JP6113401B2 - Manufacturing method of semiconductor chip with adhesive film and manufacturing method of semiconductor device - Google Patents

Description

  The present invention relates to a method for manufacturing a semiconductor chip with an adhesive layer and a method for manufacturing a semiconductor device.

  In recent years, in a semiconductor device having a multilayer structure in which a plurality of semiconductor chips are stacked, as the number of stacked semiconductor chips increases, the thickness of the chips tends to decrease. When obtaining a semiconductor chip with an adhesive layer in which an adhesive layer is bonded to such a thin chip, after bonding an adhesive film for a semiconductor to a thin semiconductor wafer, the semiconductor wafer is chipped together with the adhesive film by blade dicing or the like It may be divided into However, in this case, since members having greatly different hardnesses are cut at the same time, the chip may be damaged, or chips generated from the adhesive film may adhere to the surface of the chip, leading to a decrease in yield. It becomes a problem.

  In order to solve this problem, a process called “first dicing method” is performed in which the semiconductor wafer is separated into chips simultaneously with thinning by performing back grinding on a thick semiconductor wafer that has been half-cut in advance. (See Patent Document 1 below) and a method of obtaining a chip aggregate in which chips are arranged at intervals by a process in which a thin wafer is diced with a blade or a laser and separated into chips. Has been.

  When the above process is applied, it is necessary to form an adhesive layer for connecting chips to be stacked on a chip assembly by application or lamination after separation. In this case, the divided chips are connected to each other by the adhesive layer, and in order to re-divide the chips, the adhesive located in the gaps between the chips is removed, or the adhesive adhered to the chips It is necessary to divide the agent layer (see Patent Document 2 below).

JP-A-5-335411 JP 2005-322853 A

  However, when a process for removing the adhesive is used, since a solution that dissolves the adhesive is used, there is a concern about chip contamination by the solution. In addition, in the process of dividing the adhesive layer attached to the chip, if the adhesive layer is divided by expanding or the like, the adhesive layer is not necessarily divided in the same direction, so it is difficult to obtain a uniform adhesive layer. . Further, as in Patent Document 2, when an adhesive layer made of an uncured paste is bonded to a semiconductor chip, the adhesive located in the gap between the chips may adhere to the side surface or surface of the chip. In these cases, it is prevented to form a semiconductor chip with an adhesive layer including an adhesive layer having a shape suitable for mounting a semiconductor chip.

  The present invention has been made in view of the above circumstances, and a method of manufacturing a semiconductor chip with an adhesive layer capable of easily forming a semiconductor chip with an adhesive layer including an adhesive layer having a shape suitable for mounting of a semiconductor chip. The purpose is to provide. Another object of the present invention is to provide a method for manufacturing a semiconductor device using the semiconductor chip with an adhesive layer obtained by the manufacturing method.

  That is, in the method for manufacturing a semiconductor chip with an adhesive layer according to the present invention, a bonding step of bonding a plurality of semiconductor chips arranged at intervals to an adhesive film containing a photocurable component, and a photocurable component In the state where the adhesive film containing is disposed on the opposite side of the semiconductor chip across the adhesive film, the adhesive film adheres after the exposure process of irradiating the adhesive film and the adhesive film with light through the semiconductor chip, and after the exposure process. And picking up the semiconductor chip.

  In the manufacturing method of the semiconductor chip with an adhesive layer according to the present invention, since the film-like adhesive film is attached to the semiconductor chip in the attaching step, compared to the case where the paste-like adhesive is attached to the semiconductor chip. Thus, adhesion of the adhesive to the side surface or surface of the semiconductor chip can be suppressed. And in the manufacturing method of the semiconductor chip with an adhesive layer according to the present invention, in the exposure step, the adhesive film and the adhesive film are irradiated with light through the semiconductor chip, so that the adhesive film and the adhesive film are made of the semiconductor chip. An unexposed portion that is shielded from light and an exposed portion that is irradiated with light are formed. In this case, the reaction of the photocurable component proceeds in the exposed portion of the adhesive film and the pressure-sensitive adhesive film, so that the adhesive film and the pressure-sensitive adhesive film are hardly separated from each other in the exposed portion, and the exposed portion is compared with the unexposed portion. And become brittle. Thus, when a force in the direction in which the adhesive film peels from the adhesive film is applied to the unexposed area, the unexposed area in each of the adhesive film and the adhesive film and the exposed area in contact with the unexposed area are unexposed. The exposed portion and the exposed portion are easily peeled from each other. In such a manufacturing method, when picking up a semiconductor chip to which an adhesive film is attached, it is easy to peel the adhesive film from the adhesive film while maintaining the state where the semiconductor chip is attached to the adhesive film in the unexposed area. In addition, it is easy to leave the adhesive film and the pressure-sensitive adhesive film in a desired shape in the exposed portion. Therefore, in such a manufacturing method, a semiconductor chip with an adhesive layer including an adhesive layer having a shape suitable for mounting a semiconductor chip (for example, a shape having an adhesive surface having the same area as the main surface area of the semiconductor chip) is provided. It can be formed easily.

  Moreover, in the manufacturing method of the semiconductor chip with an adhesive layer according to the present invention, since the film-like adhesive film is attached to the semiconductor chip in the attaching step, the paste-like adhesive is attached to the semiconductor chip. Compared to the case where the adhesive is cured to form an adhesive layer, the number of steps can be reduced because a curing step is not required, and surface unevenness after bonding can be reduced. A semiconductor chip with an adhesive layer can also be obtained.

  In the attaching step, the semiconductor chip may be attached to the adhesive film of the laminated sheet including the adhesive film and the adhesive film. In this case, since the adhesive film and the adhesive film can be collectively laminated on the semiconductor chip, the semiconductor chip with an adhesive layer can be obtained more efficiently. Further, in the attaching step, the adhesive film may be attached to the adhesive film after the semiconductor chip is attached to the adhesive film.

  The method for manufacturing a semiconductor chip with an adhesive layer according to the present invention includes dicing a semiconductor wafer so that the semiconductor wafer is cut from one main surface to the other main surface of the semiconductor wafer before the attaching step. A step of obtaining a plurality of semiconductor chips, or after dicing the semiconductor wafer from one main surface side of the semiconductor wafer so that at least a part of the thickness direction of the semiconductor wafer remains without being cut, You may further provide the process of grinding from the other main surface side of a wafer and obtaining a some semiconductor chip. In the method of manufacturing a semiconductor chip with an adhesive layer according to the present invention, an adhesive layer having an adhesive layer having a shape suitable for mounting a semiconductor chip is provided even when a semiconductor chip separated in advance is attached to an adhesive film. A semiconductor chip with an agent layer can be easily formed.

  A method for manufacturing a semiconductor device according to the present invention includes a step of attaching a semiconductor chip of a semiconductor chip with an adhesive layer obtained by the above manufacturing method to a support member via an adhesive film of the semiconductor chip with an adhesive layer. . According to the method for manufacturing a semiconductor device according to the present invention, the semiconductor chip can be suitably attached to the support member, and thus the semiconductor device can be obtained efficiently.

  ADVANTAGE OF THE INVENTION According to this invention, the semiconductor chip with an adhesive layer provided with the adhesive layer of the shape suitable for mounting of a semiconductor chip can be formed easily. In addition, according to the present invention, a semiconductor device can be obtained efficiently and a decrease in yield can be suppressed.

FIG. 1 is a drawing showing a laminated sheet for a semiconductor. FIG. 2 is a drawing showing a step of the method of manufacturing a semiconductor chip with an adhesive layer according to the first embodiment of the present invention. FIG. 3 is a drawing showing a step subsequent to FIG. FIG. 4 is a drawing showing a step subsequent to FIG. FIG. 5 is a drawing showing a step subsequent to FIG. FIG. 6 is a drawing showing a step subsequent to FIG. FIG. 7 is a drawing showing one step in a method for manufacturing a semiconductor chip with an adhesive layer according to the second embodiment of the present invention. FIG. 8 is a drawing showing a step subsequent to FIG. FIG. 9 is a drawing showing one step in a method for manufacturing a semiconductor chip with an adhesive layer according to a third embodiment of the present invention. FIG. 10 is a drawing showing a step subsequent to FIG. FIG. 11 is a drawing showing one step in a method of manufacturing a semiconductor device according to an embodiment of the present invention.

  Hereinafter, embodiments for carrying out the present invention will be described in detail with reference to the drawings as necessary. However, the present invention is not limited to the following embodiments. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.

  In the present specification, “(meth) acryl” means acryl or methacryl corresponding thereto. The same applies to those having a (meth) acrylic structure such as “(meth) acrylate”.

[Laminated sheet for semiconductor]
FIG. 1 is a drawing showing a laminated sheet for semiconductor, FIG. 1 (a) and FIG. 1 (c) are plan views of the laminated sheet for semiconductor, and FIG. 1 (b) is a plan view of FIG. It is Ib-Ib sectional view taken on the line. A laminated sheet for semiconductor 100 (hereinafter referred to as “laminated sheet 100” in some cases) is a laminated sheet used for semiconductor applications, and includes a film-like (A) adhesive film (semiconductor adhesive film) 110 and a film-like sheet. (B) A laminate including the adhesive film 120 and the base film 130. The adhesive film 110 is disposed on the adhesive film 120 in a state where the adhesive film 110 is attached to one main surface 120 a of the adhesive film 120. The adhesive film 120 is disposed on the base film 130 in a state where the adhesive film 120 is attached to the main surface 130 a of the base film 130.

  The adhesive film 110 may be circular (see FIG. 1 (a)) or rectangular (see FIG. 1 (c)). 1-100 micrometers is preferable and, as for the thickness of the adhesive film 110, 5-75 micrometers is more preferable.

