mm or less. Thereby, the adhesive force of the photosensitive adhesive composition before curing after being subjected to the UV irradiation treatment to the backgrind film 90 can be sufficiently reduced. Therefore, for example, when the backgrinding film 90 is peeled off from the coating film 601a of the photosensitive adhesive composition after the backgrinding treatment, the backgrinding film 90 can be smoothly peeled off without exerting a large load on the coating film 601a. In addition, the backgrind film 90 can be peeled off without impairing the adhesion between the coating film 601a and the semiconductor chip 20. As a result, for example, when the individual pieces 21 and 22 are picked up after the dicing process, it is possible to prevent problems such as chipping of the semiconductor chip 20 from occurring.

Further, by reducing the adhesive force after the UV irradiation treatment, for example, the photosensitive adhesive composition adheres to the dicing blade 110 in the dicing step, or the photosensitive adhesive composition adheres to the collet 121 in the mounting step. It is possible to suppress the dicing. As a result, it is possible to suppress the occurrence of dicing failure and pickup failure.

The adhesive strength after the UV irradiation treatment is more preferably 0.05 N / 25 mm or more and 0.40 N / 25 mm or less.

Further, in the UV irradiation treatment, light having a wavelength of 365 nm is irradiated to the coating film 601a through the backgrind film 90 so that the integrated light amount is 600 mJ / cm ² .

The UV peeling type back grind film 90 is made of an acrylic resin.

The above-mentioned measurement of the adhesive strength after the UV irradiation treatment is the above-mentioned measurement of the adhesive strength of the photosensitive adhesive composition before curing after being subjected to the etching treatment and the ashing treatment to the backgrinding film 90 at 25 ° C. It can be done in the same way as the method.

Although the present invention has been described above, 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.

Next, specific examples of the present invention will be described.
(Example 1)
[1] (A) Synthesis of Alkali-Soluble Resin (Cyclic Olefin Resin A-1) A plurality of glass instruments were prepared and dried at 60 ° C. under 0.1 torr (Torr) for 18 hours. After that, all the glass equipment was installed in the glove box.

Next, in one glass device (glass device X), toluene (992 g), dimethoxyethane (116 g), 1,1-bistrifluoromethyl-2- (bicyclo [2.2.1] hept-2-en-5). -Il) Ethyl alcohol (hereinafter, HFANB) (148 g, 0.54 mol), ethyl 3- (bicyclo [2.2.1] hept-2-ene-2-yl) propanate (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). It was charged and a mixture containing each monomer was obtained. Then, the mixture was purged (nitrogen purge) by flowing nitrogen for 30 minutes while heating at 45 ° C.

Further, in another glass device (glass device Y), EPEsNB (14.2 g, 0.073 mol) and NBTON (46.7 g, 0.159 mol) were mixed and nitrogen purged. After the nitrogen purge was completely completed, bis (toluene) bis (perfluorophenyl) nickel (5.82 g, 0.012 mol) dissolved in 60.5 ml of toluene was put into the glass device Y. At the same time, the above-mentioned mixture in the glass device X was added into the glass device Y over 3 hours at a rate at which the polymerization reaction proceeded at a constant level to obtain a reaction solution.

Next, the unreacted monomer in the reaction solution was removed by dissolving the reaction solution in about 1 L of methanol / tetrahydrofuran (THF) (= 4 mol / 5 mol). Next, the ester in the reaction solution was hydrolyzed with a sodium hydroxide solution of sodium hydroxide / sodium acetate (= 4.8 mol / 1 mol) at 60 ° C. for 4 hours to obtain solution A. Then, methanol (405 g), THF (87 g), acetic acid (67 g), formic acid (67 g), and deionized water (21 g) were added to Solution A, and the mixture was stirred at 50 ° C. for 15 minutes. When stirring is stopped, solution A
Was separated into an aqueous layer and an organic layer, the aqueous layer of the upper layer was removed, and the organic layer was washed 3 times with a methanol / deionized water (= 390 g / 2376 g) solution at 60 ° C. for 15 minutes. Then, the obtained polymer was diluted in propylene glycol methyl ether acetate and solvent-substituted so that the concentration of the polymer was 40%. In this way, the 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 dispersion (PD) of the cyclic olefin resin A-1 was 2.52.

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

（式（７）中、ｌ：ｍ：ｎ＝４５：１５：４０である。）

(In the formula (7), l: m: n = 45: 15: 40.)

