CN102160163A - Semiconductor device and method for manufacturing same - Google Patents

Abstract

The present invention aims to provide a semiconductor device having excellent heat resistance, wherein a semiconductor element and an object to be bonded are bonded together through a patterned film-like photosensitive adhesive by means of thermal compression bonding. In the semiconductor device, the water content in the patterned film-like photosensitive adhesive right before the thermal compression bonding is not more than 1.0% by weight.

Description

Semiconductor device and manufacturing method thereof

technical field

The present invention relates to a semiconductor device and its manufacturing method.

Background technique

In recent years, semiconductor devices having various forms have been proposed along with improvements in performance and functionality of electronic components. In this type of semiconductor device, in order to bond and fix the semiconductor element and the supporting substrate (adhered body) for mounting the semiconductor element, it is preferable to use a photosensitive film-like photosensitive adhesive capable of patterning to achieve low Stress resistance, low temperature adhesiveness, moisture resistance reliability, solder reflow resistance, etc., as well as the function, form and simplified assembly process of semiconductor devices.

Photosensitivity refers to the function that the part irradiated by light undergoes a chemical change and becomes insoluble or soluble to an aqueous alkali solution or an organic solvent. When this photosensitive film-like photosensitive adhesive is used, it can be exposed through a photomask, processed by a developer to form a pattern, and the semiconductor element and the supporting substrate for semiconductor element mounting can be bonded by thermocompression via the pattern, Accordingly, a semiconductor device in which a high-definition adhesive pattern is formed can be obtained (for example, refer to Patent Document 1).

prior art literature

patent documents

Patent Document 1: International Publication No. 2007/004569 Pamphlet

Contents of the invention

The problem to be solved by the invention

However, when a semiconductor device is produced using the film-like photosensitive adhesive described in Patent Document 1 or the like, there is a problem that thermal compression failure or the like occurs, and the heat resistance of the obtained semiconductor device may decrease.

Therefore, the inventors of the present invention conducted intensive studies, and as a result, found that thermocompression failure may occur by the following mechanism.

That is, the above-mentioned film-like photosensitive adhesive is designed to be soluble in alkaline aqueous solution and organic solvent, so its moisture absorption rate or water absorption rate is high, and it is easy to absorb moisture during storage or in the assembly process of a semiconductor device. The moisture absorbed by this moisture vaporizes and expands during thermocompression bonding of the semiconductor element and the semiconductor element mounting support base material, causing foaming, which causes thermocompression failure and the like to occur.

In addition, it has also been found that voids in the adhesive due to the above-mentioned foaming may cause a decrease in the heat resistance of the semiconductor device.

In view of the above circumstances, an object of the present invention is to provide a semiconductor device excellent in heat resistance, and a method of manufacturing a semiconductor device capable of manufacturing such a semiconductor device and less prone to defects such as thermocompression failure.

means of solving problems

The present invention provides a semiconductor device, which is a semiconductor device in which a semiconductor element and an adherend are thermocompressed through a patterned film-shaped photosensitive adhesive. The patterned film-shaped photosensitive adhesive is about to be heated The moisture content before crimping is 1.0% by weight or less. The heat resistance of the semiconductor device is excellent.

The reason why the semiconductor device of the present invention can obtain such an effect is unclear, but the present inventors consider the reason as follows.

That is, in order to manufacture an electronic component from a semiconductor device, it generally needs to go through a curing process for curing an adhesive and a solder reflow process, and high-temperature treatment is necessary in these processes. In the semiconductor device of the present invention, the peeling of the adhesive bond layer due to vaporization, expansion, etc. of moisture exposed to high temperature can be prevented by keeping the moisture content below a predetermined value, and thus is excellent in heat resistance.

The above-mentioned adherend is preferably a semiconductor element or a cover glass.

The film-like photosensitive adhesive preferably contains at least (A) a thermoplastic resin and (B) a thermosetting resin, and preferably further contains (C) a radiation polymerizable compound and (D) a photoinitiator.

The aforementioned (A) thermoplastic resin is preferably an alkali-soluble resin. From the viewpoint of particularly excellent developability and heat resistance, the alkali-soluble resin is preferably a polyimide resin having a carboxyl group and/or a hydroxyl group in a molecule.

The aforementioned (B) thermosetting resin is preferably an epoxy resin from the viewpoint of being able to have excellent adhesive force at high temperature.

The patterned film-like photosensitive adhesive is preferably formed through the process of forming an adhesive layer made of a film-like photosensitive adhesive on an adherend (preferably a semiconductor wafer). process; an exposure process of exposing the adhesive layer in a predetermined pattern; a development process of developing the exposed adhesive layer with an alkaline aqueous solution; and adjusting the moisture content of the developed adhesive layer The moisture content adjustment process.

In addition, the present invention provides a method for manufacturing a semiconductor device, the method having the following steps: a patterning step of patterning a film-like photosensitive adhesive provided on a circuit surface of a semiconductor element by exposure and development; The moisture content adjustment step of adjusting the moisture content of the photosensitive adhesive; the thermocompression bonding process of thermocompression bonding the adherend on the patterned photosensitive adhesive to perform direct bonding. In the amount adjustment step, the water content adjustment process is performed so that the water content of the film-shaped photosensitive adhesive patterned on the PET base material after the patterning is 1.0% by weight or less. Also provided is a semiconductor device manufactured by the manufacturing method.

The above-mentioned adherend is preferably a semiconductor element or a cover glass.

The above-mentioned water content adjustment treatment is preferably heat treatment. The heat treatment can be performed, for example, at 80 to 200° C. for 5 seconds to 30 minutes.

The film-like photosensitive adhesive preferably contains at least (A) a thermoplastic resin and (B) a thermosetting resin, and preferably further contains (C) a radiation polymerizable compound and (D) a photoinitiator.

The aforementioned (A) thermoplastic resin is preferably an alkali-soluble resin. From the viewpoint of particularly excellent developability and heat resistance, the alkali-soluble resin is preferably a polyimide resin having a carboxyl group and/or a hydroxyl group in a molecule.

The aforementioned (B) thermosetting resin is preferably an epoxy resin from the viewpoint of being able to have excellent adhesive force at high temperature.

Invention effect

According to the present invention, it is possible to provide a semiconductor device excellent in heat resistance, and a method for manufacturing a semiconductor device capable of manufacturing such a semiconductor device and less prone to defects such as thermocompression failure.

Description of drawings

FIG. 1 is a cross-sectional view showing one embodiment of a method of manufacturing a semiconductor device.

FIG. 2 is a cross-sectional view illustrating an embodiment of a method of manufacturing a semiconductor device.

3 is a plan view showing one embodiment of a method of manufacturing a semiconductor device.

4 is a plan view illustrating an embodiment of a method of manufacturing a semiconductor device.

5 is a plan view illustrating an embodiment of a method of manufacturing a semiconductor device.

6 is a plan view showing one embodiment of a method of manufacturing a semiconductor device.

7 is a plan view showing one embodiment of a method of manufacturing a semiconductor device.

FIG. 8 is a cross-sectional view showing an embodiment of a semiconductor wafer having an adhesive layer.

Fig. 9 is a plan view showing an embodiment of an adhesive pattern.

Fig. 10 is a sectional view taken along line VI-VI of Fig. 9 .

Fig. 11 is a plan view showing an embodiment of an adhesive pattern.

Fig. 12 is a cross-sectional view along line VIII-VIII of Fig. 11 .

Fig. 13 is a plan view showing a state where a cover glass is bonded to a semiconductor wafer via an adhesive pattern.

Fig. 14 is a sectional view along line X-X of Fig. 13 .

Fig. 15 is a plan view showing a state where a cover glass is adhered to a semiconductor wafer via an adhesive pattern.

Fig. 16 is a sectional view taken along line XII-XII of Fig. 15 .

FIG. 17 is a cross-sectional view showing an embodiment of a semiconductor device.

FIG. 18 is a cross-sectional view showing an embodiment of a semiconductor device.

19 is a sectional view showing an embodiment of a CCD camera module (Camera Module).

Fig. 20 is a cross-sectional view showing one embodiment of a CCD camera module.

FIG. 21 is a cross-sectional view showing an embodiment of a semiconductor device.

22 is a cross-sectional view illustrating an embodiment of a method of manufacturing a semiconductor device.

23 is a cross-sectional view illustrating an embodiment of a method of manufacturing a semiconductor device.

24 is a cross-sectional view illustrating an embodiment of a method of manufacturing a semiconductor device.

FIG. 25 is a cross-sectional view illustrating an embodiment of a method of manufacturing a semiconductor device.

26 is a cross-sectional view illustrating an embodiment of a method of manufacturing a semiconductor device.

Detailed ways

The best mode for carrying out the invention will be described in detail below. However, the present invention is not limited by the description below.

The semiconductor device of the present invention is characterized in that it is a semiconductor device in which a semiconductor element and an adherend are thermocompressed via a patterned film-like photosensitive adhesive, and the patterned film-like photosensitive adhesive is about to The moisture content before thermocompression bonding is 1.0% by weight or less.

In addition, the manufacturing method of the semiconductor device of the present invention is characterized in that the method has the following steps: a patterning step of patterning the film-like photosensitive adhesive provided on the circuit surface of the semiconductor element by exposure and development; The moisture content adjustment step of adjusting the moisture content of the photosensitive adhesive; the thermocompression bonding process of thermocompression bonding the adherend on the patterned photosensitive adhesive to perform direct bonding. In the amount adjustment step, the water content adjustment process is performed so that the water content of the film-shaped photosensitive adhesive patterned on the PET base material after the patterning is 1.0% by weight or less.

The above-mentioned moisture adjustment treatment is more preferably the following treatment: the moisture content of the film-like photosensitive adhesive formed on the PET substrate after the pattern is 0.7% by weight or less; more preferably the following treatment: the PET substrate The water content of the photosensitive film-like adhesive agent patterned on the top is 0.5% by weight or less after patterning.

If the above-mentioned moisture content adjustment treatment is not performed, when the semiconductor element and the adherend are thermocompression-bonded, the moisture remaining in the film-like photosensitive adhesive will cause foaming due to moisture vaporization and expansion, resulting in being adhered. The crimped semiconductor elements and peeling of the cover glass, etc., present obstacles to the manufacture of semiconductor devices. In addition, in the curing process and solder reflow process, when the remaining moisture is exposed to high temperature, it vaporizes and expands, causing peeling of the adhesive and the adherend.