  The adhesive film 120 may have a rectangular shape (see FIGS. 1A and 1C) or a circular shape. 1-100 micrometers is preferable, as for the thickness of the adhesive film 120, 2-60 micrometers is more preferable, and 3-30 micrometers is still more preferable.

  The area of the main surface 120a of the adhesive film 120 is preferably larger than the area of the main surface 110a of the adhesive film 110. This makes it easy to attach the adhesive film 120 to a jig such as a wafer ring when the laminated sheet 100 is installed in an expanding apparatus, a die bonding apparatus, or the like, and handling properties are improved.

  Hereinafter, (A) the adhesive film 110 and (B) the adhesive film 120 will be described in detail.

<(A) Adhesive film>
(A) The adhesive film contains a photocurable component. Examples of the photocurable component include a photocurable resin and a photo radical generator.

(A1: Thermoplastic resin)
(A) The adhesive film preferably contains (A1) a thermoplastic resin. The component (A1) is not particularly limited as long as it is a thermoplastic resin, but considering the film moldability at a low molecular weight and the adhesion to a substrate, it contains a highly polar group in the molecular skeleton. Is more preferable, and a thermoplastic resin containing an imide skeleton in the molecular skeleton is more preferable. The component (A1) preferably has an imide skeleton in the main chain or side chain. When the thermoplastic resin has an imide skeleton, excellent film moldability and adhesion to a substrate can be obtained.

  Examples of the thermoplastic resin having an imide skeleton include polyimide resin, polyamideimide resin, polyurethaneimide resin, polyetherimide resin, polyurethaneamideimide resin, siloxane polyimide resin, polyesterimide resin, and acrylic resin. It is not limited to these. These resins can be used alone or in combination of two or more. As said thermoplastic resin, a polyimide resin is preferable.

  The polyimide resin can be obtained, for example, by subjecting tetracarboxylic dianhydride and diamine to a condensation reaction by a known method.

  The mixing molar ratio of tetracarboxylic dianhydride and diamine in the condensation reaction is such that the total amount of diamine is 0.5 to 2.0 mol with respect to 1.0 mol of the total amount of tetracarboxylic dianhydride. Is preferable, and it is more preferable that it is 0.8-1.0 mol. In addition, the addition order of tetracarboxylic acid anhydride and diamine may be arbitrary.

  In the condensation reaction, when the total amount of diamine exceeds 2.0 mol with respect to the total amount of tetracarboxylic dianhydride of 1.0 mol, the amount of polyimide oligomer having an amine terminal tends to increase in the resulting polyimide resin. is there. On the other hand, when the total amount of diamine is less than 0.5 mol, the amount of the polyimide resin oligomer having an acid terminal tends to increase in the obtained polyimide resin. By setting the mixing molar ratio of tetracarboxylic dianhydride and diamine within the above range, the weight average molecular weight of the polyimide resin increases, and (A) various characteristics including heat resistance of the adhesive film are easily imparted. .

  Moreover, 80 degreeC or less is preferable and, as for the reaction temperature in the said condensation reaction, 0-60 degreeC is more preferable. As the reaction proceeds, the viscosity of the reaction solution gradually increases, and polyamic acid, which is a polyimide resin precursor, is generated. In addition, in order to suppress the fall of the various characteristics of (A) adhesive film, it is preferable that said tetracarboxylic dianhydride is what recrystallized and refined processing with acetic anhydride.

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

  There is no restriction | limiting in particular as tetracarboxylic dianhydride used as a raw material of a polyimide resin, For example, 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) ethane dianhydride, 1,1-bis (3,4-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxy) Phenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 3,4,9,10-perylenetetraca Boronic acid dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, benzene-1,2,3,4-tetracarboxylic dianhydride, 3,4,3 ′, 4′-benzophenone tetra Carboxylic dianhydride, 2,3,2 ′, 3′-benzophenone tetracarboxylic dianhydride, 3,3,3 ′, 4′-benzophenone tetracarboxylic dianhydride, 1,2,5,6- Naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 1,2,4,5-naphthalenetetra Carboxylic 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 Anhydride, thiophene-2,3,5,6-tetracarboxylic dianhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride, 3,4,3 ′, 4′-biphenyltetra Carboxylic 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 (trimellitate 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 Acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, bis (exo-bicyclo [2,2,1] heptane-2,3-dicarboxylic dianhydride, bicyclo- [2, 2,2] -o To-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-dicarboxyphenyl) hexafluoropropane dianhydride, 2,2-bis [4- (3,4-dicarboxy) Phenyl) phenyl] hexafluoropropane dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 1,4-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimerit Acid anhydride), 1,3-bis (2-hydroxyhexafluoroisopropyl) benzenebis (trimellitic anhydride), 5- (2,5-dioxotetrahydro Ryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, tetrahydrofuran-2,3,4,5-tetracarboxylic dianhydride, tetracarboxylic acid represented by the following general formula (1) Examples thereof include acid dianhydrides and tetracarboxylic dianhydrides represented by the following formula (2) or (3).

［式中、ａは２〜２０の整数を示す。］

[Wherein, a represents an integer of 2 to 20. ]

  The tetracarboxylic dianhydride represented by the general formula (1) can be synthesized from, for example, trimellitic anhydride monochloride and the corresponding diol, 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 anhydride), 1,12- (dodecamechi) Emissions) bis (trimellitate anhydride), 1,16 (hexamethylene decamethylene) bis (trimellitate anhydride), 1,18 (octadecamethylene) bis (trimellitate anhydride) and the like.

  Moreover, as tetracarboxylic dianhydride, the tetracarboxylic acid represented by the above formula (2) or (3) from the viewpoint of imparting good solubility and moisture resistance in a solvent and transparency to 365 nm light. A dianhydride is preferred.

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

  There is no restriction | limiting in particular as diamine used as a raw material of the said polyimide resin, 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′-diaminodiphenyl Sulfo 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,3′-diaminodiphenylsulfide, 3,4′-diaminodiphenylsulfide, 4,4′-diaminodiphenylsulfide, 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-amino Noenoxy) phenyl) sulfone, bis (4- (4-aminoenoxy) phenyl) sulfone, 3,3′-dihydroxy-4,4′-diaminobiphenyl, aromatic diamines such as 3,5-diaminobenzoic acid, 1,3 -Bis (aminomethyl) cyclohexane, 2,2-bis (4-aminophenoxyphenyl) propane, aliphatic ether diamine represented by the following general formula (4), siloxane diamine represented by the following general formula (5), etc. Is mentioned.

［式中、Ｑ^１、Ｑ^２及びＱ^３は各々独立に、炭素数１〜１０のアルキレン基を示し、ｂは２〜８０の整数を示す。上記アルキレン基は、直鎖であってもよく、分岐鎖であってもよい。］

[Wherein, Q ¹ , Q ² and Q ³ each independently represents an alkylene group having 1 to 10 carbon atoms, and b represents an integer of 2 to 80. The alkylene group may be linear or branched. ]

［式中、Ｑ^４及びＱ^９は各々独立に、炭素数１〜５のアルキレン基、又はフェニレン基を示し、Ｑ^５、Ｑ^６、Ｑ^７及びＱ^８は各々独立に、炭素数１〜５のアルキル基、フェニル基、又はフェノキシ基を示し、ｃは１〜５の整数を示す。なお、上記フェニレン基は、置換基を有していてもよい。］

[Wherein, Q ⁴ and Q ⁹ each independently represent an alkylene group having 1 to 5 carbon atoms or a phenylene group, and Q ⁵ , Q ⁶ , Q ⁷ and Q ⁸ each independently represent 1 to 5 carbon atoms. An alkyl group, a phenyl group, or a phenoxy group, and c represents an integer of 1 to 5. The phenylene group may have a substituent. ]

  Among the above diamines, the aliphatic ether diamines represented by the above general formula (4) are preferable from the viewpoint of imparting compatibility with other components, organic solvent solubility, and low-temperature pasteability, and ethylene glycol and / or propylene glycol-based. Diamine is more preferred.

  Specific examples of such aliphatic ether diamines include Jeffamine D-230, D-400, D-2000, D-4000 manufactured by Sun Techno Chemical Co., and polyetheramine D-230, D manufactured by BASF. Aliphatic diamines such as polyoxyalkylene diamines such as -400 and D-2000. These diamines are preferably 1 to 80 mol%, more preferably 10 to 80 mol%, still more preferably 10 to 60 mol% of the total diamine. If this amount is less than 1 mol%, it tends to be difficult to impart high-temperature adhesiveness and hot fluidity. On the other hand, if the amount of the diamine exceeds 80 mol%, the Tg of the polyimide resin becomes too low. There is a tendency for high-temperature adhesion after moisture absorption to decrease.

  Furthermore, the aliphatic ether diamine preferably has a propylene ether skeleton represented by the following general formula (6) from the viewpoint of achieving both low temperature sticking property and heat resistance, The molecular weight is more preferably 300 to 600. The content of such a diamine is preferably 80 mol% or less of the total diamine, and more preferably 60 mol% or less. In addition, the content of such a diamine is preferably 10 mol% or more, more preferably 20 mol% or more of the total diamine, from the viewpoints of thermocompression bonding and high-temperature adhesiveness. When the content of such diamine is in the above range, it becomes easy to adjust the glass transition temperature (Tg) of polyimide to 10 ° C. or more, and further improve the sticking property, thermocompression bonding property, high temperature adhesion property, and reflow resistance. It becomes possible to make it.

［式中、ｄは３〜４０の整数を示す。］

[Wherein, d represents an integer of 3 to 40. ]

  Moreover, it is preferable to use the siloxane diamine represented by the said General formula (5) from a viewpoint of improving the adhesiveness and adhesiveness in room temperature among the said diamine.