[2] Preparation of Photosensitive Adhesive Composition The cyclic olefin resin A-1 (22.0 parts by mass as a solid content) as the (A) alkali-soluble resin obtained in the above [1] and (B). As a photoacid generator B-1 (4.0 parts by mass) as a photoacid generator, (C) an epoxy compound C-1 (5.0 parts by mass) as an epoxy compound, and (D) a phenol compound. As a solvent (solvent), the phenol compound D-1 (3.0 parts by mass), the antioxidant E-1 (2.0 parts by mass), the antioxidant E-2 (3.0 parts by mass). Mix with propylene glycol methyl ether acetate (61.0 parts by mass including propylene glycol methyl ether acetate contained in the solution of cyclic olefin resin A-1) to obtain a uniform photosensitive adhesive composition. Obtained.
The materials used in the photosensitive adhesive composition of Example 1 are shown below.

<Photoacid generator B-1>
As the photoacid generator B-1, a compound represented by the following formula (8) was prepared.

<Epoxy compound C-1>
As the epoxy compound C-1, a compound represented by the following formula (9) was prepared.

<Phenol compound D-1>
As the phenol compound D-1, a compound represented by the following formula (10) (butyl 4-hydroxybenzoate) was 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 group 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'-di (α, α-dimethylbenzyl) diphenylamine) was 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.

(Examples 2 to 18, Comparative Examples 1 to 4)
The same as in Example 1 except that the materials constituting the photosensitive adhesive composition were changed as shown in Tables 1 and 2 and the content of each material was set as shown in Tables 1 and 2. To obtain a photosensitive adhesive composition.
The materials used in the photosensitive adhesive compositions of each example and each comparative example are shown below.

<Cyclic olefin resin A-2>
As the cyclic olefin resin A-2 ((A) alkali-soluble resin), a compound represented by the following formula (13) was prepared.

（式（１３）中、ｌ：ｍ：ｎ＝２５：１５：６０である。）

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

<Cyclic olefin resin A-3>
As the cyclic olefin resin A-3 ((A) alkali-soluble resin), a compound represented by the following formula (14) was prepared.

（式（１４）中、ｌ：ｍ：ｎ＝２５：３５：４０である。）

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

<Phenol compound D-2>
As the phenol compound D-2 ((D) phenol compound), a compound represented by the following formula (15) (hexyl 4-hydroxybenzoate) was 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 group 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 represented by the following formula (16) (methyl 4-hydroxybenzoate) was 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 hydroxyl group equivalent of the phenol compound D-3 was 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) was 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 group 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 represented by the following formula (18) (1,8,9-trihydroxyanthracene) was 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 group 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 represented by the following formula (19) (2,2'-dihydroxydiphenylmethane) was 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 group equivalent of the phenol compound D-6 was 100 g / eq.

<Phenol compound X-1>
As the phenol compound X-1 ((X) phenol compound), the compound represented by the following formula (20) (4,4'-[(2-hydroxyphenyl) methylene] bis [2-cyclohexyl-5-methylphenol] ) Was prepared.

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 group equivalent of the phenol compound X-1 was 161 g / eq.

〈エポキシ化合物Ｃ－２〉
エポキシ化合物Ｃ－２として、下記式（２１）で表される芳香族エポキシ化合物を用意した。

<Epoxy compound C-2>
As the epoxy compound C-2, an aromatic epoxy compound represented by the following formula (21) was prepared.

[3] Preparation of Evaluation Test Piece First, the photosensitive adhesive composition used in each Example and each Comparative Example was applied onto a silicon semiconductor chip and prebaked at 120 ° C. for 5 minutes. As a result, a coating film was obtained.

Next, the obtained coating film was heat-treated at 150 ° C. for 40 minutes to obtain a semi-cured (before curing) coating film.
Next, the semiconductor chip provided with the coating film was sequentially subjected to an etching treatment and an ashing treatment. The etching process uses a mixed gas of fluorine compound gas (CF ₄ ), argon gas (Ar) and oxygen gas (O ₂ ), the output is 2500 W, the time is 6 minutes, and the CF ₄ flow rate / Ar flow rate / O ₂ flow rate is. The procedure was performed under the conditions of 200 sccm / 200 sccm / 50 sccm. The ashing treatment was performed using a mixed gas of O ₂ and Ar under the conditions of an output of 600 W, a time of 12 minutes, and an O ₂ flow rate of 200 sccm.

Next, another semiconductor chip was placed on the coating film, and the pressure was applied for 5 seconds with a load of 10 N while heating at a temperature of 150 ° C.

In this way, an evaluation test piece in which two semiconductor chips were bonded via an adhesive layer was produced.

[4] Evaluation of photosensitive adhesive composition and evaluation test piece [4.1] Evaluation of adhesiveness [4.1.1] Evaluation of adhesion during development First, it was used in each Example and each Comparative Example. The photosensitive adhesive composition was applied onto a silicon semiconductor chip and prebaked at 120 ° C. for 5 minutes. As a result, a coating film having a thickness of 10 μm was obtained.

Next, the obtained coating film was exposed to a mask having a line-and-space pattern having a width of 100 μm. This exposure treatment was performed by irradiating light having a wavelength of 365 nm and a light intensity of 5 mW / cm ² in the air for each portion in one coating film at a different time.