In addition, there is a high possibility that voids will be generated in the adhesive due to the above-mentioned foaming, resulting in a decrease in the heat resistance of the semiconductor device.

Moreover, the moisture content of the patterned film-form photosensitive adhesive agent can be measured using the moisture measuring apparatus "AQV2100CT" manufactured by Hiranuma Sangyo, for example.

The water content in the present invention is defined as follows.

A transparent PET film as a protective film was further bonded to the film-like photosensitive adhesive with a thickness of 50 μm formed on the PET substrate, and the obtained adhesive sheet was cut into a size of 150 mm×150 mm. A mask was placed on the cut adhesive sheet, exposed (irradiated with ultraviolet rays) at an exposure amount of 1000 mJ/cm ² using a high-precision parallel exposure machine (manufactured by ORC MANUFACTURING CO., LTD.), and heated at 80°C for 30 Second. Then, the PET film on one side was peeled off, and developed using a spray developing machine manufactured by YAKO Co., Ltd. (developing solution: tetramethylammonium hydroxide (TMAH) 2.38%, 27° C.; spray pressure: 0.18 MPa; water washing: pure water at 23°C and a spray pressure of 0.02 MPa). As described above, the photosensitive adhesive pattern was formed on the PET substrate, and then, the TMAH adhering to the film was washed with pure water for 6 minutes. Then, it was left to stand at room temperature for 30 minutes, the PET substrate was peeled off, and the moisture content of the patterned film-form photosensitive adhesive was measured with the Hiranuma Sangyo moisture measuring device "AQV2100CT". The amount of moisture in the present invention refers to the amount of moisture at this time.

In addition, the water content adjustment process in this invention means to adjust a water content so that the water content at this time may be 1.0 weight% or less. The conditions of this water content adjustment treatment can be appropriately adjusted according to the type of film. For example, when the film-like photosensitive adhesive contains fluorine atoms, the amount of moisture absorbed is small, and the affinity with the absorbed moisture is also low. Therefore, the moisture content adjustment treatment in this case may be used for dehydration. Spin drying etc. in addition to moisture. In addition, in other cases, it is preferable to adjust the conditions appropriately according to the type of the film. In addition, when heat treatment is performed as moisture content adjustment treatment, it is preferably performed at 80 to 200°C for 5 seconds to 30 minutes, more preferably at 100°C to 200°C for 30 seconds to 20 minutes, and particularly preferably at 120°C. Perform at ~200°C for 1 minute to 10 minutes.

In the case of heat treatment as a moisture content adjustment treatment, if the temperature is lower than 80°C and less than 5 seconds, the moisture content of the patterned film-like photosensitive adhesive formed on the PET substrate will be 1.0% by weight or more. In addition, if the heating conditions exceed 200° C. for more than 30 minutes, the patterned film-like photosensitive adhesive will be thermally cured, and there is a tendency for thermal fluidity during thermocompression bonding to be impaired.

In the case of performing the above-mentioned heat treatment, for example, a patterned film-like photosensitive adhesive formed on the adherend may be placed on a polyvinyl fluoride-based fiber sheet or the like, together with the polyvinyl fluoride-based fiber sheet Place on a hot plate and heat at the specified temperature and time.

When the above-mentioned moisture content adjustment treatment is performed, it is possible to reduce adhesion failures caused by voids generated during thermocompression bonding, thermosetting, and solder reflow, and it is possible to manufacture a heat-resistant semiconductor device.

The thermocompression bonding of the semiconductor element and the adherend can be performed, for example, by pressure bonding at a heating temperature of 20 to 250° C. and a load of 0.01 to 20 kgf for 0.1 to 300 seconds.

The patterned film-like photosensitive adhesive is preferably formed through the following steps: an adhesive layer forming step of forming an adhesive layer made of a film-like photosensitive adhesive on an adherend; The exposure process of exposing the agent layer in a predetermined pattern; the development process of developing the exposed adhesive layer with an alkaline aqueous solution.

In the adhesive layer forming step, for example, the film-like photosensitive adhesive composition (varnish) can be laminated on an adherend such as a silicon wafer with a roll under pressure at a temperature of preferably 20 to 150° C. Thus, an adhesive layer is formed.

In the exposure process, for example, a photomask formed with a predetermined pattern can be placed on the above-mentioned adhesive layer, and the exposure amount: 100 to 1000 mJ/cm Irradiate ultraviolet light (exposure) under the conditions of ² . In addition, the above-mentioned adhesive pattern may also be formed by directly drawing and exposing the pattern on the above-mentioned adhesive layer by using a direct drawing exposure technique. After this exposure process, you may heat at 40 degreeC - 120 degreeC for 5 second - 30 second as needed.

In the development step, for example, a solution of 1.0 to 5.0%, preferably 2.38%, of tetramethylammonium hydroxide (TMAH) is used for spray development to form the adhesive layer in a pattern shape. Here, when the film-form photosensitive adhesive is positive, the exposed portion is removed, and when the film-form photosensitive adhesive is negative, the exposed portion remains.

The line width of the above pattern is preferably in the range of 0.01 mm to 20 mm.

In addition, the shape of the above-mentioned pattern is not particularly limited, and examples thereof include a frame shape, a line shape, and a through hole. Among them, a frame shape can obtain a stable patterned adhesive, and a frame shape is preferable from this point of view.

The film-like photosensitive adhesive preferably contains at least (A) a thermoplastic resin and (B) a thermosetting resin; and preferably further contains (C) a radiation polymerizable compound and (D) a photoinitiator.

(A) The thermoplastic resin is not particularly limited as long as it is soluble in an alkaline developer, and examples thereof include polyimide resins, polyamide resins, polyamideimide resins, polyetherimide resins, polyurethane imide resins, and polyimide resins. Amine resins, polyurethane amideimide resins, silicone polyimide resins, polyesterimide resins or their copolymers, and phenoxy resins, polysulfone resins, polyethersulfone resins, polyphenylene sulfide resins , polyester resin, polyether ketone resin, (meth)acrylic acid copolymer, etc. at least one or more resins from the group consisting of, among them, polyamide resin is preferable from the viewpoint of achieving both developability and heat resistance. The imine resin is more preferably a polyimide resin having an alkali-soluble group such as a carboxyl group and/or a hydroxyl group at a side chain or at a terminal.

The polyimide resin can be obtained by carrying out condensation reaction of tetracarboxylic dianhydride and diamine by a well-known method, for example. That is, in the organic solvent, tetracarboxylic dianhydride and diamine are adjusted to be equimolar, or if necessary, the composition ratio is adjusted so that the total amount of diamine is preferably 0.5 to 2.0 with respect to a total of 1.0 mol of tetracarboxylic dianhydride. mol, more preferably in the range of 0.8 to 1.0 mol (the order of addition of each component is arbitrary), and the addition reaction is carried out at a reaction temperature of 80°C or lower, preferably 0 to 60°C. As the reaction proceeds, the viscosity of the reaction liquid gradually increases, and polyamic acid, which is a precursor of the polyimide resin, is produced. In addition, it is preferable that the above-mentioned tetracarboxylic dianhydride is subjected to a recrystallization purification treatment with acetic anhydride in order to suppress a decrease in various properties of the adhesive.

In addition, regarding the composition ratio of tetracarboxylic dianhydride and diamine in the above-mentioned condensation reaction, when the total of diamine exceeds 2.0 mol with respect to the total of 1.0 mol of tetracarboxylic dianhydride, there is a polyimide resin obtained The amount of the polyimide oligomer having an amine end tends to increase. On the other hand, when the total amount of diamines is less than 0.5 mol, the amount of a polyimide oligomer having an acid end tends to increase. In both cases, the weight-average molecular weight of the polyimide resin tends to decrease, and various properties including the heat resistance of the adhesive tend to decrease.

In addition, it is preferable to determine an appropriate feed composition ratio of tetracarboxylic dianhydride and diamine so that the weight average molecular weight of the obtained polyimide resin is 10,000 to 300,000.

The polyimide resin can be obtained by dehydrating and ring-closing the above-mentioned reaction product (polyamic acid). The dehydration ring closure can be performed by a thermal ring closure method of heat treatment, a chemical ring closure method using a dehydrating agent, or the like.

Tetracarboxylic dianhydride used as a raw material for polyimide resin is not particularly limited, and examples thereof include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane Dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethanedianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethanedianhydride, bis(2,3-di Carboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, 3,4,9,10-perylenetetracarboxylic acid Dianhydride, bis(3,4-dicarboxyphenyl) ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3',4'-benzophenone tetracarboxylic Acid dianhydride, 2,3,2',3'-benzophenone tetracarboxylic dianhydride, 3,3,3',4'-benzophenone tetracarboxylic dianhydride, 1,2,5, 6-naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 1,2,4,5-naphthalene tetracarboxylic Acid dianhydride, 2,6-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2,7-dichloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 2, 3,6,7-tetrachloronaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,8,9,10-tetracarboxylic dianhydride, pyrazine-2,3,5,6 -tetracarboxylic dianhydride, thiophene-2,3,5,6-tetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 3,4,3',4' -Biphenyltetracarboxylic dianhydride, 2,3,2',3'-biphenyltetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)dimethylsilane dianhydride, bis(3,4 -Dicarboxyphenyl)methylphenylsilane dianhydride, bis(3,4-dicarboxyphenyl)diphenylsilane dianhydride, 1,4-bis(3,4-dicarboxyphenyldimethylmethane Silyl) phthalic anhydride, 1,3-bis(3,4-dicarboxyphenyl)-1,1,3,3-tetramethyldicyclohexane dianhydride, p-phenylene bis(trimellitic acid anhydride), ethylene tetracarboxylic dianhydride, 1,2,3,4-butane tetracarboxylic dianhydride, decahydronaphthalene-1,4,5,8-tetracarboxylic dianhydride, 4, 8-Dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, cyclopentane-1,2,3,4-tetracarboxylic Acid dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, bis(exo-bicyclo[2,2,1 ]heptane-2,3-dicarboxylic dianhydride, bicyclo-[2,2,2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl)propane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenyl)phenyl]propane dianhydride, 2,2-bis(3,4-bis Carboxyphenyl) hexafluoropropane dianhydride, 2,2-bis[4-(3,4-dicarboxyphenyl)phenyl]hexafluoropropane dianhydride, 4,4'-bis(3,4-dicarboxy Phenoxy) diphenylsulfide Ether dianhydride, 1,4-bis(2-hydroxyhexafluoroisopropyl)benzenebis(trimellitic anhydride), 1,3-bis(2-hydroxyhexafluoroisopropyl)benzenebis(trimellitic anhydride), 5-(2 , 5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, and the following general Tetracarboxylic dianhydride represented by formula (I), etc.

