JP5098607B2 - Manufacturing method of semiconductor device - Google Patents

Description

  The present invention relates to a method for manufacturing a semiconductor device.

  A semiconductor device constituting an image sensor such as a CMOS sensor or a CCD sensor has a structure in which a glass substrate and a semiconductor chip are bonded by an adhesive layer. The semiconductor device is manufactured by providing an adhesive layer on a circuit surface of a semiconductor chip and then bonding a glass substrate to the adhesive layer.

On the other hand, some photosensitive adhesives having both photosensitivity and adhesiveness have been proposed (see, for example, Patent Documents 1 to 3).
Japanese Patent Laid-Open No. 11-24257 JP 2000-290501 A JP 2001-329233 A

  Conventionally, in a method for manufacturing a semiconductor device constituting an image sensor, an adhesive layer is formed on a circuit surface of a semiconductor chip, so that the circuit surface is contaminated by the adhesive layer. For this reason, after forming the adhesive layer on the glass substrate, it is conceivable to bond the desired portion of the circuit surface of the semiconductor chip and the adhesive layer, but in this case, the adhesive force between the semiconductor chip and the adhesive layer is not sufficient There was a problem with.

  Therefore, the present invention has been made in view of such circumstances, and in manufacturing a semiconductor device on which an image sensor such as a CMOS sensor is mounted, it is possible to prevent contamination of the circuit surface of the semiconductor chip by the adhesive layer. Another object of the present invention is to provide a method for manufacturing a semiconductor device capable of improving the adhesive force between a semiconductor chip and a glass substrate via an adhesive layer.

  A method of manufacturing a semiconductor device according to the present invention includes a step of providing an adhesive layer made of a film-like photosensitive adhesive layer on a first main surface of a glass substrate having first and second main surfaces facing each other; Exposing the adhesive layer by irradiating light from the second main surface side, patterning the adhesive layer by development, and directly adhering the semiconductor chip to the patterned adhesive layer so that its circuit surface faces the glass substrate side And a step of performing.

  In the method of manufacturing a semiconductor device according to the present invention, an adhesive layer is provided on a glass substrate, and after patterning the adhesive layer by exposure and development, the semiconductor chip is bonded so that the circuit surface of the semiconductor chip faces the glass substrate side. It adheres to the layer. For this reason, by forming the adhesive layer in a desired pattern, the adhesive layer is adhered to a desired portion on the circuit surface of the semiconductor chip. Therefore, it is possible to prevent contamination of the circuit surface of the semiconductor chip by the adhesive layer. In the method for manufacturing a semiconductor device according to the present invention, light is irradiated from the surface (exposed surface) opposite to the glass substrate in the adhesive layer. For this reason, since the progress of photocuring of the exposed surface that directly contacts the circuit surface of the semiconductor chip is suppressed, the fluidity of the adhesive layer on the exposed surface is kept high, and the adhesive force between the glass substrate and the adhesive layer is improved. It is possible.

  In the method for manufacturing a semiconductor device according to the present invention, the photosensitive adhesive layer preferably contains an alkali-soluble polymer, a radiation polymerizable compound, and a photopolymerization initiator. Thereby, after patterning by exposure and development, adhesion to the semiconductor chip can be particularly easily imparted to the photosensitive adhesive. From the same viewpoint, the alkali-soluble polymer preferably has a carboxyl group or a phenolic hydroxyl group.

  The glass transition temperature of the alkali-soluble polymer is preferably 150 ° C. or lower. Thereby, a film-like photosensitive adhesive (hereinafter, referred to as “adhesive film” in some cases) can be attached to the semiconductor chip at a lower temperature.

  The alkali-soluble polymer is preferably polyimide. Polyimide is composed of tetracarboxylic dianhydride and an aromatic diamine represented by the following chemical formula (Ia), (Ib), (II-a), (II-b) or (II-c). It is preferable that it is a thing obtained by making it react with the diamine containing.

  In the method for manufacturing a semiconductor device according to the present invention, it is preferable that the photosensitive adhesive further contains a thermosetting resin.

  ADVANTAGE OF THE INVENTION According to this invention, in manufacture of the semiconductor device which mounts image sensors, such as a CMOS sensor, it is possible to prevent the contamination of the circuit surface of the semiconductor chip by an adhesive layer. Further, according to the present invention, it is possible to improve the adhesive force between the semiconductor chip and the glass substrate through the adhesive layer.

  Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

  1 to 8 are end views or plan views showing one embodiment of a method for manufacturing a semiconductor device. In the method for manufacturing a semiconductor device according to the present embodiment, a film-like photosensitive adhesion is formed on a surface 3a of a glass substrate 3 having a surface (first main surface) 3a and a back surface (second main surface) 3b facing each other. A step of providing an adhesive layer 7 made of an agent (FIGS. 1 and 2), a step of exposing the adhesive layer 7 by irradiating light from the back surface 3b side, and patterning the adhesive layer 7 by development (FIGS. 3 to 5) A step of directly bonding the semiconductor chip 5 to the patterned adhesive layer 7 so that its circuit surface faces the glass substrate 3 side (FIG. 6), and dicing the glass substrate 3 and the semiconductor chip 5 bonded to each other. And a step of dividing the semiconductor device 1 into a plurality of semiconductor devices 1 (FIGS. 7 and 8).

  An adhesive layer 7 made of a film-like photosensitive adhesive is provided on the surface 3a of the glass substrate 3 shown in FIG. 1 (FIG. 2). A method of preparing a photosensitive adhesive previously formed in a film shape and attaching it to the glass substrate 3 is simple.

  The photosensitive adhesive is a negative photosensitive adhesive that has adhesiveness to an adherend after being patterned by exposure and development and is capable of alkali development. More specifically, a resist pattern formed by patterning a film-like photosensitive adhesive by exposure and development has adhesion to adherends such as semiconductor chips and glass substrates. For example, it is possible to bond the resist pattern and the adherend by applying pressure to the adherend while heating the resist pattern as necessary. Details of the photosensitive adhesive having such a function will be described later.