  Specifically, as the siloxane diamine represented by the general formula (5), it is assumed that c in the formula (5) 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- And methoxy-1,3-bis (4-aminobutyl) disiloxane, etc., where c is 2, 1,1,3,3,5,5-hexamethyl-1,5-bis (4-amino) Phenyl) 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, 1,5,5-tetramethyl-3,3-dimethoxy-1,5-bis (2-aminoethyl) trisiloxane, 1,1,5,5-tetramethyl-3,3-dimethoxy-1,5- Bis (4-aminobutyl) trishi Xanthone, 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-1,5-bis (3-aminopropyl) trisiloxane, 1,1,3,3,5,5 -Hexapropyl-1,5-bis (3-aminopropyl) trisiloxane and the like.

  The said siloxane diamine can be used individually by 1 type or in combination of 2 or more types. Moreover, it is preferable that content of the said siloxane diamine is 1-80 mol% of all the diamine, It is more preferable that it is 2-50 mol%, It is still more preferable that it is 5-50 mol%. When the content of the siloxane diamine is less than 1 mol%, the effect of adding the siloxane diamine tends to be small. When the content of the siloxane diamine is more than 80 mol%, compatibility with other components, high-temperature adhesiveness, and There exists a tendency for developability to fall.

  As the diamine, a diamine containing a hydroxyl group or a carboxyl group can also be used separately in order to form a crosslinking point at the time of thermosetting. Examples of such diamines include diaminophenols such as 2,4-diaminophenol; 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl. 4,4′-diamino-2,2′-dihydroxybiphenyl, hydroxybiphenyl compounds such as 4,4′-diamino-2,2 ′, 5,5′-tetrahydroxybiphenyl; 3,3′-diamino- 4,4′-dihydroxydiphenylmethane, 4,4′-diamino-3,3′-dihydroxydiphenylmethane, 4,4′-diamino-2,2′-dihydroxydiphenylmethane, 2,2-bis [3-amino- 4-hydroxyphenyl] propane, 2,2-bis [4-amino-3-hydroxyphenyl] propane, 2,2-bis 3-amino-4-hydroxyphenyl] hexafluoropropane, hydroxydiphenylalkanes such as hydroxydiphenylmethane such as 4,4′-diamino-2,2 ′, 5,5′-tetrahydroxydiphenylmethane; 3,3′-diamino -4,4'-dihydroxydiphenyl ether, 4,4'-diamino-3,3'-dihydroxydiphenyl ether, 4,4'-diamino-2,2'-dihydroxydiphenyl ether, 4,4'-diamino-2,2 ' , 5,5'-tetrahydroxydiphenyl ether and the like; 3,3'-diamino-4,4'-dihydroxydiphenyl sulfone, 4,4'-diamino-3,3'-dihydroxydiphenyl sulfone, 4,4 '-Diamino-2,2'-dihydro Diphenylsulfone compounds such as sidiphenylsulfone and 4,4′-diamino-2,2 ′, 5,5′-tetrahydroxydiphenylsulfone; 2,2-bis [4- (4-amino-3-hydroxyphenoxy) phenyl Bis [(hydroxyphenyl) phenyl] alkane compounds such as propane; bis (hydroxyphenoxy) biphenyl compounds such as 4,4′-bis (4-amino-3-hydroxyphenoxy) biphenyl; Bis [(hydroxyphenoxy) phenyl] sulfone compounds such as bis [4- (4-amino-3-hydroxyphenoxy) phenyl] sulfone; Diaminobenzoic acids such as 3,5-diaminobenzoic acid: 4,4′-diamino- 3,3′-dihydroxydiphenylmethane, 4,4′-diamino-2,2′-dihai Bis (hydroxyphenoxy) biphenyl compounds such as droxydiphenylmethane, 2,2-bis [3-amino-4-carboxyphenyl] propane, 4,4′-bis (4-amino-3-hydroxyphenoxy) biphenyl Can be mentioned.

  During the synthesis of the polyimide resin, a monofunctional acid anhydride and / or a monofunctional amine such as a compound represented by the following formula (7), (8), (9) or (10) is added to the condensation reaction solution. By this, functional groups other than acid anhydrides or diamines can be introduced at the polymer ends, and various functionalities can be imparted.

  The polyimide resin mentioned above can be used individually by 1 type or in mixture of 2 or more types as needed.

  The transmittance of the polyimide resin with respect to light having a wavelength of 400 nm is preferably 1% or more and preferably 3% or more when formed into a film having a thickness of 10 μm from the viewpoint of improving photocurability and peel strength. More preferred. Such a polyimide resin is represented by, for example, an acid anhydride represented by the above formula (2), an aliphatic ether diamine represented by the above general formula (4), and / or the above general formula (5). It can be synthesized by reacting with siloxane diamine.

  The content of the component (A1) is preferably 10 to 70 parts by mass, more preferably 15 to 50 parts by mass, with the total mass of the (A) adhesive film being 100 parts by mass.

  The glass transition temperature (Tg) of the component (A1) is preferably 10 ° C. or higher, more preferably 20 ° C. or higher, and further preferably 30 ° C. or higher. When the Tg is 10 ° C. or more, it becomes easier to form a semiconductor chip with an adhesive layer including an adhesive layer having a shape suitable for mounting of the semiconductor chip. The Tg of the component (A1) is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, and further preferably 100 ° C. or lower. When this Tg exceeds 150 degreeC, there exists a tendency for thermocompression bonding to fall.

  Here, “Tg” of the component (A1) is a film-forming component of the component (A1), and a temperature increase rate of 5 ° C. using a viscoelasticity analyzer (trade name: RSA-2, manufactured by Rheometrics). It is a tan δ peak temperature when measured under the conditions of / min, frequency 1 Hz, measurement temperature −150 to 300 ° C.

  The weight average molecular weight of the component (A1) is preferably 500,000 or less, more preferably 300,000 or less, still more preferably 150,000 or less, and particularly preferably 100,000 or less. The weight average molecular weight of the component (A1) is preferably 5000 or more, and more preferably 10,000 or more. When the weight average molecular weight is in the above range, (A) the strength, flexibility and tackiness of the adhesive film are improved. Further, since the thermal fluidity is good, it is possible to ensure good embedding properties with respect to the wiring step (unevenness) on the substrate surface. On the other hand, when the weight average molecular weight is less than 5000, the film formability tends to be insufficient. When the said weight average molecular weight exceeds 500,000, there exists a tendency for fluidity | liquidity at the time of heat and wettability to become insufficient. Here, the “weight average molecular weight” means the weight average molecular weight when measured in terms of polystyrene using high performance liquid chromatography (manufactured by Shimadzu Corporation, trade name: C-R4A).

  By setting the Tg and weight average molecular weight of the component (A1) within the above ranges, the heating temperature (thermocompression bonding temperature) when the semiconductor element is bonded and fixed to the semiconductor element mounting support member can be lowered. High temperature adhesiveness can be imparted while suppressing an increase in warpage.

(A2: Photocurable resin)
(A) The adhesive film preferably contains (A2) a photocurable resin as a photocurable component. Examples of the component (A2) include compounds having an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include vinyl group, allyl group, propargyl group, butenyl group, ethynyl group, phenylethynyl group, maleimide group, nadiimide group, (meth) acryl group, etc. A (meth) acrylic group is preferred.

  When using such a compound having a (meth) acryl group, it is preferable to use a combination of a monofunctional (meth) acrylate compound and a polyfunctional (meth) acrylate compound from the viewpoint of imparting low temperature stickiness and curability. .

  The 5% mass reduction temperature of the monofunctional (meth) acrylate compound is preferably 100 ° C. or higher because it can reduce generation of voids during thermocompression bonding and suppress outgassing during heating. The above “5% mass reduction temperature” means that the sample was heated at a rate of 10 ° C./min with nitrogen flow using a differential thermothermal gravimetric simultaneous measurement device (trade name: TG / DTA6300, manufactured by SII Nano Technology). It is a 5% mass reduction temperature when measured under the condition of (400 ml / min).

  As the monofunctional (meth) acrylate compound, it is preferable to use a monofunctional acrylate represented by the following formula (11) or (12) in order to improve the adhesiveness after curing.

［式中、ｅは１〜１０の整数を示す。］

[In formula, e shows the integer of 1-10. ]

  10 mass parts or more are preferable with respect to 100 mass parts of (A1) component, and, as for content of these monofunctional (meth) acrylate compounds, 500 mass parts or less are preferable. When the content is less than 10 parts by mass, the pressure-bonding property tends to be lowered, and when the content is more than 500 parts by mass, the heat resistance reliability tends to be lowered.

  The type of polyfunctional (meth) acrylate compound to be combined is not particularly limited, but a (meth) acrylate compound containing a fluorene skeleton represented by the following general formula (13) is used for adjusting the tack force during film molding. It is preferable to use it.

［式中、Ｑ^１０はシアノ基、ハロゲン原子又はアルキル基を示し、Ｑ^１１は分岐アルキレン基を示し、Ｑ^１２は水素原子又はメチル基を示し、Ｑ^１３はアルキル基を示し、ｆは１以上の整数を示し、ｇは２〜４の整数を示し、ｈは０〜４の整数を示す。］

[Wherein, Q ¹⁰ represents a cyano group, a halogen atom or an alkyl group, Q ¹¹ represents a branched alkylene group, Q ¹² represents a hydrogen atom or a methyl group, Q ¹³ represents an alkyl group, and f is 1 or more. G represents an integer of 2 to 4, and h represents an integer of 0 to 4. ]

  5 mass parts or more are preferable with respect to 100 mass parts of (A1) component, and, as for content of the (meth) acrylate compound containing these fluorene skeletons, 100 mass parts or less are preferable. If this content is less than 5 parts by mass, the tack force tends to be difficult to control, and if it exceeds 100 parts by mass, the thermocompression bondability tends to decrease.