[chemical formula 1]

[wherein, a represents an integer of 2-20. ]

The tetracarboxylic dianhydride represented by the above general formula (I) can be synthesized from, for example, trimellitic anhydride monochloride and corresponding diols, specifically, 1,2-(ethylene) bis(trimellitic anhydride) ), 1,3-(trimethylene)bis(trimellitic anhydride), 1,4-(tetramethylene)bis(trimellitic anhydride), 1,5-(pentamethylene ) bis(trimellitic anhydride), 1,6-(hexamethylene)bis(trimellitic anhydride), 1,7-(heptamethylene)bis(trimellitic anhydride) , 1,8-(octamethylene)bis(trimellitic anhydride), 1,9-(nonamethylene)bis(trimellitic anhydride), 1,10-(decamethylene ) bis(trimellitic acid anhydride), 1,12-(dodecamethylene) bis(trimellitic acid anhydride), 1,16-(hexadecyl methylene) bis(trimellitic acid anhydride) anhydride), 1,18-(octadecamethylene)bis(trimellitic anhydride), etc.

Moreover, tetracarboxylic dianhydride represented by following general formula (II) or (III) is preferable as tetracarboxylic dianhydride from a viewpoint of the good solubility to a solvent, and moisture-resistant reliability provision.

[chemical formula 2]

[chemical formula 3]

The above tetracarboxylic dianhydrides may be used alone or in combination of two or more.

It is preferable that the diamine used as a raw material of the said polyimide resin contains the aromatic diamine represented by following formula (IV)-(VII). It is preferable that the diamine represented by these following formula (IV)-(VII) accounts for 1-70 mol% of all diamines. Accordingly, a polyimide resin soluble in an alkaline developer can be prepared.

[chemical formula 4]

[chemical formula 5]

[chemical formula 6]

[chemical formula 7]

Other diamines used as raw materials for the polyimide resin are not particularly limited, and examples thereof include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3' -Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylmethane, 3,4'-diamino Aminodiphenylmethane, 4,4'-diaminodiphenylmethane, bis(4-amino-3,5-dimethylphenyl)methane, bis(4-amino-3,5-diisopropyl phenyl)methane, 3,3'-diaminodiphenyldifluoromethane, 3,4'-diaminodiphenyldifluoromethane, 4,4'-diaminodiphenyldifluoromethane, 3,3 '-Diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfide, 3,4' -Diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4' -Diaminodiphenylketone, 2,2-bis(3-aminophenyl)propane, 2,2'-(3,4'-diaminodiphenyl)propane, 2,2-bis(4-amino Phenyl)propane, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-(3,4'-diaminodiphenyl)hexafluoropropane, 2,2-bis(4-amino Phenyl)hexafluoropropane, 1,3-bis(3-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy) Benzene, 3,3'-(1,4-phenylenebis(1-methylethylene))bisaniline, 3,4'-(1,4-phenylenebis(1-methylethylene) base)) bis-aniline, 4,4'-(1,4-phenylene bis(1-methylethylene)) bis-aniline, 2,2-bis(4-(3-aminophenoxy)benzene base) propane, 2,2-bis(4-(3-aminophenoxy)phenyl)hexafluoropropane, 2,2-bis(4-(4-aminophenoxy)phenyl)hexafluoropropane, Bis(4-(3-aminophenoxy)phenyl)sulfide, bis(4-(4-aminophenoxy)phenyl)sulfide, bis(4-(3-aminophenoxy)phenyl) ) sulfone, bis(4-(4-aminophenoxy)phenyl) sulfone, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,5-diaminobenzoic acid and other aromatic di Amine, 1,3-bis(aminomethyl)cyclohexane, 2,2-bis(4-aminophenoxyphenyl)propane, 2,2-bis(3-amino-4-hydroxyphenyl)hexa Fluoropropane, aliphatic ether diamine represented by the following general formula (VIII), aliphatic diamine represented by the following general formula (X), siloxane diamine represented by the following general formula (XI), and the like.

[chemical formula 8]

[wherein, Q ¹ , Q ² and Q ³ each independently represent an alkylene group having 1 to 10 carbon atoms, and b represents an integer of 2 to 80. ]

[chemical formula 9]

[wherein, c represents an integer of 5-20. ]

[chemical formula 10]

[wherein, Q ⁴ and Q ⁹ each independently represent an alkylene group having 1 to 5 carbon atoms or a phenylene group that may have a substituent, and Q ⁵ , Q ⁶ , Q ⁷ and Q ⁸ each independently represent a carbon atom Alkyl group, phenyl group or phenoxy group of number 1-5, d represents an integer of 1-5. ]

As the aliphatic ether diamine represented by the above-mentioned general formula (VIII), specifically, the following formulas are exemplified:

[chemical formula 11]

The aliphatic diamine represented by and the aliphatic ether diamine represented by following formula (IX).

[chemical formula 12]

[wherein, e represents an integer of 0-80. ]

Specific examples of the aliphatic diamine represented by the general formula (X) include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5 -Diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane , 1,11-diaminoundecane, 1,12-diaminododecane, 1,2-diaminocyclohexane, etc.

As the siloxane diamine represented by the above-mentioned general formula (XI), specifically, as a compound in which d is 1 in the general formula (XI), 1,1,3,3-tetramethyl-1,3 -bis(4-aminophenyl)disiloxane, 1,1,3,3-tetraphenoxy-1,3-bis(4-aminoethyl)disiloxane, 1,1,3, 3-tetraphenyl-1,3-bis(2-aminoethyl)disiloxane, 1,1,3,3-tetraphenyl-1,3-bis(3-aminopropyl)disiloxane alkane, 1,1,3,3-tetramethyl-1,3-bis(2-aminoethyl)disiloxane, 1,1,3,3-tetramethyl-1,3-bis(3 -aminopropyl)disiloxane, 1,1,3,3-tetramethyl-1,3-bis(3-aminobutyl)disiloxane, 1,3-dimethyl-1,3 - Dimethoxy-1,3-bis(4-aminobutyl)disiloxane and the like.

In addition, examples of compounds where d is 2 include 1,1,3,3,5,5-hexamethyl-1,5-bis(4-aminophenyl)trisiloxane, 1,1,5, 5-tetraphenyl-3,3-dimethyl-1,5-bis(3-aminopropyl)trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethoxy Base-1,5-bis(4-aminobutyl)trisiloxane, 1,1,5,5-tetraphenyl-3,3-dimethoxy-1,5-bis(5-aminopentyl) base) trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis(2-aminoethyl)trisiloxane, 1,1,5 , 5-tetramethyl-3,3-dimethoxy-1,5-bis(4-aminobutyl)trisiloxane, 1,1,5,5-tetramethyl-3,3-di Methoxy-1,5-bis(5-aminopentyl)trisiloxane, 1,1,3,3,5,5-hexamethyl-1,5-bis(3-aminopropyl)trisiloxane Siloxane, 1,1,3,3,5,5-hexaethyl-1,5-bis(3-aminopropyl)trisiloxane, 1,1,3,3,5,5-hexa Propyl-1,5-bis(3-aminopropyl)trisiloxane and the like.

Other diamines used as raw materials for the above-mentioned polyimide resin are preferably diamines containing fluorine atoms, more preferably 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (hereinafter referred to as " BIS-AP-AF"). Using the diamine containing a fluorine atom can adjust the moisture content of a film-form photosensitive adhesive agent low. It is considered that the amount of absorbed water decreases and the affinity with absorbed water is lowered by including fluorine atoms in the molecule, so that water evaporates easily.

The said diamine can be used individually by 1 type or in combination of 2 or more types.

In addition, the said polyimide resin can be used individually by 1 type or in mixture (blend) of 2 or more types as needed.

(B) A thermosetting resin refers to a reactive compound capable of undergoing a crosslinking reaction by heat. Examples of such compounds include epoxy resins, cyanate resins, bismaleimide resins, phenolic resins, urea resins, melamine resins, alkyd resins, acrylic resins, unsaturated polyester resins, ophthalmic resins, Diallyl diformate resin, silicone resin, resorcinol formaldehyde resin, xylene resin, furan resin, polyurethane resin, ketone resin, triallyl cyanurate resin, polyisocyanate resin, containing three (2- Hydroxyethyl) isocyanurate resin, resin containing triallyl trimellitate, thermosetting resin synthesized from cyclopentadiene, thermosetting resin obtained by trimerization of aromatic dicyandiamide Sexual resin, etc.

Among them, epoxy resins, cyanate resins, and bismaleimide resins are preferable from the viewpoint of having excellent adhesive force at high temperatures, and epoxy resins are particularly preferable from the viewpoints of workability and productivity. resin. These (B) thermosetting resins can be used individually by 1 type or in combination of 2 or more types.

As the above-mentioned epoxy resin, an epoxy resin containing at least two or more epoxy groups in the molecule is more preferable, and a glycidyl ether type epoxy resin of phenol is particularly preferable from the viewpoint of curability and properties of a cured product. Such resins include, for example, bisphenol A type (or AD type, S type, F type) glycidyl ether, hydrogenated bisphenol A type glycidyl ether, bisphenol A type ethylene oxide addition Glycidyl ether of bisphenol A propylene oxide adduct, glycidyl ether of phenol novolac resin, glycidyl ether of cresol novolac resin, glycidyl ether of bisphenol A novolac resin Glyceryl ether, glycidyl ether of naphthalene resin, 3-functional (or 4-functional) glycidyl ether, glycidyl ether of dicyclopentadiene phenolic resin, glycidyl ester of dimer acid, 3-functional (or 4-functional) Functional type) glycidyl amine, glycidyl amine of naphthalene resin, etc. These can be used individually by 1 type or in combination of 2 or more types.