Next, the exposed coating film was developed with an alkaline developer (2.38% tetramethylammonium hydroxide aqueous solution) at 23 ° C. for 40 seconds, and then rinsed with pure water for 20 seconds. The coating film (adhesive layer) having an opening with a width of 100 μm after development was observed with an optical microscope, and the degree of peeling of the coating film from the semiconductor chip (presence or absence of pattern peeling) was evaluated based on the following evaluation criteria. ..

<Evaluation criteria>
A: The entire coating film did not peel off from the semiconductor chip.
B: Less than 30% of the coating film was peeled off from the semiconductor chip.
C: 30% or more and less than 50% of the coating film was peeled off from the semiconductor chip.
D: More than 50% of the coating film was peeled off from the semiconductor chip.

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

[4.1.2] Evaluation of Adhesive Strength For the obtained evaluation test piece, use Dage4000 (manufactured by Daige Japan Co., Ltd.) and use a share tool from the side (side surface) of the semiconductor chip to horizontally hold one of the semiconductor chips. Pushed in the direction, the die shear strength per chip when the joint surface between the chips was broken was measured. The chip size was 4 mm × 4 mm.
Then, the measured die share strength was evaluated based on the following evaluation criteria.

<Evaluation criteria>
A: Die share strength is very high.
B: Die share strength is high.
C: Die share strength is low.
D: Die share strength is very low.

In Comparative Example 4, the coating film (adhesive layer) was peeled off from the semiconductor chip, and the adhesive strength could not be evaluated.

[4.2] Evaluation of Reworkability First, the photosensitive adhesive composition used in each Example and each Comparative Example was applied onto a silicon semiconductor chip and prebaked at 120 ° C. for 5 minutes. As a result, a coating film was obtained.

Next, the obtained coating film was heat-treated at 150 ° C. for 40 minutes.
Next, the semiconductor chip on which the heat-treated coating film was formed was immersed in propylene glycol-1-monomethyl ether-2-acetate and left for 20 hours.

Next, the semiconductor chip was taken out from the propylene glycol-1-monomethyl ether-2-assetate, and the presence or absence of a residue on the coating film was visually observed, and the reworkability was evaluated based on the following evaluation criteria.

<Evaluation criteria>
A: No residue of the coating film is observed.
B: A slight residue of the coating film is observed.
C: A large amount of residue of the coating film is observed.
D: The coating film is hardly removed.

[4.3] Evaluation of Photosensitivity of Photosensitive Adhesive Composition First, the photosensitive adhesive composition used in each Example and each comparative example was applied onto a silicon semiconductor chip, and the temperature was 120 ° C. for 5 minutes. Was pre-baked. As a result, a coating film having a thickness of 10 μm was obtained.

Next, the obtained coating film was exposed to a mask having a line-and-space pattern having a width of 100 μm. This exposure treatment was performed by irradiating light having a wavelength of 365 nm and a light intensity of 5 mW / cm ² in the air while changing the time for each coating film.

Next, the coating film subjected to the exposure treatment was subjected to a development treatment. The minimum exposure amount (unit: mJ / cm) 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%. ² ) was requested.
Residual film ratio of unexposed area = 100 x film thickness after development of unexposed area / film thickness after prebaking Residual film ratio of exposed area = 100 x film thickness after development of exposed area / film thickness after prebaking The exposure amount is shown in Table 1.

The coating film of each comparative example did not react with light at the time of exposure, and the coating film could not be removed by the developing process. Therefore, it was not possible to evaluate the photosensitivity (measurement of the exposure amount) of the coating film of each comparative example.

[4.5] Evaluation of Remaining Film Ratio (Residual Rate) of Photosensitive Adhesive Composition First, in the same manner as in [4.4], a coating film subjected to exposure treatment for each Example and each Comparative Example was prepared. did. Next, the exposed coating film was developed and then heat-treated at 150 ° C. for 40 minutes. Then, the residual film ratio of the unexposed portion defined as follows was obtained.

Residual film ratio = 100 × Film thickness after development of unexposed area / Film thickness after prebaking Table 1 shows the determined residual film ratio.

The coating film of each comparative example did not react with light at the time of exposure, and the coating film could not be removed by the developing process. Therefore, it was not possible to evaluate the residual film ratio for the coating films of each comparative example.