  By combining these monofunctional (meth) acrylate compounds and polyfunctional (meth) acrylate compounds, it becomes possible to further improve both peel strength and resolution at the time of exposure, and efficiently remain. It becomes possible to make it.

  The photocurable resin that can be used is not particularly limited, but a bifunctional or higher functional (meth) acrylate compound is preferable. Such (meth) acrylate compounds include diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, triethylene glycol diacrylate, Methylolpropane triacrylate, trimethylolpropane dimethacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol Dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraa Relate, 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, methylenebisacrylamide, N, N-dimethylacrylamide, N-methylolacrylamide, tris (2- Hydroxyethyl) isocyanurate triacrylate, tris (2-hydroxypropyl) isocyanurate urethane acrylate , Tris (2-hydroxybutyl) isocyanurate or urethane methacrylate, and urea acrylate.

  These (A2) components can be used individually by 1 type or in combination of 2 or more types. Among the two types of combinations, the combination of urethane acrylate and methacrylate, the combination of isocyanuric acid diacrylate and methacrylate, and the combination of isocyanuric acid triacrylate and methacrylate are the ones after the curing in that the solvent resistance after curing can be sufficiently imparted. It is preferable at the point which can fully provide high adhesiveness.

  The component (A2) is preferably a tri- or higher functional acrylate compound because it can further improve the adhesiveness after curing and can suppress outgassing during heating. At this time, it is more preferable to contain isocyanuric acid ethylene oxide-modified diacrylate and isocyanuric acid ethylene oxide-modified triacrylate in that heat resistance after curing can be sufficiently imparted.

  As for content of (A2) component, 5-300 mass parts is preferable with respect to 100 mass parts of (A1) component, and 10-250 mass parts is more preferable. When this content exceeds 300 parts by mass, the adhesiveness during thermocompression tends to decrease. On the other hand, when the content is 5 parts by mass or more, the crosslinking density due to exposure tends to be high, and it becomes easier to divide the adhesive film (A) at the time of pickup in the gap between the semiconductor chips.

(A3: Photoradical generator)
(A) The adhesive film preferably contains (A3) a photoradical generator as a photocurable component. The molecular extinction coefficient of the component (A3) with respect to light having a wavelength of 365 nm is preferably 1000 ml / g · cm or more, more preferably 2000 ml / g · cm or more, from the viewpoint of improving sensitivity. The molecular extinction coefficient is obtained by preparing a 0.001 mass% acetonitrile solution of the sample and measuring the absorbance of this solution using a spectrophotometer (trade name: U-3310, manufactured by Hitachi High-Technologies Corporation). It is done.

  The component (A3) is preferably bleached by light irradiation from the viewpoint of improving sensitivity and improving internal curability. Examples of such component (A3) include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2,2-dimethoxy-1,2-diphenylethane-1-one. 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropanone-1, 2,4-diethylthioxanthone, 2-ethylanthraquinone, phenanthrenequinone, etc. Aromatic ketones; 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- ( -Methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4-di (p-methoxyphenyl) -5-phenylimidazole Dimer, 2,4,5-triarylimidazole dimer such as 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazole dimer; 9-phenylacridine, 1,7-bis ( Acridine derivatives such as 9,9'-acridinyl) heptane; bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, bis (2,4,6, -trimethylbenzoyl) -phenyl Examples include bisacyl phosphine oxides such as phosphine oxide, which are photobleached by UV irradiation. . These can be used alone or in combination of two or more.

  0.1-20 mass parts is preferable with respect to 100 mass parts of (A1) component, and, as for content of (A3) component, 0.5-10 mass parts is more preferable.

(A4: thermosetting resin)
(A) The adhesive film preferably further contains (A4) a thermosetting resin (however, excluding a resin corresponding to (A2) a photocurable resin).

  The component (A4) is not particularly limited, but is preferably one containing at least two epoxy groups in the molecule. From the viewpoint of curability and cured product properties, phenol glycidyl ether type epoxy resins are further included. preferable. As such an epoxy resin, for example, glycidyl ether of bisphenol A type (or AD type, S type, F type), glycidyl ether of water-added bisphenol A type, ethylene oxide adduct bisphenol A type glycidyl ether, propylene oxide addition Bisphenol A type glycidyl ether, phenol novolac resin glycidyl ether, cresol novolac resin glycidyl ether, bisphenol A novolak resin glycidyl ether, naphthalene resin glycidyl ether, trifunctional (or tetrafunctional) glycidyl ether, di Glycidyl ether of cyclopentadiene phenol resin, glycidyl ester of dimer acid, trifunctional (or tetrafunctional) glycidyl amine, glycidyl amino of naphthalene resin Etc. The. These can be used alone or in combination of two or more. Among the above, the epoxy resin represented by the following formula (14) is particularly preferable from the viewpoints of thermocompression bonding and adhesiveness after curing.

  In addition, for these epoxy resins, it is possible to use high-purity products in which alkali metal ions, alkaline earth metal ions, halogen ions (especially chlorine ions and hydrolyzable chlorine), which are impurity ions, are reduced to 300 ppm or less, It is preferable for preventing electromigration and preventing corrosion of metal conductor circuits.

  Examples of thermosetting resins other than epoxy resins include resins having an oxazoline group and a maleimide group. A thermosetting resin can be used individually by 1 type or in combination of 2 or more types.

  Further, the 5% mass reduction temperature of the component (A4) (for example, epoxy resin) is preferably 150 ° C. or higher, more preferably 180 ° C. or higher, still more preferably 200 ° C. or higher, and particularly preferably 260 ° C. or higher. When the 5% mass reduction temperature is 150 ° C. or higher, low outgassing property, high temperature adhesiveness, and reflow resistance are improved.

  The above “5% mass reduction temperature” means that the sample was heated at a rate of 10 ° C./min with nitrogen flow using a differential thermothermal gravimetric simultaneous measurement device (trade name: TG / DTA6300, manufactured by SII Nano Technology). It is a 5% mass reduction temperature when measured under the condition of (400 ml / min).

  Moreover, 5-300 mass parts is preferable with respect to 100 mass parts of (A1) component, and, as for content of (A4) component (for example, epoxy resin), 10-100 mass parts is more preferable. When this content exceeds 300 parts by mass, the film formability tends to decrease and becomes brittle, and when the content is less than 5 parts by mass, sufficient thermocompression bonding and high-temperature adhesiveness tend to be difficult to obtain. is there.

(A5: Fila)
(A) The adhesive film may further contain (A5) filler. As the component (A5), for example, a metal filler such as silver powder, gold powder, copper powder, nickel powder; alumina, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, Examples include inorganic fillers such as magnesium oxide, aluminum oxide, aluminum nitride, crystalline silica, amorphous silica, boron nitride, titania, glass, iron oxide and ceramics; organic fillers such as carbon and rubber fillers, etc. Regardless of the shape, it can be used without particular limitation.

  The component (A5) can be used properly according to the desired function. For example, the metal filler can impart conductivity, thermal conductivity, thixotropy and the like to the adhesive film. The non-metallic inorganic filler can impart thermal conductivity, low thermal expansion, low hygroscopicity and the like to the adhesive layer. The organic filler can impart toughness and the like to the adhesive film.

  These metal fillers, inorganic fillers, or organic fillers can be used alone or in combination of two or more. Among these, metal fillers, inorganic fillers, and insulating fillers are preferable because they are provided with conductivity, thermal conductivity, low moisture absorption characteristics, insulating properties, and the like required for adhesive materials for semiconductor devices. Furthermore, among inorganic fillers or insulating fillers, silica filler is more preferable because it has good dispersibility with respect to the resin varnish and can impart a high adhesive force during heating.

  As the component (A5), it is preferable to use a filler whose surface is coated with a coupling agent. By coating with a coupling agent, it becomes possible to prevent aggregation of the filler in the varnish when mixing the other components and the filler into a varnish, and by appropriately changing the coupling agent to be coated ( A) The characteristics of the adhesive film can be improved. As the coupling agent, those described later can be used. In this embodiment, when the filler is coated with a coupling agent treated with methacrylic silane, the peel strength is further improved and the splitting property tends to be improved.

  The average particle size of the component (A5) is preferably 10 μm or less, and preferably 5 μm or less. The component (A5) preferably has an average particle size of 10 μm or less and a maximum particle size of 30 μm or less, more preferably an average particle size of 5 μm or less and a maximum particle size of 20 μm or less. preferable. When the average particle diameter exceeds 10 μm and the maximum particle diameter exceeds 30 μm, the effect of improving fracture toughness tends to be insufficient. Further, the lower limits of the average particle diameter and the maximum particle diameter are not particularly limited, but both are preferably 0.001 μm or more from the viewpoint of handleability.

  Although content of the said (A5) component is determined according to the characteristic or function to provide, 0-90 mass% is preferable with respect to the sum total of a resin component and a filler, 1-80 mass% is more preferable, 3 -70 mass% is still more preferable. By increasing the amount of filler, low alpha, low moisture absorption, and high elastic modulus can be achieved, and dicing performance (cutability with a dicer blade), wire bonding properties (ultrasonic efficiency), and adhesive strength during heating are effectively improved. Can be made.

  When the content of the component (A5) exceeds 90% by mass, film moldability and thermocompression bonding tend to be difficult to obtain. Determine the optimum filler content to balance the required properties. Mixing and kneading in the case of using a filler can be carried out by appropriately combining dispersers such as a normal stirrer, a raking machine, a three-roller, and a ball mill.

((A) Other components of adhesive film)
The component (A) can further contain various coupling agents. By using the coupling agent, interfacial bonding between different materials is improved. Examples of the coupling agent include silane-based, titanium-based, and aluminum-based ones. Among them, silane-based coupling agents are preferable because of their high effects, and thermosetting groups such as epoxy groups, methacrylates, and the like. A compound having a radiation polymerizable group such as acrylate or a compound containing a hetero atom is more preferable. The amount of the coupling agent used is preferably 0.01 to 20 parts by mass with respect to 100 parts by mass of the component (A1) from the viewpoints of effects, heat resistance, and cost.