In addition, in order to prevent electromigration and corrosion of metal conductor circuits, it is preferable to use alkali metal ions, alkaline earth metal ions, halogen ions, especially chloride ions and hydrolyzable chlorine as impurity ions in these epoxy resins as low as 300 ppm or less. High purity product.

The content of (B) the thermosetting resin is preferably 5 to 200 parts by mass, more preferably 10 to 100 parts by mass, based on 100 parts by mass of the total solid content of the adhesive. When the content is less than 5 parts by mass, heat resistance tends to decrease, and when it exceeds 200 parts by mass, film formability tends to deteriorate.

(C) The radiation-polymerizable compound is not particularly limited as long as it is polymerized and/or cured by irradiation with radiation such as ultraviolet rays or electron beams. Specific examples of radiation polymerizable compounds include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, methyl 2-ethylhexyl acrylate, pentenyl acrylate, tetrahydrofurfuryl acrylate, tetrahydrofurfuryl methacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate Acrylates, Diethylene Glycol Dimethacrylate, Triethylene Glycol Dimethacrylate, Tetraethylene Glycol Dimethacrylate, Trimethylolpropane Diacrylate, Trimethylolpropane Triacrylate , Trimethylolpropane Dimethacrylate, Trimethylolpropane Trimethacrylate, 1,4-Butanediol Diacrylate, 1,6-Hexanediol Diacrylate, 1,4-Butane Diol dimethacrylate, 1,6-hexanediol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate , dipentaerythritol hexamethacrylate, styrene, divinylbenzene, 4-vinyltoluene, 4-vinylpyridine, N-vinylpyrrolidone, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate , 1,3-acryloyloxy-2-hydroxypropane, 1,2-methacryloyloxy-2-hydroxypropane, methylene-bisacrylamide, N,N-dimethylacrylamide, N -Methylolacrylamide, triacrylate of tris(β-hydroxyethyl)isocyanurate, compound represented by the following general formula (XII), urethane acrylate, urethane methacrylate, and urea Acrylic etc.

[chemical formula 13]

[wherein, R ⁴¹ and R ⁴² each independently represent a hydrogen atom or a methyl group, and f and g each independently represent an integer of 1 or more. ]

The above-mentioned urethane acrylate and urethane methacrylate are produced, for example, by reaction of diols, an isocyanate compound represented by the following general formula (XIII), and a compound represented by the following general formula (XIV).

[chemical formula 14]

[wherein, R ⁴³ represents a divalent or trivalent organic group with 1 to 30 carbon atoms, and h represents 0 or 1. ]

[chemical formula 15]

[In the formula, R ⁴⁴ represents a hydrogen atom or a methyl group, and R ⁴⁵ represents an ethylene group or a propylene group. ]

The said urea methacrylate is produced by reaction of the diamine represented by the following general formula (XV), and the compound represented by the following general formula (XVI), for example.

[chemical formula 16]

H ₂ NR ⁴⁶ -NH ₂ (xv)

[wherein, R ⁴⁶ represents a divalent organic group with 2 to 30 carbon atoms. ]

[chemical formula 17]

[wherein, i represents 0 or 1. ]

In addition to the above-mentioned compounds, radiation polymerizable copolymers having ethylenically unsaturated groups in side chains, etc., which can be obtained by having at least one ethylene It is obtained by the addition reaction of compounds with functional groups such as unsaturated groups and epoxy rings, isocyanate groups, hydroxyl groups, and carboxyl groups with vinyl copolymers containing functional groups.

These radiation polymerizable compounds can be used individually by 1 type or in combination of 2 or more types. Among these, the radiation polymerizable compound represented by the above general formula (XII) is preferable from the viewpoint of being able to sufficiently impart solvent resistance after curing, and ammonia is preferable from the viewpoint of being able to sufficiently impart high adhesiveness after curing. ester acrylates and urethane methacrylates.

It is preferable that it is 20-200 mass parts with respect to 100 mass parts of (A) thermoplastic resins, and, as for content of (C), a radiation polymerizable compound, More preferably, it is 30-100 mass parts. When this content exceeds 200 mass parts, there exists a tendency for the fluidity|fluidity at the time of heat fusion to fall by polymerization, and the adhesiveness at the time of thermocompression bonding to fall. On the other hand, when it is less than 20 parts by mass, the solvent resistance after exposure and photocuring tends to be low, and pattern formation tends to be difficult.

(D) The photoinitiator refers to a photopolymerization initiator that generates free radicals by irradiation with radiation, a photobase generator that generates a base by irradiation with radiation, and the like.

In order to improve sensitivity, it is preferable that the photopolymerization initiator which generates free radicals by irradiation with radiation has an absorption band at 300 to 500 nm.

Specific examples of the photopolymerization initiator include benzophenone, N, N'-tetramethyl-4,4'-diaminobenzophenone (Michler's ketone), N, N'-tetraethyl Base-4,4'-diaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1-(4-methoxy (Linophenyl)-butanone-1, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl-one, 2-methyl -1-(4-(methylthio)phenyl)-2-morpholinoacetone-1, 2,4-diethylthioxanthone, 2-ethylanthraquinone and phenanthrenequinone and other aromatic ketones, benzene Benzoin ethers such as azoin methyl ether, benzoin ethyl ether and benzoin phenyl ether, benzoin such as methyl benzoin and ethyl benzoin, and benzoin such as dibenzoyl dimethyl acetal Acyl derivatives, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-bis(m-methoxyphenyl)imidazole dimer 2-(o-fluorophenyl)-4,5-phenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methyl oxyphenyl)-4,5-diphenylimidazole dimer, 2,4-bis(p-methoxyphenyl)-5-phenylimidazole dimer and 2-(2,4-dimethyl 2,4,5-triaryl imidazole dimer, 9-phenylacridine and 1,7-bis(9,9'-acridine Acridine derivatives such as pyridyl)heptane, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphosphine oxide and bis(2,4,6- Bisacylphosphine oxides such as trimethylbenzoyl)-phenylphosphine oxide, etc. These can be used individually or in combination of 2 or more types.

In addition, the photobase generator is not particularly limited as long as it is a compound that generates a base when irradiated with radiation. From the viewpoint of reactivity and curing speed, the base to be generated is preferably a strongly basic compound. Generally, the pKa value, which is the logarithm of the acid dissociation constant, is used as an index of basicity, and a base having a pKa value of 7 or more in aqueous solution is preferred, and a base having a pKa value of 9 or more in aqueous solution is more preferred.

Such bases generated when irradiated with radiation include, for example, imidazole derivatives such as imidazole, 2,4-dimethylimidazole, and 1-methylimidazole; piperazines such as piperazine and 2,5-dimethylpiperazine; Derivatives; piperidine derivatives such as piperidine and 1,2-dimethylpiperidine; proline derivatives, trimethylamine, triethylamine, triethanolamine and other trialkylamine derivatives; 4-form Pyridine derivatives substituted with amino or alkylamino groups at the 4-position, such as aminopyridine and 4-dimethylaminopyridine; pyrrole derivatives such as pyrrole and n-methylpyrrole; triethylenediamine, 1,8-diazo Alicyclic amine derivatives such as heterobicyclo(5,4,0)undecane-1(DBU); benzylamine derivatives such as benzylmethylamine, benzyldimethylamine and benzyldiethylamine wait.

The above-mentioned photobase generators that generate bases by irradiating radiation can be used, for example, in Journal of Photopolymer Science and Technology (Photopolymer Science and Technology Journal) 12 volumes, 313-314 items (1999), Chemistry of Materials (Materials Quaternary ammonium salt derivatives described in Vol. 11, Items 170-176 (1999) of Chemistry).

In addition, as the photobase generator, carbamic acid described in Journal of American Chemical Society (Journal of American Chemical Society) vol. 118, p. 12925 (1996), Polymer Journal (Polymer Journal) 28, p. derivative.

In addition, oxime derivatives that generate primary amino groups by irradiation with active light, commercially available photoradical generators 2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropane -1-ketone (manufactured by Ciba Specialty Chemicals, IRGACURE907), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 (manufactured by Ciba Specialty Chemicals, IRGACURE369 ), hexaarylbisimidazole derivatives (the phenyl group may be substituted by substituents such as halogen, alkoxy, nitro, cyano, etc.), benzisoxazolone derivatives, etc.

In addition, on the basis of using the above-mentioned photobase generator that generates a base by irradiation with radiation, or instead of the above-mentioned photobase generator, photo-Fries (Fries) rearrangement, photo-Claisen rearrangement (photo-Cleisen rearrangement) can be used. Reaction), Curtius rearrangement (Curtius rearrangement), Stevens rearrangement (Stevens rearrangement) and other reactions generate alkali to cure the epoxy resin.

Since these compounds do not show reactivity with epoxy resins at room temperature in a state where they are not irradiated with radiation, they are characterized by very excellent storage stability at room temperature.

(D) Content of a photoinitiator is not specifically limited, It is 0.01-30 mass parts normally with respect to 100 mass parts of (A) thermoplastic resins.

Moreover, a hardening accelerator may be contained in the said film-form photosensitive adhesive agent as needed. The above-mentioned curing accelerator is not particularly limited as long as it is capable of curing the (B) thermosetting resin, and examples thereof include imidazoles, dicyandiamide derivatives, dicarboxylic acid dihydrazides, triphenylphosphine, tetraphenyl Phosphonium tetraphenyl borate, 2-ethyl-4-methylimidazolium-tetraphenyl borate, 1,8-diazabicyclo[5.4.0]undecane-7-tetraphenylboronic acid salt etc.

When using the said epoxy resin, a hardening|curing agent may be contained in the said film-form photosensitive adhesive agent as needed. Examples of the curing agent include phenolic compounds, aliphatic amines, alicyclic amines, aromatic polyamines, polyamides, aliphatic acid anhydrides, alicyclic acid anhydrides, aromatic acid anhydrides, dicyandiamide, organic acid dihydrazides , boron trifluoride amine complexes, imidazoles, tertiary amines, etc. Among these, phenolic compounds are preferable, and phenolic compounds having at least two or more phenolic hydroxyl groups in the molecule are more preferable.