As is clear from Tables 1 and 2, in the photosensitive adhesive composition and the evaluation test piece of each example, the semiconductor chip and the adhesive layer are formed while suppressing the remaining bubbles at the interface with the semiconductor chip. It was confirmed that there was sufficient adhesive strength (adhesive strength) between the two. In addition, the coating film (adhesive layer) used in each example after the predetermined heat treatment had sufficient solubility in an organic solvent and had good so-called reworkability. Further, it was confirmed that the evaluation test piece of each example had a high residual rate of the unexposed portion. The semiconductor device provided with the laminated semiconductor element in which the semiconductor elements were bonded to each other by the cured product of the photosensitive adhesive composition of each embodiment had high reliability. On the other hand, as described in [4.3] above, the coating film formed by using the photosensitive adhesive composition of each Comparative Example could not be removed by the development treatment. Therefore, it has not been possible to obtain a semiconductor device provided with a laminated semiconductor element.

By using the cured product of the photosensitive adhesive composition of the present invention as an adhesive layer for adhering semiconducting elements to each other, it is possible to reduce the generation of bubbles (voids) at the interface between the semiconductor element and the adhesive layer. Also, even if bubbles are generated at the interface, the generated bubbles can be removed. As a result, the adhesiveness (adhesion) between the semiconductor elements can be improved. Therefore, the present invention has industrial applicability.

Claims (14)

(A) An alkali-soluble resin composed of a norbornene-based resin,
(B) Photoacid generator and
(C) An epoxy compound containing two or more glycidyl groups in the molecule (excluding organosilicon compounds having an epoxy structure) and
(D) A phenol compound having a melting point of 50 to 150 ° C., a substituent containing an alkyl chain (-CH _2- ) _n (where n is 1 to 6), and a hydroxyl group equivalent of 150 to 250 g / eq. When,
(X) Phenolic compound A phenol compound having a melting point higher than that of (D),
A photosensitive adhesive composition comprising. (A) An alkali-soluble resin composed of a norbornene-based resin,
(B) Photoacid generator and
(C) An epoxy compound containing two or more glycidyl groups in the molecule (excluding organosilicon compounds having an epoxy structure) and
(D) A phenol compound having a melting point of 50 to 150 ° C., a plurality of phenol skeletons, and a hydroxyl group equivalent of 50 to 150 g / eq.
(X) Phenolic compound A phenol compound having a melting point higher than that of (D),
A photosensitive adhesive composition comprising. The photosensitive adhesive composition according to claim 2, wherein the plurality of phenol skeletons of the (D) phenol compound form a linked polycyclic structure. The photosensitive adhesive composition according to any one of claims 1 to 3, wherein the phenol compound (X) has a melting point of 151 to 250 ° C. The photosensitive adhesive composition according to any one of claims 1 to 4, wherein the phenol compound (X) contains a phenol compound having a plurality of phenol skeletons. The photosensitive adhesive composition according to claim 5 , wherein the phenol compound having a plurality of phenol skeletons is a substituent containing a cyclic structure and has at least one substituent bonded to the phenol skeleton. The photosensitive adhesive composition according to any one of claims 1 to 6 , wherein the alkali-soluble resin (A) has an acidic group. (A) An alkali-soluble resin composed of a norbornene-based resin and having a linear substituent having 2 to 30 carbon atoms, and an alkali-soluble resin.
(B) Photoacid generator and
(C) An epoxy compound containing two or more glycidyl groups in the molecule (excluding organosilicon compounds having an epoxy structure) and
(D) A phenol compound having a melting point of 50 to 150 ° C., a substituent containing an alkyl chain (-CH _2- ) _n (where n is 1 to 6), and a hydroxyl group equivalent of 150 to 250 g / eq. When,
A photosensitive adhesive composition comprising. (A) An alkali-soluble resin composed of a norbornene-based resin and having a linear substituent having 2 to 30 carbon atoms, and an alkali-soluble resin.
(B) Photoacid generator and
(C) An epoxy compound containing two or more glycidyl groups in the molecule (excluding organosilicon compounds having an epoxy structure) and
(D) A phenol compound having a melting point of 50 to 150 ° C., a plurality of phenol skeletons, and a hydroxyl group equivalent of 50 to 150 g / eq.
A photosensitive adhesive composition comprising. The photosensitive adhesive composition according to claim 8 or 9, wherein the linear substituent contains an alkyl ether structure. The photosensitive adhesive composition according to any one of claims 8 to 10, wherein the linear substituent is a group represented by the following formula (1).

(In equation (1), z is an integer of 1 or more and 10 or less.) The photosensitive adhesive composition according to any one of claims 8 to 11, wherein the alkali-soluble resin (A) contains a repeating unit having a linear substituent in an amount of 20 to 60 mol%. A semiconductor device equipped with a laminated semiconductor element,
The laminated semiconductor element is
With multiple semiconductor devices,
The cured product of the photosensitive adhesive composition according to any one of claims 1 to 12, which is provided between the semiconductor elements and joins them.
A semiconductor device characterized by having. With semiconductor devices
With the member to be joined,
The cured product of the photosensitive adhesive composition according to any one of claims 1 to 12, which is provided between the semiconductor element and the member to be joined and joins them.
A semiconductor device characterized by having.

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