  A mask 11 having an opening formed at a predetermined position is arranged on the back surface 3b of the glass substrate 3 with respect to the adhesive layer 7 provided on the front surface 3a of the glass substrate 3, and the back surface 3b side through the mask 11 To actinic rays (typically ultraviolet rays) (FIG. 3). As a result, the actinic rays pass through the glass substrate 3 and are applied to the adhesive layer 7, and the adhesive layer 7 is exposed to light in a predetermined pattern as photocuring proceeds.

  After the exposure, the adhesive layer 7 is patterned by removing an unexposed portion of the adhesive layer 7 by development using an alkaline developer (FIG. 4). The adhesive layer 7 is formed so as to have a pattern along a substantially square side (FIG. 5). Note that a positive photosensitive adhesive can be used instead of the negative type, and in this case, the exposed portion of the adhesive layer 7 is removed by development.

  A plurality of effective pixel regions 15 provided on the circuit surface of the semiconductor chip 5 are each surrounded by an adhesive layer 7 formed in a pattern along a substantially square side, and the circuit surface of the semiconductor chip 5 is on the glass substrate 3 side. The semiconductor chip 5 is directly bonded to the adhesive layer 7 so as to face (FIG. 6). The adhesive layer 7 serves as a spacer for adhering the semiconductor chip 5 and securing a space surrounding the effective pixel region 15. The semiconductor chip 5 is bonded by, for example, a method of thermocompression bonding while heating to a temperature at which the adhesive layer 7 exhibits fluidity. After thermocompression bonding, the adhesive layer 7 is heated as necessary to further cure.

  After the semiconductor chip 5 is bonded, a plurality of semiconductor devices 1 shown in FIG. 8 are obtained by dicing along the broken line D (FIG. 7). In this case, a plurality of semiconductor devices 1 are obtained by sticking a dicing film on the surface opposite to the circuit surface of the semiconductor chip 5 and cutting the glass substrate 3 and the semiconductor chip 5 together with the dicing film. For example, the dicing is performed using a dicing blade in a state where the whole is fixed to the frame by a dicing film.

  The manufacturing method of the semiconductor device is not limited to the embodiment described above, and can be appropriately changed without departing from the gist of the present invention.

  The semiconductor device 1 is suitably used for manufacturing electronic components such as a CMOS sensor and a CCD sensor. FIG. 9 is an end view showing a CMOS sensor using a semiconductor device manufactured by the method of manufacturing a semiconductor device according to the present invention. The CMOS sensor 30 is an electronic component including the semiconductor device 1 as a solid-state image sensor. The semiconductor device 1 is electrically connected to connection terminals (not shown) on the semiconductor element mounting support base 34 via a plurality of conductive bumps 32. Instead of the configuration in which the semiconductor device 1 is bonded using the conductive bumps 32, the semiconductor device 1 has a configuration in which the semiconductor device 1 is connected to the connection terminals on the semiconductor element mounting support base 34 via conductive wires. You may do it.

  The CMOS sensor 30 includes a lens 38 provided so as to be positioned immediately above the effective pixel region 15, a side wall 40 provided so as to enclose the semiconductor device 1 together with the lens 38, and a lens 38 fitted therein. The fitting member 42 interposed between the lens 38 and the side wall 40 has a configuration in which the semiconductor element mounting support base 34 is mounted.

  After manufacturing the semiconductor device 1 as described above, the CMOS sensor 30 connects the semiconductor device 1 to the connection terminals on the semiconductor element mounting support base 34 and the semiconductor chip 5 via the conductive bumps 32. The lens 38, the side wall 40, and the fitting member 42 are formed on the semiconductor element mounting support base 34 so as to enclose them.

  Hereinafter, preferred embodiments of the photosensitive adhesive used in the method of manufacturing a semiconductor device according to the above embodiment will be described.

  The photosensitive adhesive according to this embodiment contains an alkali-soluble polymer, a radiation polymerizable compound, and a photopolymerization initiator.

  The alkali-soluble polymer may be soluble in an alkaline developer, and is preferably soluble in an aqueous tetramethylammonium hydride solution. For example, a polymer having a carboxyl group and / or a phenolic hydroxyl group often has good solubility in an alkaline developer.

  When the alkali-soluble polymer has a carboxyl group, the acid value is preferably 80 to 180 mg / KOH. When the acid value is 80 to 180 mg / KOH, the pattern formability with an alkali developer and the re-adhesion after exposure are particularly good. If the acid value of the alkali-soluble polymer is less than 80 mg / KOH, the solubility in an alkali developer tends to decrease, and if it exceeds 180 mg / KOH, the photosensitive adhesive peels off from the adherend during development. The possibility increases. From the same viewpoint, the acid value of the alkali-soluble polymer is more preferably 150 mg / KOH or less. In particular, it is preferable that the photosensitive adhesive contains a thermosetting resin described later, and the acid value of the alkali-soluble polymer is 80 to 180 mg / KOH.

  In order to ensure good adhesion after exposure, the glass transition temperature (Tg) of the alkali-soluble polymer is preferably 30 to 150 ° C. If the Tg of the alkali-soluble polymer is less than 30 ° C., voids tend to be easily generated during thermocompression bonding after exposure. When Tg exceeds 150 ° C., the temperature for pasting to the adherend before exposure and the pressure-bonding temperature after exposure tend to increase, and the peripheral members tend to be damaged. The above Tg is the peak temperature of tan δ when the temperature change of the viscoelasticity of the film-like photosensitive adhesive is measured using a viscoelasticity measuring device (Rheometric).