Such compounds include, for example, phenol novolac, cresol novolac, tert-butylphenol novolac, dicyclopentadiene cresol novolac, dicyclopentadiene phenol novolak, xylylene-modified phenol novolac Varnishes, naphthol-based compounds, triphenol-based compounds, tetraphenol novolaks, bisphenol A novolacs, poly-p-vinylphenol, phenol aralkyl resins, and the like. Among these, those having a number average molecular weight in the range of 400 to 1,500 are preferable. Thereby, it is possible to suppress outgassing that would cause contamination of semiconductor elements, devices, and the like during thermocompression bonding.

The said film-form photosensitive adhesive agent may contain a filler. The aforementioned fillers include, for example, alumina, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, alumina, aluminum nitride, crystalline silica, Inorganic fillers such as amorphous silica, boron nitride, titanium dioxide, glass, iron oxide, and ceramics, organic fillers such as carbon, and rubber-based fillers, etc., are not particularly limited in terms of type and shape.

The content of the filler can be determined according to the properties or functions to be imparted, and is usually 1 to 50% by mass, preferably 2 to 40% by mass, more preferably 5 to 30% by mass based on the total of the resin component and filler. By increasing the amount of filler, a high modulus of elasticity can be achieved, and it is possible to effectively improve cutting properties (property of cutting with a dicer), wire bonding properties (ultrasonic efficiency), and adhesive strength during heating.

When the filler is increased beyond the necessary amount, thermocompression bondability tends to be impaired, so the content of the filler is preferably controlled within the above range. Optimal filler levels can be determined to achieve the desired balance of properties. When using a filler, mixing and kneading can be performed by appropriately combining a usual dispersing machine such as a mixer, a sand mixer, a three-roll mill, or a ball mill.

In order to improve the interfacial bonding between different materials, the above-mentioned film-like photosensitive adhesive may contain a silane coupling agent, etc. In addition, in order to absorb ionic impurities and improve the insulation reliability during moisture absorption, an ion-capturing agent may also be included. agent. Furthermore, in order to react the unreacted acrylate remaining at the time of thermosetting, you may contain a thermal radical generating agent.

The above-mentioned film-like photosensitive adhesive can be prepared by dissolving the above-mentioned components in, for example, dimethylformamide, toluene, benzene, xylene, methyl ethyl ketone, tetrahydrofuran, ethyl cellosolve, ethyl cellosolve, etc. Prepare a varnish in organic solvents such as acetate, dioxane, cyclohexanone, ethyl acetate, and N-methyl-pyrrolidone, apply it on a substrate such as a release agent-treated PET, and dry it to achieve preparation.

The film-like photosensitive adhesive preferably has both a function as an adhesive for die bonding and a function as a photosensitive resin for forming a patterned insulating resin film.

Embodiments of the semiconductor device and the manufacturing method of the semiconductor device according to the present invention include a semiconductor device having a structure in which semiconductor elements are stacked, a semiconductor device for a camera module, and a semiconductor device having a flip-chip structure. These embodiments are shown below, but the present invention is not limited to the following forms.

1, 2, 3, 4, 5 and 6 are cross-sectional views or plan views showing one embodiment of a method of manufacturing a semiconductor device. The manufacturing method of the semiconductor device according to this embodiment may include the step of providing a film-like photosensitive adhesive 1 on the circuit surface 25 of the semiconductor element 20 formed in the semiconductor wafer 2 ( FIG. 1( a ), (b)); The process of patterning the film-like photosensitive adhesive 1 provided on the circuit surface 25 of the semiconductor element 20 by exposure and development ((c) of FIG. 1 , (a) of FIG. 2 ); The process of grinding the semiconductor wafer 2 from the surface opposite to the circuit surface 25 to make the semiconductor wafer 2 thin ((b) of FIG. 2 ); the process of dividing the semiconductor wafer 2 into a plurality of semiconductor elements 20 by dicing ( FIG. (c), Fig. 4 (a)); After picking up the semiconductor element 20, it is mounted on the plate-shaped support substrate 7 for semiconductor devices (Fig. 4 (b), Fig. 5 (a)); The process of directly bonding the semiconductor element 21 of the second layer to the photosensitive adhesive 1 patterned on the circuit surface of the semiconductor element 20 mounted on the support base 7 (Fig. 5 (b)); A process of connecting the elements 20, 21 to external connection terminals (FIG. 6).

In the semiconductor wafer 2 shown in FIG. 1( a ), a plurality of semiconductor elements 20 divided by dicing lines 90 are formed. A film-like photosensitive adhesive 1 is provided on the circuit surface 25 side of the semiconductor element 20 ( FIG. 1( b )). A relatively simple method is to prepare a photosensitive adhesive 1 previously formed into a film and bond it to the semiconductor wafer 2 .

The photosensitive adhesive 1 is an alkali-developable negative-type photosensitive adhesive that has adhesiveness to an adherend after being patterned by exposure and development. More specifically, the resist pattern formed by patterning the film-like photosensitive adhesive 1 by exposure and development has adhesiveness to an adherend. For example, the resist pattern and the adherend can be adhered by pressing the adherend onto the resist pattern while heating as necessary. As the said to-be-adhered body, a semiconductor element, a glass substrate, etc. are mentioned. In addition, a patterned film-form photosensitive adhesive may be formed on a semiconductor element as an adherend.

The photosensitive adhesive 1 laminated on the semiconductor wafer 2 is irradiated with active light rays (typically ultraviolet rays) through a mask 3 having openings formed at predetermined positions ( FIG. 1( c )). Thereby, the photosensitive adhesive 1 is exposed in a predetermined pattern.

After exposure, the unexposed portion of the photosensitive adhesive 1 is removed by development with an alkaline developer, so that the photosensitive adhesive 1 can be patterned to form openings 11 ( FIG. 2( a ) ). In addition, a positive photosensitive adhesive may be used instead of a negative photosensitive adhesive, and in this case, the exposed portion of the film-like photosensitive adhesive is removed by development.

FIG. 3 is a plan view showing a state where the photosensitive adhesive 1 is patterned. The opening 11 exposes a bonding pad of the semiconductor element 20 . That is, the patterned photosensitive adhesive 1 is a buffer coating film of the semiconductor element 20 . A plurality of rectangular openings 11 are formed in parallel on each semiconductor element 20 . The shape, arrangement, and number of openings 11 are not limited to those shown in this embodiment, and may be appropriately deformed so that predetermined portions such as pads can be exposed.

After patterning, the surface of the semiconductor wafer 2 opposite to the photosensitive adhesive 1 is ground to thin the semiconductor wafer 2 to a predetermined thickness ( FIG. 2( b )). Polishing can be performed, for example, by attaching an adhesive film to the photosensitive adhesive 1 and fixing the semiconductor wafer 2 to a polishing jig through the adhesive film. In addition, the process of thinning the semiconductor wafer can also be performed before patterning. In addition, when the semiconductor wafer is thinned after patterning, the above-mentioned adhesive film may not be required.

After grinding, the composite film 5 having the die-bonding film 30 and the dicing film 40 and the two being in a laminated state is bonded to the photosensitive film 5 of the semiconductor wafer 2 in the direction that the die-bonding film 30 contacts the semiconductor wafer 2. on the side opposite to Adhesive 1. Lamination can be carried out while heating as needed.

Next, the semiconductor wafer 2 is cut together with the composite film 5 along the cutting line 90, whereby the semiconductor wafer 2 can be divided into a plurality of semiconductor elements 20 ((a) of FIG. 4 ). This cutting can be performed using a cutting blade, for example, in a state where the entire body is fixed to the frame by cutting the film 40 .

After dicing, the semiconductor element 20 is picked up together with the die-bonding film 30 attached to the back surface thereof ((b) of FIG. 4 ). The semiconductor element 20 picked up can be mounted on the support base material 7 via the die-bonding film 30 ((a) of FIG. 5).

The semiconductor element 21 of the second layer can be directly bonded to the photosensitive adhesive 1 mounted on the semiconductor element 20 of the support base 7 ( FIG. 5( b )). In other words, the semiconductor element 20 and the semiconductor element 21 located above it can be bonded with the patterned photosensitive adhesive 1 (buffer coating film) interposed therebetween. The semiconductor element 21 is bonded in the patterned photosensitive adhesive 1 at a position where the opening 11 will not be blocked. In addition, it is preferable that the patterned photosensitive adhesive 1 (buffer coating film) is further formed on the circuit surface of the semiconductor element 21 .

The bonding of the semiconductor element 21 can be performed, for example, by thermocompression bonding while heating to a temperature at which the photosensitive adhesive 1 exhibits fluidity. At this time, a heat-resistant semiconductor device can be obtained by subjecting the film-form photosensitive adhesive to the water content adjustment treatment. After thermocompression bonding, the photosensitive adhesive 1 may be further cured by heating as needed.

Then, the semiconductor element 20 is connected to the external connection terminal on the support substrate 7 via the lead wire 80 connected on its pad, and the semiconductor element 21 is connected to the external connection terminal on the support substrate 7 via the lead wire 81 connected to the pad. Connect terminal connections. Then, the laminated body including the plurality of semiconductor elements is sealed with the sealing resin layer 60 to obtain the semiconductor device 100 ( FIG. 6 ).

The method of manufacturing a semiconductor device is not limited to the embodiments described above, and can be appropriately changed within a range not departing from the gist of the present invention. For example, the order of the steps of laminating the adhesive film, dicing, exposing and developing, and polishing the semiconductor wafer can be appropriately changed. As shown in FIG. 7 , the semiconductor wafer 2 bonded with the film-like photosensitive adhesive 1 can be thinned by grinding and then diced. In this case, after dicing, the photosensitive adhesive 1 is patterned by exposure and development to obtain a laminate similar to FIG. 4( a ). Alternatively, after thinning by grinding and dicing the semiconductor wafer, bonding of the photosensitive adhesive 1 in the form of a film, exposure, and development may be performed. In addition, three or more layers of semiconductor elements may be stacked. In this case, at least one set of adjacent semiconductor elements is preferably directly bonded with a patterned photosensitive adhesive (buffer coating film on the lower layer side).