  (A) The adhesive film may further contain an ion scavenger. By the ion scavenger, ionic impurities are adsorbed to improve insulation reliability during moisture absorption. Such an ion scavenger is not particularly limited. For example, a triazine thiol compound; a compound known as a copper damage inhibitor for preventing copper from being ionized and dissolved, such as a phenol-based reducing agent; powder And inorganic compounds such as bismuth-based, antimony-based, magnesium-based, aluminum-based, zirconium-based, calcium-based, titanium-based, zuzu-based and mixed systems thereof.

  Specific examples of the ion scavenger are not particularly limited, but trade names: IXE-300 (antimony), IXE-500 (bismuth), IXE-600 as inorganic ion scavengers manufactured by Toa Gosei Co., Ltd. (Antimony and bismuth mixed system), IXE-700 (magnesium and aluminum mixed system), IXE-800 (zirconium based), IXE-1100 (calcium based), and the like. These can be used individually by 1 type or in mixture of 2 or more types. The amount of the ion scavenger used is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the component (A1) from the viewpoints of the effect of addition, heat resistance, cost, and the like.

  In the present embodiment, a sensitizer can be used as necessary. Examples of the sensitizer include camphorquinone, benzyl, diacetyl, benzyldimethyl ketal, benzyl diethyl ketal, benzyl di (2-methoxyethyl) ketal, 4,4′-dimethylbenzyl-dimethyl ketal, anthraquinone, 1-chloroanthraquinone. 2-chloroanthraquinone, 1,2-benzanthraquinone, 1-hydroxyanthraquinone, 1-methylanthraquinone, 2-ethylanthraquinone, 1-bromoanthraquinone, thioxanthone, 2-isopropylthioxanthone, 2-nitrothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chloro-7-trifluoromethylthioxanthone, Oxanthone-10,10-dioxide, thioxanthone-10-oxide, benzoin methyl ether, benzoin ethyl ether, isopropyl ether, benzoin isobutyl ether, benzophenone, bis (4-dimethylaminophenyl) ketone, 4,4′-bisdiethylaminobenzophenone, Examples thereof include a compound containing an azide group. These can be used alone or in combination of two or more.

  (A4) When using an epoxy resin as a thermosetting resin, it is preferable that the (A) adhesive film further contains an epoxy resin curing agent. As an epoxy resin hardening | curing agent, the well-known hardening | curing agent used normally can be used. Examples of the epoxy resin curing agent include amines such as aliphatic amines, alicyclic amines, and aromatic polyamines; polyamides; acid anhydrides such as aliphatic acid anhydrides, alicyclic acid anhydrides, and aromatic acid anhydrides. Polysulfide; Boron trifluoride; Bisphenol compounds having two or more phenolic hydroxyl groups in one molecule such as bisphenol A, bisphenol F, and bisphenol S; Phenol resin; Dicyandiamide; Organic acid dihydrazide; Boron trifluoride amine Complexes; imidazoles; tertiary amines and the like. These epoxy resin curing agents can be used singly or in combination of two or more.

  Preferable examples of the phenolic resin include phenol novolak resin, cresol novolak resin, t-butylphenol novolak resin, dicyclopentagencresol novolak resin, dicyclopentagen phenol novolak resin, xylylene-modified phenol novolak resin, naphthol novolak resin, tris Phenol novolak resin, tetrakisphenol novolak resin, bisphenol A novolak resin, poly-p-vinylphenol resin, phenol aralkyl resin are mentioned. Among them, phenol novolak resin, bisphenol A novolak resin, Phenol resins such as cresol novolac resins are preferred. Examples of the phenolic resin include trade names manufactured by Dainippon Ink and Chemicals, Inc .: Phenolite LF2882, Phenolite LF2822, Phenolite TD-2090, Phenolite TD-2149, Phenolite VH-4150, Phenolite VH4170. And trade name: TrisP-PA manufactured by Honshu Chemical Co., Ltd. These can be used alone or in combination of two or more.

  When an epoxy resin is used as the thermosetting resin, it is preferable to use a curing accelerator together with the epoxy resin curing agent. The curing accelerator is not particularly limited, and examples thereof include imidazoles, dicyandiamide derivatives, dicarboxylic acid dihydrazide, triphenylphosphine, tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, 1,8- Diazabicyclo (5,4,0) undecene-7-tetraphenylborate can be used. These can be used alone or in combination of two or more.

  0.1-5 mass parts is preferable with respect to 100 mass parts of total amounts of an epoxy resin and an epoxy resin hardening | curing agent, and, as for the addition amount at the time of adding a hardening accelerator, 0.2-3 mass parts is more preferable. When the addition amount is less than 0.1 parts by mass, the curability tends to decrease, and when the addition amount exceeds 5 parts by mass, the storage stability tends to decrease.

  (A4) When an epoxy resin is used as the thermosetting resin, (A) the adhesive film contains a photoinitiator that expresses a function of promoting a curing reaction such as polymerization and / or addition reaction of the epoxy resin. Also good. Examples of such a photoinitiator include a photobase generator that generates a base by irradiation, a photoacid generator that generates an acid by irradiation, and the photobase generator is particularly preferable. Examples of the photoacid generator include sulfonium salts and iodonium salts.

  Examples of the radiation include ionizing radiation and non-ionizing radiation. Specifically, excimer laser light such as ArF and KrF; electron beam extreme ultraviolet light; vacuum ultraviolet light; X-ray; ion beam; Examples include ultraviolet light such as g-line.

  By using the photobase generator, the generated base acts efficiently as a curing catalyst for the epoxy resin used as the component (A4). As a result, the crosslink density of the adhesive film is further increased, and the splitting property is improved.

  The photobase generator can be used without particular limitation as long as it is a compound that generates a base upon irradiation with radiation. Examples of the base generated upon irradiation with radiation include imidazole derivatives such as imidazole, 2,4-dimethylimidazole and 1-methylimidazole; piperazine derivatives such as piperazine and 2,5-dimethylpiperazine; piperidine, 1,2 -Piperidine derivatives such as dimethylpiperidine; proline derivatives; trialkylamine derivatives such as trimethylamine, triethylamine and triethanolamine; an amino group or an alkylamino group substituted at the 4-position of 4-methylaminopyridine, 4-dimethylaminopyridine, etc. Pyridine derivatives; pyrrolidine derivatives such as pyrrolidine and n-methylpyrrolidine; dihydropyridine derivatives; alicyclic amine derivatives such as triethylenediamine and 1,8-diazabiscyclo (5,4,0) undecene-1 (DBU) Benzyl methylamine, benzyl dimethylamine, and the like benzylamine derivatives such as benzyl diethylamine.

  Examples of photobase generators that generate a base as described above upon irradiation with radiation include, for example, Journal of Photopolymer Science and Technology 1999, 12, 313-314, Chemistry of Materials 1999, 11-17, 170-17. The quaternary ammonium salt derivatives described on page etc. can be used. Since these produce highly basic trialkylamines by irradiation, they are optimal for curing epoxy resins.

  Further, carbamic acid derivatives described in Journal of American Chemical Society 1996, 118, 12925, Polymer Journal 1996, 28, 795, and the like can also be used.

  Further, an oxime derivative that generates a primary amino group upon irradiation, and 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one that is commercially available as a photo radical generator ( Ciba Japan, trade name: Irgacure 907), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Ciba Japan, trade name: Irgacure 369), 2- ( Dimethylamino) -2-((4-methylphenyl) methyl) -1- (4- (4-morpholinyl) phenyl) -1-butanone (manufactured by Ciba Japan, trade name: Irgacure 379), 3,6-bis -(2methyl-2morpholino-propionyl) -9-N-octylcarbazole (trade name: Optomer N-1414, manufactured by ADEKA) , Hexaarylbisimidazole derivatives (halogen, alkoxy group, nitro group, or a substituted group such as a cyano group substituted by a phenyl group), can be used benzisoxazole pyrazolone derivatives.

  As the photobase generator, a compound in which a group capable of generating a base is introduced into the main chain and / or side chain of the polymer may be used. In this case, the weight average molecular weight of the epoxy resin is preferably from 1,000 to 100,000, more preferably from 5,000 to 30,000, from the viewpoints of adhesiveness, fluidity, and heat resistance as an adhesive.

  (A) The adhesive film may further contain a thermal radical generator as required. As the thermal radical generator, an organic peroxide is preferable. The one minute half-life temperature of the organic peroxide is preferably 120 ° C. or higher, and more preferably 150 ° C. or higher. The organic peroxide can be selected in consideration of the preparation conditions of the photosensitive adhesive composition, the film forming temperature, the curing (bonding) conditions, other process conditions, storage stability, and the like.

  Although it does not specifically limit as a peroxide which can be used, For example, 2,5-dimethyl-2,5-di (t-butylperoxyhexane), dicumyl peroxide, t-butylperoxy-2 -Ethyl hexanate, t-hexyl peroxy-2-ethyl hexanate, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-hexyl peroxy) ) -3,3,5-trimethylcyclohexane, bis (4-t-butylcyclohexyl) peroxydicarbonate, etc., and one of these can be used alone or two or more can be used in combination. .

  0.01-20 mass parts is preferable with respect to 100 mass parts of (A1) component, as for content of the said thermal radical generating agent, 0.1-10 mass parts is more preferable, and 0.5-5 mass parts is further. preferable. When this content is less than 0.01 part by mass, curability is lowered and the effect of addition tends to be small. Moreover, when the said content exceeds 20 mass parts, there exists a tendency for the amount of outgas to increase and for storage stability to fall.