  The weight average molecular weight of the alkali-soluble polymer is preferably 5,000 to 150,000, more preferably 20,000 to 50,000, still more preferably 30,000 to 40,000. If the weight average molecular weight of the alkali-soluble polymer is less than 5,000, the film-forming property of the photosensitive adhesive tends to be lowered, and if it exceeds 150,000, the solubility in an alkali developer is lowered and the development time tends to be longer. is there. By setting the weight average molecular weight of the alkali-soluble polymer to 5000 to 150,000, an effect that the heating temperature for re-adhesion after exposure can be lowered is also obtained. In addition, said weight average molecular weight is a standard polystyrene conversion value measured using a high performance liquid chromatography (For example, "C-R4A" (brand name) by Shimadzu Corporation).

  The alkali-soluble polymer may have a radiation polymerizable functional group such as an ethylenically unsaturated group. In this case, the alkali-soluble polymer also functions as a radiation polymerizable compound. As the radiation-polymerizable compound, only an alkali-soluble polymer having a radiation-polymerizable functional group may be used, or such an alkali-soluble polymer and another radiation-polymerizable compound may be used in combination.

  The alkali-soluble polymer preferably contains at least one polymer selected from the group consisting of polyimide, polyamideimide, polyamic acid, polybenzoxazole, acrylic polymer, styrene-maleic acid copolymer, novolac resin, and polynorbornene resin. . Among these, polyimide, polyamide, polybenzoxazole and acrylic polymer are preferable.

  The polyimide used as the alkali-soluble polymer is composed of one or more polymers having an imide skeleton in the main chain. The polyimide preferably has a carboxyl group and / or a phenolic hydroxyl group.

  A polyimide having a carboxyl group can be obtained by a reaction between a tetracarboxylic dianhydride and a diamine having a carboxyl group and an amino group. A polyimide having a phenolic hydroxyl group can be obtained by a reaction between a tetracarboxylic dianhydride and a diamine having a phenolic hydroxyl group and an amino group. Through these reactions, a carboxyl group or a phenolic hydroxyl group derived from diamine is introduced into the polyimide. The acid value of the polyimide can be controlled within a desired range by appropriately adjusting the type of diamine, its charging ratio, reaction conditions, and the like.

  The reaction (condensation reaction) between tetracarboxylic dianhydride and diamine can be carried out by a known method, as will be understood by those skilled in the art. For example, in this reaction, first, tetracarboxylic dianhydride and diamine are added in an organic solvent in an equimolar or almost equimolar ratio at a reaction temperature of 80 ° C. or less, preferably 0 to 60 ° C. Let The order of adding each component is arbitrary. As the reaction proceeds, the viscosity of the reaction solution gradually increases, and polyamic acid, which is a polyimide precursor, is generated. The molecular weight can be adjusted by heating the produced polyamic acid to a temperature of 50 to 80 ° C. for depolymerization. A polyimide is produced by dehydrating and ring-closing the produced polyamic acid. The dehydration ring closure can be performed by a thermal ring closure method by heating or a chemical ring closure method using a dehydrating agent.

  More specifically, regarding the charging ratio of tetracarboxylic dianhydride and diamine, more specifically, the total amount of diamine is preferably 0.5 to 2.0 mol with respect to 1.0 mol of the total amount of tetracarboxylic dianhydride. More preferably, it is in the range of 0.8 to 1.0 mol. When the ratio of the diamine exceeds 2.0 mol, many polyimide oligomers having amino groups at the ends are produced, and when the proportion is less than 0.5 mol, many polyimide oligomers having carboxyl groups at the ends tend to be produced. When the amount of the polyimide oligomer is increased, the weight average molecular weight of the polyimide is decreased, and various characteristics such as heat resistance of the photosensitive adhesive composition are easily decreased. By adjusting the charging ratio, the weight average molecular weight of the polyimide can be adjusted to be in the range of 5000 to 150,000.

  As the diamine used for the synthesis of the polyimide, in order to particularly improve the solubility in an alkali developer, the above formulas (Ia), (Ib), (II-a), (II The aromatic diamine represented by II-b) or (II-c) is preferable.

In order to reduce the Tg of polyimide and reduce thermal stress, the diamine preferably further contains an aliphatic ether diamine represented by the following general formula (III). In formula (III), Q ¹ , Q ² and Q ³ each independently represent an alkylene group having 1 to 10 carbon atoms, and n ₁ represents an integer of ₁ to 80.

  More specific examples of the aliphatic ether diamine of the formula (III) include those represented by the following chemical formula (IIIa), (IIIb) or (IIIc). Among these, the aliphatic ether diamine of the formula (IIIa) is preferable in that it can secure a low-temperature sticking property before exposure and a good re-adhesion property to an adherend after exposure.

  Commercially available products of aliphatic ether diamines include, for example, Jeffamine “D-230”, “D-400”, “D-2000”, “D-4000”, “ED-600” manufactured by Sun Techno Chemical Co., Ltd. ”,“ ED-900 ”,“ ED-2001 ”,“ EDR-148 ”(trade name), BASF (manufactured) polyetheramine“ D-230 ”,“ D-400 ”,“ D-2000 ” (Product name).

Furthermore, in order to further improve the re-adhesion after exposure, it is preferable to use a siloxane diamine represented by the following general formula (IV). In formula (IV), R ¹ and R ² each independently represent an alkylene group having 1 to 5 carbon atoms or a phenylene group which may have a substituent, and R ³ , R ⁴ , R ⁵ and R ⁶ are each Independently, it represents an alkyl group having 1 to 5 carbon atoms, a phenyl group or a phenoxy group, and n ₂ represents an integer of 1 to 5.

As the siloxane diamine represented by the chemical formula (IV), for example, when n _{2 in} the formula is 1, 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, 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 may be mentioned. When n ₂ is 2, 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-1,5-bis (4-aminobutyl) trisiloxane, 1,1 , 5,5-tetraphenyl-3,3-dimethoxy-1,5-bis (5-aminopentyl) 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-dimethoxy-1,5-bis ( 5-aminopentyl) trisiloxane, 1,1,3,3,5,5-hexamethyl-1,5-bis (3-aminopropyl) trisiloxane, 1,1,3,3,5,5-hexaethyl- Examples include 1,5-bis (3-aminopropyl) trisiloxane and 1,1,3,3,5,5-hexapropyl-1,5-bis (3-aminopropyl) trisiloxane.