In addition, FIGS. 8 to 20 are diagrams showing one embodiment of a method of manufacturing a semiconductor device. The semiconductor wafer 120 having the adhesive layer can be obtained by laminating the adhesive film (adhesive layer) 101 on the semiconductor wafer 105 while heating. The semiconductor wafer 120 having the adhesive layer is suitable for manufacturing electronic components such as CCD camera modules and CMOS camera modules through the process of bonding an adherend to the semiconductor wafer 105 through the adhesive layer 101 . An example of the case of manufacturing a CCD camera module will be described below. CMOS camera modules can also be manufactured by the same method.

FIG. 9 is a plan view showing an embodiment of an adhesive pattern, and FIG. 10 is a cross-sectional view along line VI-VI of FIG. 9 . On the semiconductor wafer 105 as an adherend, the adhesive pattern 101a shown in FIGS. graphics.

FIG. 11 is a plan view showing one embodiment of an adhesive pattern, and FIG. 12 is a cross-sectional view along line VIII-VIII of FIG. 11 . The adhesive pattern 101b shown in FIGS. 11 and 12 is formed on the semiconductor wafer 105 as an adherend in such a manner that an approximately square opening is formed to expose the effective pixel area 107 provided on the semiconductor wafer 105. Graphical.

The adhesive patterns 101a and 101b are formed by forming an adhesive layer 101 made of a photosensitive adhesive composition on a semiconductor wafer 105 as an adherend to obtain a semiconductor wafer 120 having an adhesive layer, The adhesive bond layer 101 is exposed through a photomask, and the exposed adhesive bond layer 101 is developed with an aqueous alkali solution to form. That is, the adhesive patterns 101a and 101b are composed of an exposed photosensitive adhesive composition.

Next, the cover glass 109 as another adherend is bonded on the semiconductor wafer 120 via the adhesive pattern 101a or 101b. 13 is a plan view showing a state where cover glass 109 is bonded to semiconductor wafer 120 via adhesive pattern 101a, and FIG. 14 is a cross-sectional view taken along line X-X in FIG. 13 . 15 is a plan view showing a state where cover glass 109 is bonded to semiconductor wafer 120 via adhesive pattern 101b, and FIG. 16 is a cross-sectional view taken along line XI-XI in FIG. 15 . The cover glass 9 is bonded to the semiconductor wafer 120 with the heat-cured adhesive pattern 101a or 101b interposed therebetween. The cover glass 109 is placed on the adhesive pattern 101a or 101b, and the cover glass 109 is adhered by thermocompression bonding. At this time, by performing the water content adjustment treatment on the film-form photosensitive adhesive, it is possible to prevent defects of the semiconductor device such as peeling of the cover glass. Furthermore, the adhesive patterns 101 a and 101 b function as an adhesive for bonding the cover glass 109 , and also function as a spacer for securing a space surrounding the effective pixel region 107 .

After the cover glass 109 is adhered, the semiconductor device 130 a shown in FIG. 17 or the semiconductor device 130 b shown in FIG. 18 is obtained by cutting along the dotted line D. The semiconductor device 130 a is composed of a semiconductor wafer 105 , an effective pixel region 107 , an adhesive pattern (adhesive layer) 101 a and a cover glass 109 . The semiconductor device 130 b is composed of a semiconductor wafer 105 , an effective pixel region 107 , an adhesive pattern (adhesive layer) 101 b , and a cover glass 109 .

The semiconductor device described above can be suitably used in electronic components such as CCD camera modules.

FIG. 19 is a cross-sectional view showing an embodiment of a CCD camera module including the above semiconductor device. A CCD camera module 150a shown in FIG. 19 is an electronic component including a semiconductor device 130a as a solid-state imaging element. The semiconductor device 130 a is bonded to the semiconductor element mounting support base 115 via the die-bonding film 111 . The semiconductor device 130 a is electrically connected to an external connection terminal via a lead 112 .

The CCD camera module 150a has the following configuration: a lens 140 to be provided directly above the effective pixel area 107, a lens 140, a side wall 116 provided to include the semiconductor device 130a and the lens 140, and a lens 140 embedded therein. The embedding member 117 interposed between the lens 140 and the side wall 116 is mounted on the semiconductor element mounting support base 115 .

FIG. 20 is a cross-sectional view showing an embodiment of a CCD camera module as an electronic component. The CCD camera module 150b shown in FIG. 19 has a structure in which the semiconductor device 130a is bonded to the semiconductor element mounting support substrate 115 via solder 113, instead of bonding the semiconductor device using the die-bonding film shown in the above-mentioned embodiment. composition.

FIG. 21 is a cross-sectional view showing one embodiment of a semiconductor device. The semiconductor device 201 includes a substrate (first adherend) 203 having a connection terminal (first connection part: not shown), and a semiconductor chip (second connection part: not shown) having a connection electrode part (second connection part: not shown). adherend) 205, an insulating resin layer 207 made of a photosensitive adhesive, and a conductive layer 209 made of a conductive material. The substrate 203 has a circuit surface 211 facing the semiconductor chip 205 and is arranged at a predetermined interval from the semiconductor chip 205 . The insulating resin layer 207 is located between the substrate 203 and the semiconductor chip 205, is formed in contact with the substrate 203 and the semiconductor chip 205, and has a predetermined pattern. The conductive layer 209 is formed on a portion between the substrate 203 and the semiconductor chip 205 where the insulating resin layer 207 is not arranged. The connection electrode portion of the semiconductor chip 205 is electrically connected to the connection terminal of the substrate 203 via the conductive layer 209 . The semiconductor device 201 can be suitably used for electronic components including a flip chip structure.

22 to 26 are cross-sectional views illustrating an embodiment of a method of manufacturing a semiconductor device. The manufacturing method of the semiconductor device according to this embodiment includes the steps of providing an insulating resin layer 207 made of a photosensitive adhesive on a substrate 203 having connection terminals (first step: FIG. 22 and FIG. 23 ); The resin layer 207 is patterned by exposure and development to form an opening 213 exposing the connection terminal (second step: FIG. 24 and FIG. 25 ), and a step of filling the opening 213 with a conductive material to form a conductive layer 209 (third step : FIG. 26), and the semiconductor chip 205 having the electrode portion for connection is directly bonded on the insulating resin layer 207 of the laminated body made of the substrate 203 and the insulating resin layer 207, and the connection of the substrate 203 is made through the conductive layer 209. A step of electrically connecting the terminal to the connection electrode portion of the semiconductor chip 205 (fourth step).

An insulating resin layer 207 made of a photosensitive adhesive is provided on the circuit surface 211 of the substrate 203 shown in FIG. 22 (FIG. 23). A relatively simple method is to prepare a photosensitive adhesive (hereinafter sometimes referred to as “adhesive film”) formed in the form of a film in advance, and bond it to the substrate 203 . In addition, the photosensitive adhesive can be provided by applying a liquid varnish containing a photosensitive adhesive on the substrate 203 by a spin coating method or the like, followed by heating and drying.

The photosensitive adhesive is an alkali-developable negative-type photosensitive adhesive that has adhesiveness to an adherend after being patterned by exposure and development. More specifically, the resist pattern formed by patterning the photosensitive adhesive by exposure and development has adhesiveness to adherends such as semiconductor chips and substrates. For example, the resist pattern and the adherend can be adhered by pressing the adherend onto the resist pattern while heating as necessary. Details of the photosensitive adhesive having this function will be described later.

The insulating resin layer 207 provided on the substrate 203 is irradiated with active light rays (typically ultraviolet rays) through a mask 215 having openings formed at predetermined positions ( FIG. 24 ). Thereby, the insulating resin layer 207 is exposed in a predetermined pattern.

After exposure, the unexposed portion of the insulating resin layer 207 is removed by development with an alkaline developer, whereby the insulating resin layer 207 can be patterned to form openings 213 exposing the connection terminals of the substrate 203 ( FIG. 25 ). In addition, a positive photosensitive adhesive may be used instead of a negative photosensitive adhesive, and in this case, the exposed portion of the insulating resin layer 207 is removed by development.

The opening 213 of the obtained resist pattern is filled with a conductive material to form a conductive layer 209 (FIG. 26). Various methods such as gravure printing, roll pressing, and pressure-reduced filling can be used for the filling method of the conductive material. Examples of the conductive material used here include solder, electrode materials made of metals such as gold, silver, nickel, copper, platinum, palladium, or ruthenium oxide, or metal oxides, the above-mentioned metal protrusions, and at least conductive particles and resin components. substances etc. As said electroconductive particle, electroconductive particle, such as metal or metal oxide, such as gold, silver, nickel, copper, platinum, palladium, or ruthenium oxide, or an organometallic compound, can be used, for example. In addition, as the resin component, the aforementioned curable resin composition, such as an epoxy resin and its curing agent, can be used, for example.

The semiconductor chip 205 can be directly bonded to the insulating resin layer 207 on the substrate 203 . The connection electrode portion of the semiconductor chip 205 is electrically connected to the connection terminal of the substrate 203 via the conductive layer 209 . In addition, a patterned insulating resin layer (buffer coating film) may be formed on the circuit surface of the semiconductor chip 205 on the opposite side to the insulating resin layer 207 .

The bonding of the semiconductor chip 205 can be performed, for example, by thermocompression bonding while heating to a temperature at which the photosensitive adhesive exhibits fluidity. At this time, a heat-resistant semiconductor device can be obtained by subjecting the film-form photosensitive adhesive to the water content adjustment treatment. After thermocompression bonding, the insulating resin layer 207 may be further cured by heating as needed.

On the circuit surface (back surface) of the semiconductor chip 205 opposite to the insulating resin layer 207, a back surface protection film is preferably bonded.

As described above, the semiconductor device 201 having the configuration shown in FIG. 21 can be obtained. The method of manufacturing a semiconductor device is not limited to the embodiments described above, and can be appropriately changed without departing from the gist of the present invention.