  The thermal radical generator is preferably a compound having a 1 minute half-life temperature of 120 ° C. or higher. For example, perhexa 25B (manufactured by NOF Corporation), 2,5-dimethyl-2,5-di (t-butylperoxy) Hexane) (1 minute half-life temperature: 180 ° C.), Parkmill D (manufactured by NOF Corporation), dicumyl peroxide (1 minute half-life temperature: 175 ° C.) and the like.

  (A) The adhesive film may further contain a polymerization inhibitor such as quinones, polyhydric phenols, phenols, phosphites, and sulfur, or an antioxidant as long as the curability is not impaired. . This provides storage stability, process adaptability, or antioxidant properties.

<(B) Adhesive film>
(B) The adhesive film contains a photocurable component. Examples of the photocurable component include (B1) acrylic copolymer polymer and (B2) photoradical generator.

  (B) The adhesive film has adhesiveness. “Adhesiveness” means that when an adhesive layer composed of a mixture of the component (B1) and the component (B2) is formed as a (B) adhesive film on a substrate film, the (B) adhesive film is at room temperature. (A) It means that it can adhere to an adhesive film. The tack strength at 30 ° C. of the pressure-sensitive adhesive layer is preferably 1 g or more.

Here, the tack strength is a tack strength with respect to SUS304 having a diameter of 5.1 mm. The tack strength was determined by using a tacking tester (trade name “TAC-II” manufactured by Reska Co., Ltd.), temperature: 30 ° C., pushing speed: 2 mm / sec, lifting speed: 10 mm / sec, stop load: 100 gf / cm ² , Stop time: measured under the condition of 1 second.

(B1: Acrylic copolymer)
The component (B1) is a tacky acrylic copolymer. Here, the “acrylic copolymer” means a copolymer obtained by polymerizing a monomer having a (meth) acryloyl group as an essential component.

  The component (B1) can be produced by a combination of various monomers. For example, the (meth) acrylic acid alkyl ester monomer having an alkyl group having 4 or more carbon atoms, a crosslinkable functional group-containing monomer, and further necessary Depending on the case, it can be obtained by copolymerizing with other copolymerizable monomers by a conventional method.

  Examples of the alkyl group (meth) acrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group include butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ( Examples include isooctyl (meth) acrylate and decyl (meth) acrylate. Moreover, as said (meth) acrylic-acid alkylester, the alkylester which has alicyclic groups or aromatic groups, such as (meth) acrylic-acid cycloalkyl ester and (meth) acrylic-acid benzyl ester, may be sufficient. These may be used alone or in combination of two or more.

  The crosslinkable functional group-containing monomer is a monomer having a functional group such as hydroxyl group, carboxyl group, amino group, substituted amino group, and epoxy group in the molecule, preferably a hydroxyl group-containing unsaturated compound, carboxyl group-containing unsaturated compound. A compound. Specific examples of such functional group-containing monomers include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-methacrylic acid 2- (Meth) acrylic acid hydroxyalkyl esters such as hydroxybutyl, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; acetoacetoxymethyl (meth) acrylate; monomethylaminoethyl (meth) acrylate (Meth) acrylic acid monoethylaminoethyl, (meth) acrylic acid monomethylaminopropyl, (meth) acrylic acid monoethylaminopropyl (meth) acrylic acid monoalkylaminoalkyl; acrylic acid, methacrylic acid, crotonic acid, Maleic acid, itaconic acid, cytosine Such as ethylenically unsaturated carboxylic acids such as Con acid. These monomers may be used individually by 1 type, and may be used in combination of 2 or more types.

  Examples of other copolymerizable monomers used as needed include (meth) acrylic acid alkyl esters having an alkyl group with 3 or less carbon atoms. Specific examples of such monomers include methyl (meth) acrylate, ethyl (meth) acrylate and propyl (meth) acrylate, and vinyl esters such as acrylonitrile, acrylamide, vinyl acetate, and vinyl butyrate. Is mentioned. These may be used alone or in combination of two or more.

  By introducing the above copolymerizable other monomer as the component (B1), the glass transition temperature (Tg) of the (B) pressure-sensitive adhesive film can be controlled. For example, the adhesive force and cohesive force of the pressure-sensitive adhesive layer itself can be changed to adjust the chip holding force and pick-up property.

  The glass transition temperature (Tg) of the component (B1) is preferably 0 ° C. or lower, more preferably −5 ° C. or lower, and still more preferably −10 ° C. or lower. When the Tg is 0 ° C. or lower, it becomes easier to form a semiconductor chip with an adhesive layer including an adhesive layer having a shape suitable for mounting a semiconductor chip. The Tg of the component (B1) is preferably −50 ° C. or higher, and more preferably −40 ° C. or higher.

  Here, “Tg” of the component (B1) is a temperature rise rate of 5 ° C. using a viscoelasticity analyzer (trade name: RSA-2, manufactured by Rheometrics Co., Ltd.) for the component (B1) formed into a film. It is a tan δ peak temperature when measured under the conditions of / min, frequency 1 Hz, measurement temperature −150 to 300 ° C.

  The weight average molecular weight of the component (B1) is preferably 2 million or less, and more preferably 1.5 million or less. (B1) The viscosity required in order to apply | coat an adhesive can be obtained as the weight average molecular weight of a component is 2 million or less. The weight average molecular weight of the component (B1) is preferably 100,000 or more, more preferably 200,000 or more, and still more preferably 300,000 or more. When the weight average molecular weight of the component (B1) is 100,000 or more, adverse effects such as odor caused by residual monomers and contamination on the adherend can be eliminated. The weight average molecular weight of the component (B1) is preferably larger than the weight average molecular weight of the component (A1) as described later.

  The content of the component (B1) is preferably 30 to 90 parts by mass, and more preferably 40 to 80 parts by mass with the total mass of the (B) adhesive film being 100 parts by mass.

(B2: Photoradical generator)
As the component (B2), the above-mentioned photo radical generator can be used as a component of the adhesive film (A).

  The content of the component (B2) is preferably 0.1 parts by mass or more with respect to 100 parts by mass of the component (B1), and preferably 50 parts by mass or less in order to obtain sufficient storage stability.

(B3: (meth) acrylate compound)
(B) It is preferable that the adhesive film further contains a (meth) acrylate compound (a compound having a (meth) acryl group) as a photoreactive resin. As such a (meth) acrylate compound, the above-described resin can be used as a constituent component of the adhesive film (A).

  Among the (meth) acrylate compounds, monofunctional (meth) acrylate compounds are preferable. As such a monofunctional (meth) acrylate compound, the above-described resin can be used as a constituent component of the adhesive film (A). Moreover, as a monofunctional (meth) acrylate compound, you may use the monofunctional (meth) acrylate shown by following General formula (15).

  (B) When the pressure-sensitive adhesive film contains the monofunctional (meth) acrylate represented by the general formula (15), (B) the pressure-sensitive adhesive film is discolored by irradiating light to the pressure-sensitive adhesive film (B). It becomes easy to distinguish between before and after exposure. Furthermore, since it is not necessary to add an additive whose color changes with light, which will be described later, it is easy to control the characteristics of the (B) adhesive film.

  The content of the component (B3) is preferably 0.01 to 50 parts by mass, more preferably 0.1 to 30 parts by mass, and still more preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the component (B1). . When this content is less than 0.01 parts by mass, the function manifestation for improving the peel strength tends to be reduced. When the content exceeds 50 parts by mass, the peel strength before exposure increases. Therefore, the pick-up property tends to decrease.

(B4: Fila)
(B) The adhesive film may further contain (B4) filler. (B4) As a component, the above-mentioned filler can be used as a structural component of (A) adhesive film. Among them, a filler whose surface is treated with a silane coupling agent is preferred, and a silica filler treated with (meth) acrylic silane is more preferred. By using such a filler, the peel strength after exposure can be further improved. As for content of (B4) component, 5 mass parts or more are preferable with respect to 100 mass parts of (B1) component, and 50 mass parts or less are preferable.

((B) Other components of the adhesive film)
(B) The pressure-sensitive adhesive film may contain various additive components conventionally used in acrylic pressure-sensitive adhesive compositions as desired, as long as the object of the present invention is not impaired. For example, a sensitizer can be used as necessary. As this sensitizer, the above-described sensitizer can be used as a constituent of (A) the adhesive film.

  In the (B) pressure-sensitive adhesive film, since the component (B1) has crosslinkability, it is preferable to use the component (B1) and a crosslinking agent in combination. Thereby, cohesive force can be added and adhesive force can be controlled. 0.1-50 mass parts is preferable with respect to 100 mass parts of (B1) component, and, as for the usage-amount of a crosslinking agent, 1-30 mass parts is more preferable.

  (B) It is preferable that the color of the adhesive film changes after exposure. In this case, there is no restriction | limiting in particular in the material mix | blended with (B) adhesive film, The (B) adhesive film can contain the compound from which a color changes after irradiating light. As such a compound, azobenzene; a compound derived from spiropyran or diarylethene; a compound represented by the following general formula (16) derived from 1,4-dihydroxynaphthalene is preferable, and since it has high heat resistance, the general formula The compound represented by (16) is more preferred.

［Ｑ^１４及びＱ^１５は各々独立に、Ｈ、ＣＨ_３、アクリル基又はメタクリル基を示す。］

^{[Q 14} and ^{Q 15} each independently represent H, CH _3, an acryl group or a methacryl group. ]

  When the adhesive film 110 contains the component (A1), the component (A2) and the component (A3) and the adhesive film 120 exposes the laminated sheet 100 containing the component (B1) and the component (B2), The peel strength of the exposed portion (peel strength of the adhesive film 110 and the adhesive film 120) tends to be higher than the peel strength before exposure at the laminate interface. Thereby, when the force of the direction which peels the adhesive film 110 from the adhesive film 120 is applied with respect to an exposure part, it becomes easy to suppress that the adhesive film 110 and the adhesive film 120 peel from each other.