  These diamines can be used alone or in combination of two or more. For example, the aromatic diamine represented by the formula (Ia), (Ib), (II-a), (II-b) or (II-c) is added in an amount of 10 to 50 mol% of the total diamine, and the general formula (IV) 1 to 20 mol% (more preferably 5 to 10 mol%) of the total diamine, and the aliphatic ether diamine represented by the general formula (III) is 10 to 90 mol% of the total diamine. It is preferable. By using the aromatic diamine represented by the formula (Ia) or (Ib) at the above ratio, the acid value of the polyimide can be usually 80 to 180 mg / KOH or 80 to 150 mg / KOH. When the siloxane diamine is less than 1 mol% of the total diamine, the re-adhesion property after exposure tends to decrease, and when it exceeds 20 mol%, the solubility in an alkali developer tends to decrease. If the aliphatic ether diamine is less than 10 mol% of the total diamine, the Tg of the polyimide tends to be high and the low-temperature processability (sticking property at low temperature) tends to decrease. Voids tend to be easily generated during subsequent thermocompression bonding.

  The diamine may further contain a diamine other than those described above. For example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenylmethane, 3 , 4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethermethane, bis (4-amino-3,5-dimethylphenyl) methane, bis (4-amino-3,5-diisopropylphenyl) methane, 3,3 ′ -Diaminodiphenyldifluoromethane, 3,4'-diaminodiphenyldifluoromethane, 4,4'-diaminodiphenyldifluoromethane, 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diamino Diphenyls Phon, 3,3′-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl ketone, 3,4′-diaminodiphenyl ketone, 4,4 '-Diaminodiphenyl ketone, 2,2-bis (3-aminophenyl) propane, 2,2'-(3,4'-diaminodiphenyl) propane, 2,2-bis (4-aminophenyl) propane, 2, 2-bis (3-aminophenyl) hexafluoropropane, 2,2- (3,4'-diaminodiphenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) 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-methylethylidene)) bisaniline, 3,4 ′-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 4,4 '-(1,4-phenylenebis (1-methylethylidene)) bisaniline, 2,2-bis (4- (3-aminophenoxy) phenyl) propane, 2,2-bis (4- (3-aminophenoxy) Phenyl) hexafluoropropane, 2,2-bis (4- (4-aminophenoxy) phenyl) hexafluoropropane, bis (4- (3-aminoenoxy) phenyl) sulfide, bis (4- (4-aminoenoxy) phenyl) Sulfide, bis (4- (3-aminoenoxy) phenyl) sulfone, bis (4- (4-aminoenoxy) phenyl ) Sulfone, 1,3-bis (aminomethyl) cyclohexane and 2,2-bis (4-aminophenoxyphenyl) propane.

  Tetracarboxylic dianhydride used as a raw material for the synthesis of polyimide is preferably purified by recrystallization from acetic anhydride in order to suppress deterioration of various properties of the adhesive. Alternatively, the tetracarboxylic dianhydride may be dried by heating at a temperature lower by 10 to 20 ° C. than its melting point for 12 hours or more. The purity of tetracarboxylic dianhydride can be evaluated by the difference between the endothermic onset temperature measured by a differential scanning calorimeter (DSC) and the endothermic peak temperature, and this difference is within 20 ° C. due to recrystallization or drying. More preferably, carboxylic dianhydride purified so as to be within 10 ° C. is used for the synthesis of polyimide. The endothermic start temperature and endothermic peak temperature are measured using DSC (DSC-7, manufactured by Perkin Elmer Co.) under the conditions of sample amount: 5 mg, temperature increase rate: 5 ° C./min, measurement atmosphere: nitrogen.

  Examples of the tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and 2,2 ′, 3,3′-biphenyltetracarboxylic acid. Dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4 -Dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) Ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ′, 4′-benzophenone tetracarboxylic 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- Naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetracarboxylic 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-Tetracar Acid 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-dicarboxyphenyldimethylsilyl) benzene dianhydride, 1,3-bis (3,4-dicarboxyphenyl) -1,1, 3,3-tetramethyldicyclohexane dianhydride, p-phenylenebis (trimellitic anhydride), ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic 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 dianhydride, pyrrolidine-2,3,4,5-tetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride Anhydride, bis (exo-bicyclo [2,2,1] heptane-2,3-dicarboxylic dianhydride, bicyclo- [2,2,2] -oct-7-ene-2,3,5,6 -Tetracarboxylic acid 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenyl) phenyl] propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis [4- (3,4-dicarboxyphenyl) phenyl] hexafluoropropane dianhydride, 4,4′-bis (3 , 4-Dicarboxyphenoxy) diphenyl sulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzene bis (trimellitic anhydride), 1,3-bis (2-hydroxyhexafluoroisopropyl) benzene Bis (trimellitic anhydride), 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-di Carboxylic acid dianhydride, and tetrahydrofuran-2,3,4,5-tetracarboxylic acid dianhydride.

  In particular, a tetracarboxylic dianhydride represented by the following chemical formula (V) or (VI) is preferable in order to impart good solubility in a solvent. In this case, it is preferable that the ratio of the tetracarboxylic dianhydrides represented by these formulas be 50 mol% or more with respect to 100 mol% of all tetracarboxylic dianhydrides. When this proportion is less than 50 mol%, the effect of improving solubility tends to be reduced.