For example, the photosensitive adhesive is initially provided on the substrate 203 , but is not limited thereto, and may be first provided on the semiconductor chip 205 . In this case, the manufacturing method of the semiconductor device includes, for example, a first step of providing an insulating resin layer 207 made of a photosensitive adhesive on a semiconductor chip 205 having an electrode portion for connection, exposing the insulating resin layer 207 to The second process of forming the opening 213 that exposes the electrode portion for connection by patterning and developing, the third process of filling the opening 213 with a conductive material to form the conductive layer 209, and directly bonding the substrate 203 with the connection terminal on the A fourth step of electrically connecting the connection terminal of the substrate 203 and the connection electrode portion of the semiconductor chip 205 via the conductive layer 209 on the insulating resin layer 207 of the laminate composed of the semiconductor chip 205 and the insulating resin layer 207 .

In the above-mentioned manufacturing method, since it is the connection between the substrate 203 and the semiconductor chip 205 that are respectively singulated, the connection between the connection terminal on the substrate 203 and the connection electrode portion on the semiconductor chip 205 is relatively easy. method.

In addition, the photosensitive adhesive may be initially provided on a semiconductor wafer including a plurality of semiconductor chips 205 . In this case, the manufacturing method of the semiconductor device includes, for example, a first step ( 7), the second process of forming the opening 213 that exposes the electrode portion for connection by patterning the insulating resin layer 207 through exposure and development, and the third process of filling the opening 213 with a conductive material to form the conductive layer 209 will include A wafer-sized substrate (substrate having a size equivalent to that of a semiconductor wafer) 203 of the connection terminal is directly bonded to the insulating resin layer 207 of the laminated body composed of the semiconductor wafer 217 and the insulating resin layer 207, and is connected via the conductive layer 209. The fourth step of electrically connecting the connection terminal of the substrate 203 to the connection electrode portion of the semiconductor chip 205 constituting the semiconductor wafer 217, and dicing the laminate composed of the semiconductor wafer 217, the insulating resin layer 207 and the substrate 203 into individual semiconductor chips 205 ( Cutting) the fifth process.

In addition, the above manufacturing method may also be: in the first step, an insulating resin layer 207 made of a photosensitive adhesive is provided on the wafer-sized substrate 203, and the semiconductor wafer 217 is directly bonded to the substrate 203 in the fourth step. 203 and the insulating resin layer 207 on the insulating resin layer 207 of the laminated body made of the insulating resin layer 207, and through the conductive layer 209, the connecting terminal of the substrate 203 and the connecting electrode part of the semiconductor chip 205 constituting the semiconductor wafer 217 are electrically connected. In the process, the laminated body composed of the semiconductor wafer 217 , the insulating resin layer 207 and the substrate 203 is diced into individual semiconductor chips 205 .

In the above manufacturing method, the steps up to the connection of the semiconductor wafer 217 and the substrate 203 (the fourth step) can be performed in a wafer size, which is preferable from the viewpoint of work efficiency. In addition, it is preferable to stick a back surface protective film on the circuit surface (back surface) on the side opposite to the insulating resin layer 207 in the semiconductor wafer 217 .

In addition, another method of manufacturing a semiconductor device includes: a first step of providing an insulating resin layer 207 made of a photosensitive adhesive on a semiconductor wafer 217 composed of a plurality of semiconductor chips 205 having connection electrode parts; 207 is patterned by exposure and development to form the second step of opening 213 exposing the connection electrode part, the third step of filling the opening 213 with a conductive material to form the conductive layer 209, and forming the semiconductor wafer 217 and the insulating resin layer 207 The fourth step of cutting the laminated body into individual semiconductor chips 205 (dicing), and directly bonding the substrate 203 having connection terminals to the insulating resin of the laminated body composed of the singulated semiconductor chips 205 and the insulating resin layer 207 The fifth step is to electrically connect the connection terminal of the substrate 203 and the connection electrode portion of the semiconductor chip 205 on the layer 207 through the conductive layer 209 .

In addition, the above-mentioned manufacturing method may also be: in the first step, the insulating resin layer 207 made of photosensitive adhesive is provided on the wafer-sized substrate 203, and the wafer-sized substrate 203 and the insulating resin layer are placed in the fourth step. 207 is cut into individual semiconductor chips 205, and in the fifth step, the semiconductor chips 205 are directly bonded to the insulating resin layer 207 of the laminate composed of the singulated substrate 203 and the insulating resin layer 207, and interposed The connection terminals of the substrate 203 and the connection electrode portions of the semiconductor chip 205 are electrically connected by the conductive layer 209 .

In the above-mentioned production method, the steps from formation of the photosensitive adhesive to filling of the conductive material (third step) can be performed in a wafer size, and the dicing step (fourth step) can be smoothly performed, so it is preferable.

In addition, a semiconductor laminate can be formed by bonding semiconductor wafers or semiconductor chips together using a photosensitive adhesive. Penetrating electrodes may also be formed in this laminated body.

In this case, the method of manufacturing a semiconductor device includes, for example, a first step of providing an insulating resin layer 207 made of a photosensitive adhesive on a first semiconductor chip 205 having a connecting electrode portion as a through-electrode, The insulating resin layer 207 is patterned by exposure and development to form the second step of opening 213 exposing the above-mentioned connection electrode portion, the third step of filling the opening 213 with a conductive material to form a through-electrode connection, and forming the connection electrode portion. The second semiconductor chip 205 is directly bonded to the insulating resin layer 207 of the laminated body made of the first semiconductor chip 205 and the insulating resin layer 207, and the first and second semiconductor chips 205 are connected through the conductive layer 209. The fourth step of electrical connection between electrode parts. In the above manufacturing method, a semiconductor wafer may be used instead of a semiconductor chip.

In addition, the above-mentioned electronic components can generally be manufactured through a curing step of curing an adhesive and a solder reflow step.

Example

Hereinafter, the present invention will be described more specifically based on examples and comparative examples, but the present invention is not limited by the following examples.

(Synthesis of polyimide PI-1)

Add 3.43 g of 5,5'-methylene-bis(anthranilic acid) (molecular weight 286.3, hereinafter referred to as "MBAA"), aliphatic ether diamine (BASF Made by the company, "D-400" (trade name), molecular weight 452.4) 31.6 g, 1,1,3,3-tetramethyl-1,3-bis(4-aminophenyl)disiloxane (Dow Corning "BY16-871EG" (trade name), manufactured by Corporation, molecular weight 248.5) 2.48 g, and N-methyl-2-pyrrolidone (hereinafter referred to as NMP) 105 g.

Next, while cooling the flask in an ice bath, 4,4'-oxydiphthalic anhydride (molecular weight: 326.3, hereinafter referred to as "ODPA") was continuously added in small amounts to the flask, and a total of 32.6 g was added. After completion of the addition, the mixture was further stirred at room temperature for 5 hours.

Next, a reflux cooler equipped with a water receiver was attached to the flask, 70 g of xylene was added, and the temperature was raised to 180° C. while nitrogen gas was blown in. The temperature was maintained for 5 hours, and xylene was azeotropically removed with water. Thus, a polyimide (hereinafter referred to as "polyimide PI-1") was obtained.

When the weight average molecular weight (Mw) of the obtained polyimide PI-1 was measured by GPC, Mw=31000 in terms of polystyrene.

In addition, Tg of obtained polyimide PI-1 was 55 degreeC.

(Synthesis of polyimide PI-2)

Add 2.86 g of MBAA, 14.0 g of D-400, 2.48 g of BY16-871EG, and 8.17 g of ether diamine (manufactured by BASF, "B-12" (commercial name), molecular weight 204.3) and 110 g of NMP.

Next, while cooling the flask in an ice bath, ODPA was continuously added in small amounts to the above-mentioned flask, and a total of 32.6 g was added. After completion of the addition, the mixture was further stirred at room temperature for 5 hours.

Next, a reflux cooler equipped with a water receiver was attached to the flask, 73 g of xylene was added, and the temperature was raised to 180° C. while nitrogen gas was blown in. The temperature was maintained for 5 hours, and xylene was azeotropically removed with water. Thus, a polyimide (hereinafter referred to as "polyimide PI-2") was obtained.

When the weight average molecular weight (Mw) of the obtained polyimide PI-2 was measured by GPC, Mw=28000 in terms of polystyrene.

In addition, Tg of obtained polyimide PI-2 was 60 degreeC.

(Synthesis of polyimide PI-3)

14.65 g of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (molecular weight 366.26, hereinafter referred to as "BIS-AP-AF"), Aliphatic ether diamine (manufactured by BASF Corporation, "D-400" (trade name), molecular weight 452.4) 18.09 g, 1,1,3,3-tetramethyl-1,3-bis(4-aminophenyl) Disiloxane (manufactured by Dow Corning Corporation, "BY16-871EG" (trade name) molecular weight 248.5) 2.48 g and N-methyl-2-pyrrolidone (hereinafter referred to as NMP) 105 g.

Next, while cooling the flask in an ice bath, 4,4'-oxydiphthalic anhydride (molecular weight: 326.3, hereinafter referred to as "ODPA") was continuously added in small amounts to the flask, and a total of 32.6 g was added. After completion of the addition, the mixture was further stirred at room temperature for 5 hours.

Next, a reflux cooler equipped with a water receiver was attached to the flask, 70 g of xylene was added, and the temperature was raised to 180° C. while nitrogen gas was blown in. The temperature was maintained for 5 hours, and xylene was azeotropically removed with water. Thus, a polyimide (hereinafter referred to as "polyimide PI-3") was obtained.

When the weight average molecular weight (Mw) of the obtained polyimide PI-3 was measured by GPC, Mw=33000 in terms of polystyrene.

In addition, Tg of obtained polyimide PI-3 was 75 degreeC.

(Synthesis of polyimide PI-4)

Add 27.1g (0.06mol) of D-400, 2.48g (0.01mol) of BY16-871EG, 8.58g (0.03mol) of MBAA and 113g N-methyl-2-pyrrolidone (NMP), and the reaction solution was stirred. After the diamine was dissolved, 32.62 g (0.1 mol) of ODPA and 5.76 g (0.03 mol) of trimellitic anhydride (molecular weight: 192.1, hereinafter referred to as TAA) were continuously added in small amounts. After stirring at room temperature for 8 hours, 75.5 g of xylene was added, heated at 180° C. while blowing in nitrogen gas, xylene was azeotropically removed with water, and a varnish of polyimide resin (PI-4) was obtained.