  The inventor presumes the reason for this as follows. That is, the adhesive film 110 contains the component (A1), the component (A2), and the component (A3) and the adhesive film 120 contains the component (B1) and the component (B2). A part flows into the area of the adhesive film 120 in the vicinity of the interface between the adhesive film 110 and the adhesive film 120. Then, when light is irradiated to such a region near the interface, components existing in the region near the interface react to integrate fine portions near the interface. Thereby, it is estimated that the peel strength is improved in the exposed portion.

  On the other hand, even in the unexposed portion of the laminated sheet 100, a part of the components contained in the adhesive film 110 flows into the area of the adhesive film 120 in the vicinity of the interface between the adhesive film 110 and the adhesive film 120. However, in the unexposed part, since light is not irradiated, it is suppressed that the fine part near the interface is integrated. In this case, when a force in a direction in which the adhesive film 110 peels from the adhesive film 120 is applied to the unexposed portion, the adhesive film 110 peels from the adhesive film 120, but a part of the components contained in the adhesive film 110 is sticky. Since the adhesive film 110 flows into the region of the film 120, bulk destruction of the adhesive film 110 occurs, and a part of the adhesive film 110 remains attached to the adhesive film 120, and the remaining part of the adhesive film 110 is removed from the adhesive film 120. It will peel off.

  Here, in the case where a part of the components contained in the adhesive film 110 does not flow into the area of the adhesive film 120, the adhesive film 110 is bonded to the unexposed portion when a force in the direction in which the adhesive film 110 peels from the adhesive film 120 is applied. There is a tendency for interface peeling at the interface between the film 110 and the adhesive film 120. In this case, the surface exposed by interfacial peeling in the adhesive film 110 peeled from the pressure-sensitive adhesive film 120 tends to have a reduced adhesive force due to the transfer of the components contained in the pressure-sensitive adhesive film 120. On the other hand, in the laminated sheet 100, the surface exposed by bulk fracture in the adhesive film 110 peeled from the pressure-sensitive adhesive film 120 has sufficient adhesive force because the components contained in the pressure-sensitive adhesive film 120 are not transferred.

  Furthermore, when the weight average molecular weight of the component (B1) is larger than the weight average molecular weight of the component (A1), the fluidity of the components contained in the adhesive film 110 increases, so that a part of the components contained in the adhesive film 110 is adhesive film. It becomes easy to flow into the area | region of the adhesive film 120 in the interface vicinity of 110 and the adhesive film 120. FIG. Thereby, it becomes easy to give sufficient adhesive force to the surface exposed by the bulk fracture in the adhesive film 110 peeled from the adhesive film 120.

  The reaction that occurs in a fine portion near the interface can be analyzed using TOF-SIMS on the peeled surface near the interface between the adhesive film 110 and the adhesive film 120.

  In such a laminated sheet 100, when the unexposed portions of the adhesive film 110 and the pressure-sensitive adhesive film 120 are peeled off before irradiation with light (for example, ultraviolet rays), the laminated sheet 100 is fine in the region of the adhesive film 110 in the vicinity of the interface between the adhesive film 110 and the pressure-sensitive adhesive film 120. It is preferable that some destruction occurs, and when the exposed portions of the adhesive film 110 and the adhesive film 120 are peeled off after irradiation with light (for example, ultraviolet rays), the destruction occurs in the area of the adhesive film 120 in the vicinity of the interface between the adhesive film 110 and the adhesive film 120. Is preferably happening.

(Manufacturing method of laminated sheet for semiconductor)
The laminated sheet 100 can be obtained by, for example, laminating the adhesive film 120 on the base film 130 (Step 1) and then laminating the adhesive film 110 on the adhesive film 120 (Step 2).

  The adhesive film 110 can be obtained by the following procedure. First, the (A1) component, the (A2) component, and the (A3) component are mixed and kneaded in an organic solvent to prepare a varnish. The varnish may contain an optional component (A4), component (A5) and other components as necessary. Next, after applying the varnish to the surface of the base film by a conventional method to form a varnish layer, the varnish layer is dried by heating. And the adhesive film 110 can be obtained by removing a base film. The adhesive film 110 can also be obtained by applying the varnish to the surface of the pressure-sensitive adhesive film 120 by a conventional method to form a varnish layer and then drying the varnish layer by heating.

  The adhesive film 120 can be obtained by the following procedure. First, the (B1) component and the (B2) component are mixed and kneaded in an organic solvent to prepare a varnish. The varnish may contain an optional component (B3), component (B4) and other components as necessary. Next, the varnish is coated on the surface of the base film 130 by a conventional method to form a varnish layer, and then the varnish layer is heated and dried, whereby the pressure-sensitive adhesive film 120 laminated on the base film 130. Can be obtained.

  In the production of the adhesive film 110 and the pressure-sensitive adhesive film 120, the above mixing and kneading can be performed by appropriately combining dispersers such as a normal stirrer, a raking machine, a triple roll, and a ball mill. Examples of the varnish coating method include spin coating, printing, and spray coating. It is preferable that the conditions of said heat drying are conditions which the used solvent volatilizes sufficiently, and it heats normally at 60-200 degreeC for 0.1 to 90 minutes.

  The organic solvent used for the preparation of the varnish is preferably capable of uniformly dissolving, kneading or dispersing the material, and conventionally known ones can be used. Examples of such an organic solvent include ketone solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, acetone, methyl ethyl ketone, and cyclohexanone, toluene, xylene, and the like.

  As the amount of the organic solvent used, for example, the residual volatile content after the production of the adhesive film 110 is preferably 0.01 to 3% by mass based on the total mass of the adhesive film 110, and is 0 from the viewpoint of heat resistance reliability. 0.01-2.0 mass% is more preferable, and 0.01-1.5 mass% is still more preferable.

  Examples of the base film 130 include polyethylene film, polypropylene film, polybutene film, polybutadiene film, polymethylpentene film, polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, Plastic films such as ethylene vinyl acetate film, ionomer resin film, ethylene / (meth) acrylic acid copolymer film, ethylene / (meth) acrylic acid ester copolymer film, polystyrene film, polycarbonate film, and fluororesin film are used.

  The base film 130 may be a multilayer film of these plastic films or a crosslinked film. Further, the base film 130 may be colored or colorless. 30-300 micrometers is preferable and, as for the thickness of the base film 130, 50-200 micrometers is more preferable.

  In order to improve the adhesion at the interface between the base film 130 and the adhesive film 120 so that the base film 130 and the adhesive film 120 do not peel off during the operation, sandblasting on one side (main surface 130a) of the base film 130 A roughening treatment by a solvent treatment, or a corona discharge treatment, a plasma treatment, an ozone / ultraviolet irradiation treatment, a flame treatment, a chromic acid treatment, an oxidation treatment such as hot air treatment, a primer treatment or the like can be performed.

  The base film 140 to be described later on which the adhesive film 110 is laminated is not particularly limited as long as it can withstand the above drying conditions. As the base film, 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 film, the multilayer film which combined 2 or more types of films may be sufficient, and the film by which the surface was processed by mold release agents, such as a silicone type and a silica type, may be sufficient.

<Method for manufacturing semiconductor chip with adhesive layer>
[First Embodiment]
The manufacturing method of the semiconductor chip with an adhesive layer according to the first embodiment includes an individualization step, an attaching step, an exposure step, and a pickup step in this order. Hereinafter, each step will be described.

(Individualization process)
The singulation process will be described with reference to FIG. In the individualization step, first, the semiconductor wafer 21 is prepared. Examples of the semiconductor wafer 21 include a logic IC, a memory IC, and an image sensor. Subsequently, a peelable dicing tape 23 is attached to one main surface 21 a of the semiconductor wafer 21 to obtain a laminate 25.

  Next, the laminated body 25 is fixed to the stage of the dicing apparatus with the other main surface 21b of the semiconductor wafer 21 facing upward. Subsequently, the semiconductor wafer 21 is diced so that the semiconductor wafer 21 is cut (full cut) from the main surface 21 a to the main surface 21 b of the semiconductor wafer 21 to obtain a plurality of semiconductor chips 27. Specifically, as shown in FIGS. 2A and 2B, the laminated body 25 is diced from the main surface 21b side of the semiconductor wafer 21 to form grooves 29 in a lattice shape in the laminated body 25, and the semiconductor The wafer 21 is cut into a plurality of semiconductor chips 27. In this case, the bottom surface of the groove 29 only needs to reach at least the interface between the semiconductor wafer 21 and the dicing tape 23. For example, in FIG. 2, the bottom surface of the groove 29 forms the bottom surface of the recess formed in the dicing tape 23, and a part of the dicing tape 23 in the thickness direction remains without being cut.

  The laminated body 25 may be diced by a dicing blade 31 as shown in FIGS. 2A and 2B, or may be diced by a laser. For dicing, for example, a dicing machine manufactured by Disco Corporation can be used. The thickness of the semiconductor chip 27 is, for example, 5 to 700 μm.

  As shown in FIG. 2 (c), a plurality of semiconductor chips 27 that are fixed to a peelable adhesive material and have a gap as a chip aggregate are arranged by a separation process. A laminated body 35 including the dicing tape 23 attached to one main surface 27a of the plurality of semiconductor chips 27 is obtained. In the stacked body 35, the other main surface 27b of the semiconductor chip 27 is exposed.