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

A radiation-polymerizable compound is a compound that polymerizes upon irradiation with radiation such as ultraviolet rays or electron beams. The radiation polymerizable compound is preferably a compound having an ethylenically unsaturated group such as an acrylate group and a methacrylate group. Specific examples of the radiation polymerizable compound include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, pentenyl acrylate, tetrahydro Furfuryl acrylate, tetrahydrofurfuryl methacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, trimethylolpropane Triacrylate, trimethylolpropane dimethacrylate, tri Tyrolpropane trimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol 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-methan Acryloyloxy-2-hydroxypropane, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, triacrylate of tris (β-hydroxyethyl) isocyanurate, a compound represented by the following general formula (10), Examples include urethane acrylate or urethane methacrylate, and urea acrylate. In formula (10), R ³ and R ⁴ each independently represent a hydrogen atom or a methyl group, and q and r each independently represent an integer of 1 or more.

  Urethane acrylate and urethane methacrylate are produced, for example, by a reaction of a diol, an isocyanate compound represented by the following general formula (21), and a compound represented by the following general formula (22).

In the formula (21), s represents 0 or 1, and R ⁵ represents a divalent or trivalent organic group having 1 to 30 carbon atoms. In formula (22), R ⁶ represents a hydrogen atom or a methyl group, and R ⁷ represents an ethylene group or a propylene group.

  Urea methacrylate is produced, for example, by a reaction between a diamine represented by the following general formula (31) and a compound represented by the following general formula (32).

In formula (31), R ⁸ represents a divalent organic group having 2 to 30 carbon atoms. In formula (32), t represents 0 or 1.

  In addition to the above compounds, a compound having at least one ethylenically unsaturated group and a functional group such as an oxirane ring, an isocyanate group, a hydroxyl group, and a carboxyl group is added to a vinyl copolymer containing a functional group. A radiation-polymerizable copolymer having an ethylenically unsaturated group in the side chain and the like obtained by the reaction can be used.

  These radiation polymerizable compounds can be used alone or in combination of two or more. Among these, the radiation polymerizable compound represented by the general formula (10) is preferable in that it can provide solvent resistance after curing, and urethane acrylate and urethane methacrylate are preferable in that they can provide flexibility after curing.

  The molecular weight of the radiation polymerizable compound is preferably 2000 or less. When the molecular weight exceeds 2000, the solubility of the photosensitive adhesive in an alkaline developer tends to be reduced, and the tackiness of the adhesive film is reduced, so that the adhesive is stuck to an adherend such as a semiconductor wafer at a low temperature. Tend to be difficult.

  The content of the radiation-polymerizable compound is preferably 20 to 80 parts by weight, more preferably 30 to 60 parts by weight with respect to 100 parts by weight of the alkali-soluble polymer. When the amount of the radiation polymerizable compound exceeds 80 parts by weight, the adhesiveness after thermocompression bonding tends to decrease due to the polymerized radiation polymerizable compound. If it is less than 5 parts by weight, the solvent resistance after exposure tends to be low, and it tends to be difficult to form a pattern.

  The photopolymerization initiator preferably has an absorption band at 300 to 400 nm in order to improve sensitivity during pattern formation. Specific examples of the photopolymerization initiator include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone, 4-methoxy- 4′-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxy- Aromatic ketones such as cyclohexyl-phenyl-ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropanone-1,2,4-diethylthioxanthone, 2-ethylanthraquinone and phenanthrenequinone, benzoin Methyl ether, benzoin ethyl ether and benzoin phenyl Benzoin ether such as ether, benzoin such as methylbenzoin and ethylbenzoin, benzyl derivatives such as benzyldimethyl ketal, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4 , 5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-phenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer 2-mer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole dimer and 2- (2,4-dimethoxy) 2,4,5-triarylimidazole dimers such as phenyl) -4,5-diphenylimidazole dimer Acridine derivatives such as 9-phenylacridine and 1,7-bis (9,9′-acridinyl) heptane, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide and bis (2 , 4,6, -trimethylbenzoyl) -phenylphosphine oxide and the like. These can be used alone or in combination of two or more.

  The amount of the photopolymerization initiator is not particularly limited, but is usually 0.01 to 30 parts by weight with respect to 100 parts by weight of the alkali-soluble polymer.

  It is preferable that the photosensitive adhesive further contains a thermosetting resin. In the present specification, the thermosetting resin refers to a reactive compound capable of causing a crosslinking reaction by heat. Examples of such compounds include epoxy resins, cyanate resins, bismaleimide resins, phenol resins, urea resins, melamine resins, alkyd resins, acrylic resins, unsaturated polyester resins, diallyl phthalate resins, silicone resins, resorcinol formaldehyde resins, From xylene resin, furan resin, polyurethane resin, ketone resin, triallyl cyanurate resin, polyisocyanate resin, resin containing tris (2-hydroxyethyl) isocyanurate, resin containing triallyl trimellitate, cyclopentadiene Examples thereof include a thermosetting resin synthesized and a thermosetting resin by trimerization of aromatic dicyanamide. Among these, an epoxy resin, a cyanate resin, and a bismaleimide resin are preferable in that an excellent adhesive force can be imparted at a high temperature, and an epoxy resin is particularly preferable in terms of handling properties and compatibility with polyimide. These thermosetting resins can be used alone or in combination of two or more.

  As the epoxy resin, a compound having at least two epoxy groups in the molecule is preferable. From the viewpoints of curability and cured product properties, phenol glycidyl ether type epoxy resins are extremely preferred. Examples of such epoxy resins include glycidyl ether of bisphenol A, AD, S or F, glycidyl ether of hydrogenated bisphenol A, glycidyl ether of ethylene oxide adduct of bisphenol A, and glycidyl ether of propylene oxide adduct of bisphenol A. Glycidyl ether of phenol novolac resin, glycidyl ether of cresol novolac resin, glycidyl ether of bisphenol A novolak resin, glycidyl ether of naphthalene resin, trifunctional or tetrafunctional glycidyl ether, glycidyl ether of dicyclopentadiene phenol resin, dimer Examples thereof include glycidyl esters of acids, trifunctional or tetrafunctional glycidyl amines, and glycidyl amines of naphthalene resins. These can be used alone or in combination of two or more.