When the weight average molecular weight Mw of the obtained polyimide PI-4 was measured by GPC, it was 25000 in terms of polystyrene. In addition, Tg of obtained polyimide PI-4 was 70 degreeC.

(preparation of varnish)

Mix polyimide, radiation polymerizable compound, photopolymerization initiator, epoxy resin, curing agent, filler and coating solvent according to the mixing ratio shown in Table 1 and 2 to prepare varnishes F-01 to F-05.

Table 1

Table 2

In addition, the meanings of various symbols in Tables 1 and 2 are as follows.

・BPE-100: manufactured by Shin-Nakamura Chemical Co., Ltd., epoxidized bisphenol A dimethacrylate

・U-2PPA: manufactured by Shin-Nakamura Chemical Co., Ltd., urethane acrylate

・M-313: Toagosei Co., Ltd., isocyanuric acid EO-modified diacrylate and triacrylate

・I-819: manufactured by Ciba Specialty Chemicals Inc., bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide

・I-OXE02: Ciba Specialty Chemicals Inc., 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime) Ethyl ketone, compound containing oxime ester group

・VG3101: Trifunctional epoxy resin manufactured by Printec Co., Ltd.

·YDF-8170: Bisphenol F epoxy resin manufactured by Dongdu Chemical Industry Co., Ltd.

・TriSP-PA: manufactured by Honshu Chemical Co., Ltd., triphenol compound (α, α, α'-tris(4-hydroxyphenol)-1-ethyl-4-isopropylbenzene)

・R972: Made by NIPPON AEROSIL CO., LTD, hydrophobic fumed silica (average particle size: about 16nm)

PERCUMYL D: manufactured by NOF, dicumyl peroxide (half-life of 1 minute temperature: 175°C)

·EA-1010NT: New Nakamura Chemical, double A type acrylic modified monofunctional epoxy resin

・NMP: Kanto Chemical, N-methyl-2-pyrrolidone

(Examples 1-7 and Comparative Examples 1-3)

Each of the above-mentioned varnishes is coated on a substrate (release agent-treated PET) to a thickness of 50 μm, heated in an oven at 80°C for 30 minutes, and then heated at 120°C for 30 minutes to obtain a film-like adhesion with the substrate agent.

Next, the properties of the film-form adhesives of Examples 1 to 7 and Comparative Examples 1 to 3 were evaluated under the conditions shown below. The results are shown in Tables 3-5.

A transparent PET film as a protective film was further bonded to the film-like photosensitive adhesive with a thickness of 50 μm formed on the transparent PET substrate, and the adhesive sheet thus obtained was cut into a size of 150 mm×150 mm. Place a mask on the cut adhesive sheet, expose (irradiate ultraviolet rays) under the condition of exposure amount: 1000mJ/cm ² using a high-precision parallel exposure machine (manufactured by ORC MANUFACTURING CO., LTD.), and heat at 80°C for 30 Second. Then, the PET film on one side was peeled off, and developed using a spray developing machine manufactured by YAKO Co., Ltd. (developing solution: tetramethylammonium hydroxide (TMAH) 2.38%, 27° C., spray pressure 0.18 MPa, washing: pure water 23°C and spray pressure 0.02MPa).

A pattern was formed on the PET substrate on the other side, and then, the TMAH attached to the film was washed with pure water for 6 minutes. Then, it was left to stand at room temperature for 30 minutes, the PET substrate was peeled off, and the water content of the patterned film-form photosensitive adhesive was measured using the Hiranuma Sangyo moisture meter "AQV2100CT".

Furthermore, in the case of performing heat treatment as moisture content adjustment treatment after patterning, the obtained sample is placed on a vinyl fluoride fiber sheet, etc., and placed on a hot plate together with the polyvinyl fluoride fiber sheet. Heating at temperature for specified time.

(Thermal history stability after thermocompression bonding)

Using a laminating device, under the conditions of bonding temperature: 80°C, linear pressure: 4kgf/cm, and conveying speed: 0.5m/min, the film-like photosensitive adhesive with the base material is bonded to a diameter of 6 inches, on a silicon wafer with a thickness of 400 μm.

Next, a negative pattern mask was placed on the side of the PET base material of the film-like photosensitive adhesive with the base material, and a high-precision parallel exposure machine (manufactured by ORC MANUFACTURING CO., LTD.: EXM-1172-B-∞ ) was exposed (irradiated with ultraviolet rays) under the conditions of exposure amount: 1000 mJ/cm ² , and further heat-treated at 80° C. for 30 seconds. Then, the substrate was peeled off, and spray development was carried out using a conveyor belt developer (manufactured by YAKO Co., Ltd.) (developing solution: tetramethylammonium hydroxide (TMAH) 2.38%, 27° C., spray pressure 0.18 MPa, washing with water: pure water at 23° C. and a spray pressure of 0.02 MPa) to pattern the film-like photosensitive adhesive.

After developing, wash the adhered TMAH with pure water for 6 minutes, and then leave it at room temperature for 30 minutes. Then, if necessary, prolong the standing time or perform moisture absorption treatment, and perform moisture content adjustment treatment under specified conditions after patterning.

Immediately after heating and drying, place 30mm×30mm×thickness 0.35mm glass on the patterned film-like photosensitive adhesive, and use the flat type thermal compression bonding device OH-105ATF manufactured by Ohashi Seisakusho. The bonding temperature: 150°C , Crimping load: 0.5MPa and crimping time: 10 minutes for heating and crimping.

The obtained samples were heated and cured in an oven under the conditions of 160° C. for 3 hours and 180° C. for 3 hours. Then, it was heated on a hot plate at 260° C., and the time until the glass/adhesive interface was peeled or foamed to cause voids was measured. The case where peeling or foaming occurred immediately after heating at 260° C. was regarded as NG.

table 3

Table 4

table 5

As shown in Tables 3 to 5, Examples 1 to 7 are superior to Comparative Examples 1 to 3 in thermal history stability (heat resistance) after thermocompression bonding.

Symbol Description

1...film-like photosensitive adhesive (adhesive film), 2...semiconductor wafer, 3, 215...mask, 5...composite film, 7...support substrate, 9...protective glass, 11...opening, 20, 21...semiconductor element, 25...circuit surface, 30...die bonding film, 40...cutting film, 60...sealing resin layer, 80, 81...lead wire, 90...cutting line, 100, 130a, 130b, 201...semiconductor device, 101...adhesive layer, 101a...adhesive pattern, 101b...adhesive pattern, 107...effective pixel area, 109...cover glass, 111...die bonding film, 112...lead wire, 115...semiconductor Support base material for element mounting, 116...side wall, 117...member for embedding, 120...semiconductor wafer with adhesive layer, 140...lens, 150a, 150b...CCD camera module, 203...substrate, 205...semiconductor chip, 207...insulating resin layer, 209...conductive layer, 211...circuit surface, 213...opening, 217...semiconductor wafer.

Claims (17)

1. A semiconductor device, which is a semiconductor device in which a semiconductor element and an adherend are thermocompression-bonded via a patterned film-like photosensitive adhesive, The moisture content of the patterned film-like photosensitive adhesive immediately before thermocompression bonding is 1.0% by weight or less. 2. The semiconductor device according to claim 1, wherein the adherend is a semiconductor element or a cover glass. 3. The semiconductor device according to claim 1 or 2, wherein the film-like photosensitive adhesive contains at least (A) a thermoplastic resin and (B) a thermosetting resin. 4. The semiconductor device according to claim 3, wherein the film-like photosensitive adhesive further contains (C) a radiation polymerizable compound and (D) a photoinitiator. 5. The semiconductor device according to claim 3 or 4, wherein the (A) thermoplastic resin is an alkali-soluble resin. 6. The semiconductor device according to claim 5, wherein the alkali-soluble resin is a polyimide resin having a carboxyl group and/or a hydroxyl group in a molecule. 7. The semiconductor device according to claim 3, wherein the (B) thermosetting resin is an epoxy resin. 8. The semiconductor device according to any one of claims 1 to 7, wherein the patterned film-like photosensitive adhesive is formed through the following steps: An adhesive layer forming process of forming an adhesive layer composed of a film-like photosensitive adhesive on an adherend; an exposure step of exposing the adhesive layer in a predetermined pattern; A developing step of developing the exposed adhesive layer with an aqueous alkaline solution; and A moisture content adjustment process of adjusting the moisture content of the adhesive bond layer after development. 9. A method of manufacturing a semiconductor device, the method comprising the steps of: A patterning process of patterning the film-like photosensitive adhesive provided on the circuit surface of the semiconductor element by exposure and development; a moisture content adjustment step of adjusting the moisture content of the patterned photosensitive adhesive; a thermocompression bonding process of direct bonding an adherend by thermocompression bonding on the patterned photosensitive adhesive, In the moisture content adjustment step, the moisture content adjustment treatment is performed so that the moisture content of the photosensitive film-like adhesive film patterned on the PET base material after patterning is 1.0% by weight or less. 10. The method of manufacturing a semiconductor device according to claim 9, wherein the adherend is a semiconductor element or a cover glass. 11. The method of manufacturing a semiconductor device according to claim 9 or 10, wherein the water content adjustment treatment is heat treatment. 12 . The method for manufacturing a semiconductor device according to claim 9 , wherein the film-like photosensitive adhesive contains at least (A) a thermoplastic resin and (B) a thermosetting resin. 13 . 13 . The method of manufacturing a semiconductor device according to claim 12 , wherein the film-like photosensitive adhesive further contains (C) a radiation polymerizable compound and (D) a photoinitiator. 14 . 14. The method of manufacturing a semiconductor device according to claim 12 or 13, wherein the (A) thermoplastic resin is an alkali-soluble resin. 15. The method of manufacturing a semiconductor device according to claim 14, wherein the alkali-soluble resin is a polyimide resin having a carboxyl group and/or a hydroxyl group in a molecule. 16. The method of manufacturing a semiconductor device according to claim 12, wherein the (B) thermosetting resin is an epoxy resin. 17. A semiconductor device manufactured by the manufacturing method according to any one of claims 9 to 16.

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