  Examples of the cyanate resin include 2,2′-bis (4-cyanatephenyl) isopropylidene, 1,1′-bis (4-cyanatephenyl) ethane, and bis (4-cyanate-3,5-dimethylphenyl) methane. 1,3-bis [4-cyanatephenyl-1- (1-methylethylidene)] benzene, cyanated phenol-dicyclopentanediene adduct, cyanated novolak, bis (4-cyanatophenyl) thioether, bis (4-cyanatophenyl) ether, resorcinol dicyanate, 1,1,1-tris (4-cyanatephenyl) ethane, 2-phenyl-2- (4-cyanatephenyl) isopropylidene. These can be used alone or in combination of two or more.

  Examples of the bismaleimide resin include o-, m- or p-bismaleimide benzene, 4-bis (p-maleimidocumyl) benzene, 1,4-bis (m-maleimidocumyl) benzene, and the following general formula. The maleimide compound represented by (40), (41), (42) or (43) is mentioned. These can be used alone or in combination of two or more.

In the formula (40), R ⁴⁰ represents —O—, —CH ₂ —, —CF ₂ —, —SO ₂ —, —S—, —CO—, —C (CH ₃ ) ₂ — or —C (CF _{3 2} ), 4 R ⁴¹ each independently represents a hydrogen atom, a lower alkyl group, a lower alkoxy group, fluorine, chlorine or bromine, and two Z ^{1 s} each independently represent a dicarboxylic acid having an ethylenically unsaturated double bond. Acid residues are indicated.

In the formula (41), R ⁴² represents —O—, —CH ₂ —, —CF ₂ —, —SO ₂ —, —S—, —CO—, —C (CH ₃ ) ₂ — or —C (CF _{3 2} ), 4 R ⁴³ each independently represent hydrogen, a lower alkyl group, a lower alkoxy group, fluorine, chlorine or bromine, and two Z ^{2 s} each independently represent a dicarboxylic acid having an ethylenically unsaturated double bond Acid residues are indicated.

In the formula (42), x represents an integer of 0 to 4, and a plurality of Z ³ each independently represents a dicarboxylic acid residue having an ethylenically unsaturated double bond.

In the formula (43), two R ^{44 s} each independently represent a divalent hydrocarbon group, a plurality of R ^{45 s} each independently represent a monovalent hydrocarbon group, and two Z ^{4 s} independently represent ethylenic groups. A dicarboxylic acid residue having an unsaturated double bond is shown, and y is an integer of 1 or more.

Examples of Z ¹ , Z ² , Z ³ and Z ^{4 in} formulas (40) to (43) include a maleic acid residue and a citraconic acid residue.

  Examples of the bismaleimide resin represented by the formula (41) include 4,4-bismaleimide diphenyl ether, 4,4-bismaleimide diphenylmethane, 4,4-bismaleimide-3,3′-dimethyl-diphenylmethane, 4-bismaleimide diphenyl sulfone, 4,4-bismaleimide diphenyl sulfide, 4,4-bismaleimide diphenyl ketone, 2′-bis (4-maleimidophenyl) propane, 4-bismaleimide diphenylfluoromethane, and 1,1, 1,3,3,3-hexafluoro-2,2-bis (4-maleimidophenyl) propane.

  Examples of the bismaleimide resin represented by the formula (42) include bis [4- (4-maleimidophenoxy) phenyl] ether, bis [4- (4-maleimidophenoxy) phenyl] methane, and bis [4- (4 -Maleimidophenoxy) phenyl] fluoromethane, bis [4- (4-maleimidophenoxy) phenyl] sulfone, bis [4- (3-maleimidophenoxy) phenyl] sulfone, bis [4- (4-maleimidophenoxy) phenyl] sulfide Bis [4- (4-maleimidophenoxy) phenyl] ketone, 2-bis [4- (4-maleimidophenoxy) phenyl] propane, and 1,1,1,3,3,3-hexafluoro-2,2 -Bis [4- (4-maleimidophenoxy) phenyl] propane.

  When a thermosetting resin is used, additives such as a curing agent, a curing accelerator, and a catalyst can be appropriately added to the photosensitive adhesive in order to cure the thermosetting resin. When a catalyst is added, a cocatalyst can be used as necessary.

  When using an epoxy resin, it is preferable to use an epoxy resin curing agent or curing accelerator, and it is more preferable to use these in combination. 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, and organic acid dihydrazides. , Boron trifluoride amine complexes, imidazoles, tertiary amines, phenolic compounds having at least two phenolic hydroxyl groups in the molecule, and the like. Among these, a phenol compound having at least two phenolic hydroxyl groups in the molecule is preferable from the viewpoint of excellent solubility in an alkali developer.

  Examples of the phenolic compound having at least two phenolic hydroxyl groups in the molecule include phenol novolak resin, cresol novolak resin, t-butylphenol novolak resin, dicyclopentagen cresol novolak resin, dicyclopentagen phenol novolak resin. And xylylene-modified phenol novolak resin, naphthol novolak resin, trisphenol novolak resin, tetrakisphenol novolak resin, bisphenol A novolak resin, poly-p-vinylphenol resin, phenol aralkyl resin and the like.

  The curing accelerator is not particularly limited as long as it accelerates the curing of the epoxy resin. For example, imidazoles, dicyandiamide derivatives, dicarboxylic acid dihydrazide, triphenylphosphine, tetraphenylphosphonium tetraphenylborate, 2-ethyl-4 -Methylimidazole-tetraphenylborate, 1,8-diazabicyclo [5.4.0] undecene-7-tetraphenylborate and the like.

  The amount of the epoxy resin curing agent is preferably 0 to 200 parts by weight with respect to 100 parts by weight of the epoxy resin, and the amount of the curing accelerator is preferably 0 to 50 parts by weight with respect to 100 parts by weight of the epoxy resin.

  When a cyanate resin is used as the thermosetting resin, it is preferable to use a catalyst and, if necessary, a promoter. Examples of the catalyst include metal salts such as cobalt, zinc, and copper, metal complexes, and the like, and examples of the cocatalyst include phenolic compounds such as alkylphenols, bisphenol compounds, and phenol novolacs.

  When a bismaleimide resin is used as the thermosetting resin, it is preferable to use a radical polymerization agent as the curing agent. Examples of the radical polymerization agent include acetylcyclohexylsulfonyl peroxide, isobutyryl peroxide, benzoyl peroxide, octanoyl peroxide, acetyl peroxide, dicumyl peroxide, cumene hydroperoxide, azobisisobutyronitrile and the like. Can be mentioned. At this time, the usage-amount of a radical polymerization agent has preferable 0.01-1.0 weight part with respect to 100 weight part of bismaleimide resin.

  The photosensitive adhesive may contain a coupling agent as appropriate for the purpose of increasing the adhesive strength. Examples of the coupling agent include a silane coupling agent, a titanium coupling agent, and the like, and among them, the silane coupling agent is preferable because it can provide high adhesive force.

  When using a coupling agent, the usage-amount is preferable 0-50 weight part with respect to 100 weight part of polyimide, and 0-20 weight part is more preferable. When it exceeds 50 parts by weight, the storage stability of the photosensitive adhesive tends to be lowered.

  Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, and N- (2-amino). Ethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propanamine, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine, polyoxyethylenepropyltrialkoxysilane And polyethoxydimethylsiloxane. These can be used alone or in combination of two or more.

  The photosensitive adhesive may contain a filler. Examples of the filler include metal fillers such as silver powder, gold powder, and copper powder, non-metallic inorganic fillers such as silica, alumina, boron nitride, titania, glass, iron oxide, aluminum borate, and ceramics, and organic materials such as carbon and rubber fillers. A filler etc. are mentioned.

  The filler can be used properly according to the desired function. For example, the metal filler is added for the purpose of imparting conductivity or thixotropy to the adhesive film, the non-metallic inorganic filler is added for the purpose of imparting low thermal expansion and low hygroscopicity to the adhesive film, and the organic filler is bonded. It is added for the purpose of imparting toughness to the film. These metal fillers, non-metallic inorganic fillers and organic fillers can be used alone or in combination of two or more. Mixing and kneading in the case of using a filler can be performed by appropriately combining dispersers such as a normal stirrer, a raking machine, a three-roller, and a ball mill.

  When the filler is used, the amount thereof is preferably 1000 parts by weight or less and more preferably 500 parts by weight or less with respect to 100 parts by weight of the alkali-soluble polymer. The lower limit is not particularly limited, but is generally 1 part by weight. When the amount of the filler exceeds 1000 parts by weight, the adhesiveness tends to decrease.

  The storage elastic modulus at 100 ° C. after exposure of the photosensitive adhesive is preferably 0.01 to 10 MPa. When the storage elastic modulus is less than 0.01 MPa, resistance to heat and pressure applied during thermocompression bonding after pattern formation tends to be reduced, and the pattern tends to be easily crushed. When the adhesiveness is lowered and thermocompression is applied to the adherend after pattern formation, the temperature required to obtain sufficient adhesion tends to increase.

  The value of the storage elastic modulus is obtained by measuring the dynamic viscoelasticity of a test piece made of an exposed photosensitive adhesive. The dynamic viscoelasticity is measured under conditions of a temperature rising rate: 5 ° C./min, a frequency: 1 Hz, and a measurement temperature: −50 ° C. to 200 ° C. As the measuring device, for example, Rheometrics Viscoelasticity Analyzer “RSA-2” is used.

A specimen for dynamic viscoelasticity measurement is typically prepared as follows. First, an adhesive sheet having a PET film and an adhesive film having a thickness of about 40 μm formed on one surface of the PET film is cut into a size of 35 mm × 10 mm, and an exposure amount is 1000 mJ using a high-precision parallel exposure machine (Oak Seisakusho). UV light is irradiated from the PET film side under the condition of / cm ² . After the exposure, the test piece is obtained by peeling off the PET film.

  It is preferable that the storage elastic modulus at 260 ° C. after exposure and further heat-curing of the photosensitive adhesive is 1 MPa or more. When the storage elastic modulus is less than 1 MPa, when a semiconductor device obtained using a photosensitive adhesive is mounted on a substrate by soldering, it tends to be difficult to suppress peeling or destruction due to high-temperature heating. .

  The value of the storage elastic modulus is obtained by measuring the dynamic viscoelasticity of a test piece made of a photosensitive adhesive after exposure and further heat-cured. Dynamic viscoelasticity is measured under the conditions of a temperature increase rate: 5 ° C./min, a frequency: 1 Hz, and a measurement temperature: −50 ° C. to 300 ° C. As the measuring device, for example, Rheometrics Viscoelasticity Analyzer “RSA-2” is used.

  The test piece for measuring the dynamic viscoelasticity typically includes an adhesive film exposed under the same conditions as those described above in the description of the preparation of the test piece for dynamic viscoelasticity measurement after exposure. Further, it is obtained by curing in an oven at 160 ° C. for 3 hours.

  After exposure, the temperature at which the mass reduction rate of the photosensitive adhesive in thermogravimetric analysis after further heat curing is 5% (hereinafter referred to as “5% mass reduction temperature”) is preferably 260 ° C. or higher. . When the 5% mass reduction temperature is below 260 ° C., it becomes difficult to suppress peeling or destruction due to high-temperature heating when a semiconductor device obtained using a photosensitive adhesive is mounted on a substrate by soldering. is there. In addition, there is a high possibility that the surrounding materials or members due to volatile components generated during heating are contaminated.

  The 5% mass reduction temperature has a mass reduction rate of 5 with respect to the initial mass in a thermogravimetric analysis performed under the conditions of a heating rate: 10 ° C./min, an air flow rate: 80 mL / min, and a measurement temperature: 40 ° C. to 400 ° C. %. Samples for thermogravimetric analysis were finely crushed using an mortar with an adhesive film that had been exposed and heated under the same conditions as described above in the description of the storage modulus after exposure and further heat-cured. Be prepared. As the measuring device, for example, a differential thermothermal weight simultaneous measuring device “EXSTAR 6300” manufactured by SII Nano Technology Co., Ltd. is used.

  The above properties are prepared by preparing a photosensitive adhesive using polyimide, a radiation-polymerizable compound and a photopolymerization initiator, and further using a thermosetting resin and a filler, if necessary, and adjusting their types and blending ratios. Can be achieved.

  A film-like photosensitive adhesive (adhesive film) is prepared by, for example, mixing an alkali-soluble polymer, a radiation polymerizable compound, a photopolymerization initiator, and other components as necessary in an organic solvent, and kneading the mixed solution. The varnish is prepared, a layer of this varnish is formed on the substrate, the varnish layer is dried by heating, and then the substrate is removed if necessary.

  The above mixing and kneading can be carried out by appropriately combining dispersers such as a normal stirrer, a raking machine, a triple roll, and a ball mill. When a thermosetting resin is used, drying is performed at a temperature at which the thermosetting resin does not sufficiently react during drying and under conditions where the solvent is sufficiently volatilized. Specifically, the varnish layer is dried by heating at 60 to 180 ° C. for 0.1 to 90 minutes.

  Specifically, the temperature at which the thermosetting resin does not sufficiently react is a DSC (for example, “DSC-7 type” (trade name) manufactured by PerkinElmer, Inc.), a sample amount of 10 mg, and a heating rate of 5 The temperature is equal to or lower than the peak temperature of the reaction heat when measured under the conditions of ° C / min and measurement atmosphere: air.

  The organic solvent used for preparing the varnish, that is, the varnish solvent is not particularly limited as long as the material can be uniformly dissolved or dispersed. Examples include dimethylformamide, toluene, benzene, xylene, methyl ethyl ketone, tetrahydrofuran, ethyl cellosolve, ethyl cellosolve acetate, dioxane, cyclohexanone, ethyl acetate, and N-methyl-pyrrolidinone.

  The thickness of the varnish layer is preferably 1 to 100 μm. If this thickness is less than 1 μm, the function of fixing the adherend tends to be reduced, and if it exceeds 100 μm, the residual volatile content in the resulting adhesive film 1 tends to increase.

  The residual volatile content of the adhesive film is preferably 10% by mass or less. If this residual volatile content exceeds 10%, voids are likely to remain inside the adhesive film due to foaming due to volatilization of the solvent during heating for assembly, and the moisture resistance reliability tends to be reduced. In addition, the possibility of contamination of surrounding materials or members due to volatile components generated during heating increases. This residual volatile component is the residual volatile content when the initial mass of the adhesive film cut to a size of 50 mm × 50 mm is M1, and the mass after heating this adhesive film in an oven at 160 ° C. for 3 hours is M2. It is calculated by (mass%) = {(M2-M1) / M1} × 100.

  The base material used for forming the adhesive film is not particularly limited as long as it can withstand the above drying conditions. For example, a polyester film, a polypropylene film, a polyethylene terephthalate film, a polyimide film, a polyetherimide film, a polyether naphthalate film, or a methylpentene film can be used as a base material. The film as the base material may be a multilayer film in which two or more kinds are combined, or the surface may be treated with a release agent such as silicone or silica.

It is an end view which shows one Embodiment of the manufacturing method of the semiconductor device which concerns on this invention. It is an end view which shows one Embodiment of the manufacturing method of the semiconductor device which concerns on this invention. It is an end view which shows one Embodiment of the manufacturing method of the semiconductor device which concerns on this invention. It is an end view which shows one Embodiment of the manufacturing method of the semiconductor device which concerns on this invention. It is a top view which shows one Embodiment of the manufacturing method of the semiconductor device which concerns on this invention. It is an end view which shows one Embodiment of the manufacturing method of the semiconductor device which concerns on this invention. It is a top view which shows one Embodiment of the manufacturing method of the semiconductor device which concerns on this invention. It is an end view which shows the semiconductor device manufactured by the manufacturing method of the semiconductor device which concerns on this invention. It is sectional drawing which shows the CMOS sensor using the semiconductor device manufactured by the manufacturing method of the semiconductor device which concerns on this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Semiconductor device, 3 ... Glass substrate, 3a ... The surface (1st main surface) of a glass substrate, 3b ... The back surface (2nd main surface) of a glass substrate, 5 ... Semiconductor chip, 7 ... Adhesive layer.

Claims (7)

Providing an adhesive layer made of a film-like photosensitive adhesive on the first main surface of the glass substrate having first and second main surfaces facing each other;
Irradiating light from the second main surface side to expose the adhesive layer, and patterning the adhesive layer by development;
Directly bonding the semiconductor chip to the patterned adhesive layer so that the circuit surface thereof faces the glass substrate;
A method for manufacturing a semiconductor device.   The method for manufacturing a semiconductor device according to claim 1, wherein the photosensitive adhesive contains an alkali-soluble polymer, a radiation polymerizable compound, and a photopolymerization initiator.   The method for manufacturing a semiconductor device according to claim 2, wherein the alkali-soluble polymer has a carboxyl group or a phenolic hydroxyl group.   The method for manufacturing a semiconductor device according to claim 2, wherein the alkali-soluble polymer has a glass transition temperature of 150 ° C. or lower.   The manufacturing method of the semiconductor device as described in any one of Claims 2-4 whose said alkali-soluble polymer is a polyimide. The polyimide is tetracarboxylic dianhydride and an aromatic diamine represented by the following chemical formula (Ia), (Ib), (II-a), (II-b) or (II-c) The manufacturing method of the semiconductor device of Claim 5 which is a polyimide obtained by making the diamine containing this react.

The method for manufacturing a semiconductor device according to claim 2, wherein the photosensitive adhesive further contains a thermosetting resin.

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