(Attaching process)
The attaching process will be described with reference to FIG. In the attaching step, the main surface 27 b of the semiconductor chip 27 is attached to the adhesive film 110 of the laminated sheet 100. Examples of the attaching method include a method using a roll laminator or a vacuum laminator. For example, first, the laminated body 35 is fixed to the laminator 41 with the main surface 27b of the semiconductor chip 27 facing upward, and the wafer ring 43 is installed so as to surround the periphery. In FIG. 3A, illustration of the wafer ring 43 is omitted. Subsequently, by laminating the laminated sheet 100 on the semiconductor chip 27 so that the main surface 27b of the semiconductor chip 27 and the adhesive film 110 of the laminated sheet 100 and the wafer ring 43 and the adhesive film 120 of the laminated sheet 100 are in contact with each other. A laminate 45 is obtained.

  By the way, as in Patent Document 2, when an adhesive layer made of an uncured paste is adhered to a semiconductor chip, the paste-like adhesive may adhere to the side surface or surface of the semiconductor chip, and the adhesive layer is attached. Forming a semiconductor chip may be hindered. On the other hand, in the affixing step, since the semiconductor chip 27 is affixed to the film-like adhesive film 110, adhesion of the adhesive of the adhesive film 110 to the side surface or surface of the semiconductor chip 27 is suppressed. A semiconductor chip with an agent layer can be easily formed.

(Exposure process)
The exposure process will be described with reference to FIGS. In the exposure step, first, the laminated body 45 is arranged with the dicing tape 23 facing upward, and then the dicing tape 23 is peeled from the semiconductor chip 27 to obtain the laminated body 55 as shown in FIG. Gaps 51 are formed between the semiconductor chips 27 in the stacked body 55.

  Next, the semiconductor chip 27 is affixed to one side of the adhesive film 110, and the adhesive film 120 is affixed to the other side of the adhesive film 110 on the opposite side of the semiconductor chip 27 across the adhesive film 110. In this state, the light L from the light source 61 is applied to the adhesive film 110 and the adhesive film 120 from the main surface 27 a side of the semiconductor chip 27 through the semiconductor chip 27. In this case, since the semiconductor chip 27 is interposed between the light source 61 and the adhesive film 110 and the adhesive film 120, the semiconductor chip 27 serves as a mask and is covered by the semiconductor chip 27 in the adhesive film 110 and the adhesive film 120. It is suppressed that the light L is irradiated to the area. On the other hand, light L is irradiated to a region corresponding to the gap 51 of the chip assembly in the adhesive film 110 and the adhesive film 120 (a region exposed from between the semiconductor chips 27) and a region around the semiconductor chip 27.

  As a result, as shown in FIG. 5, a lattice-like photoreactive portion 115a is formed in the region of the adhesive film 110 irradiated with the light L, and a region of the adhesive film 120 irradiated with the light L is lattice-shaped. A photoreactive portion 125a is formed. Thereby, the laminated body 65 provided with the photoreaction part 115a and the photoreaction part 125a laminated | stacked in the state which mutually contacted is obtained. In the adhesive film 110, unexposed portions 115b are arranged between the linear portions constituting the photoreactive portions 115a. An unexposed portion 125b is disposed between each linear portion constituting the photoreactive portion 125a in the adhesive film 120.

  Examples of the light L include actinic rays such as ultraviolet rays and radiation. The exposure amount is preferably 10 to 5000 mJ. For the exposure, for example, an exposure machine manufactured by Oak Manufacturing Co., Ltd. can be used. In addition to the semiconductor chip 27, a mask having an opening corresponding to the gap 51 of the chip assembly may be provided.

(Pickup process)
The pickup process will be described with reference to FIG. In the pickup process, as shown in FIG. 6, the semiconductor chip 75 with an adhesive layer including the semiconductor chip 27 and the unexposed portion 115 b having the same size (same area) as the semiconductor chip 27 is picked up. For example, the semiconductor chip 75 with the adhesive layer is picked up by the collet 73 while the lower portion of the base film 130 corresponding to the position of the semiconductor chip 75 with the adhesive layer to be picked up is pushed up by the pin 71. Thereby, the unexposed portion 115b of the semiconductor chip 75 with the adhesive layer is peeled off from the unexposed portion 125b without being accompanied by the photoreactive portion 115a of the adhesive film 110 located in the gap 51 of the chip assembly, A semiconductor chip 75 with an adhesive layer in which the semiconductor chip 27 and the unexposed portion 115b are laminated can be obtained.

  Further, in the above manufacturing method, there is a tendency for bulk destruction to occur inside the unexposed portion 115b during pick-up, and a part of the unexposed portion 115b is located at the position where the picked-up semiconductor chip 75 with the adhesive layer is disposed. Tend to remain. In this case, the surface exposed by bulk fracture in the unexposed portion 115b of the semiconductor chip 75 with the adhesive layer has a sufficient adhesive force because the component contained in the unexposed portion 125b is not transferred.

  The semiconductor chip 75 with an adhesive layer can be picked up using a die bond apparatus (pickup apparatus) such as a flexible die bonder manufactured by Renesas East Japan Semiconductor. Note that the interval between the semiconductor chips 27 may be widened by expanding after the exposure step and before the pickup step.

  In the above method using the adhesive sheet 100, in the exposure step, the adhesive film 110 and the pressure-sensitive adhesive film 120 are irradiated with light through the semiconductor chip 27. An exposed portion 115b is formed, and a photoreactive portion 125a and an unexposed portion 125b are formed on the adhesive film 120. In this case, the reaction of the photocurable component (such as crosslinking of the resin component) proceeds in the photoreactive portion 115a and the photoreactive portion 125a, so that the photoreactive portion 115a and the photoreactive portion 125a are difficult to separate from each other, The photoreactive portion 115a becomes brittle compared to the unexposed portion 115b, and the photoreactive portion 125a becomes brittle compared to the unexposed portion 125b. Accordingly, when a force in a direction in which the adhesive film 110 is peeled from the adhesive film 120 is applied to the unexposed portion 115b and the unexposed portion 125b, the unreacted portion 115b and the photoreactive portion 115a in contact with the unexposed portion 115b. Are easily peeled from each other, and the unexposed portion 125b and the photoreactive portion 125a in contact with the unexposed portion 125b are easily peeled from each other.

  In such a manufacturing method, when picking up the semiconductor chip 75 with the adhesive layer including the unexposed portion 115b in the pickup process, the unexposed portion is maintained while the unexposed portion 115b is attached to the semiconductor chip 27. It is easy to peel 115b from the unexposed portion 125b, and it is easy to leave the photoreactive portion 115a and the photoreactive portion 125a in a desired shape (for example, a lattice shape similar to the gap 51). Therefore, in the above manufacturing method, the semiconductor chip 75 with the adhesive layer including the adhesive layer (unexposed portion 115b) having a shape suitable for mounting the semiconductor chip 27 can be easily formed.

[Second Embodiment]
In the method for manufacturing a semiconductor chip with an adhesive layer according to the second embodiment, the singulation process is different from that of the first embodiment, and other processes (the pasting process, the exposure process, the pickup process, etc.) are performed in the first embodiment. It is the same. The singulation process will be described with reference to FIGS. The singulation process includes a dicing process and a grinding process in this order.

  In the dicing process, first, the laminated body 25 is obtained in the same manner as in the first embodiment, and then the laminated body 25 is fixed to the stage of the dicing apparatus with the main surface 21b of the semiconductor wafer 21 facing upward.

  Subsequently, the semiconductor wafer 21 is diced (half cut) from the main surface 21b side of the semiconductor wafer 21 so that at least a part of the semiconductor wafer 21 in the thickness direction remains without being cut. Specifically, as shown in FIGS. 7A and 7B, the laminated body 25 is diced from the main surface 21 b side of the semiconductor wafer 21 to form grooves 29 a in a lattice shape on the semiconductor wafer 21. In this case, the bottom surface of the groove 29 a is located between the main surface 21 a and the main surface 21 b of the semiconductor wafer 21 without reaching the interface between the semiconductor wafer 21 and the dicing tape 23.

  The laminated body 25 may be diced by a dicing blade 31 as shown in FIGS. 7A and 7B, or may be diced by a laser. For dicing, for example, a dicing machine manufactured by Disco Corporation can be used.

  A laminated body including a semiconductor wafer 21 having a plurality of raised portions 21c formed at intervals from each other through grooves 29a by the dicing, and a dicing tape 23 attached to the main surface 21a of the semiconductor wafer 21. can get. Subsequently, the dicing tape 23 is peeled off from the semiconductor wafer 21 and the back grind tape 81 is bonded to the main surface 21b of the semiconductor wafer 21 to obtain a laminate 83 as shown in FIG. In the stacked body 83, the main surface 21b of the semiconductor wafer 21 is in contact with the back grind tape 81, and the main surface 21a of the semiconductor wafer 21 is exposed.

  In the grinding process, first, as shown in FIGS. 8A and 8B, the stacked body 83 is fixed with the main surface 21a of the semiconductor wafer 21 facing upward. Next, the semiconductor wafer 21 is back grinded (ground) by the grinder 85 until the grinding surface reaches the position of the bottom surface of the groove 29a from the main surface 21a side, and a plurality of semiconductor chips 27 are formed as shown in FIG. obtain. For backgrinding, for example, a backgrinding device manufactured by Disco Corporation can be used. The thickness of the semiconductor chip 27 is, for example, 5 to 700 μm.

  Through the above-described singulation process, a laminated body 89 including a plurality of semiconductor chips 27 arranged at intervals from each other and a back grind tape 81 attached to the main surface 27a of the plurality of semiconductor chips 27 is obtained. It is done. In the subsequent attaching step, the laminate 89 is used in place of the laminate 35 in the first embodiment, and the laminate sheet 100 is attached to the main surface 27b of the semiconductor chip 27 in the laminate 89.

[Third Embodiment]
In the method of manufacturing the semiconductor chip with an adhesive layer according to the third embodiment, the attaching process is different from those of the first and second embodiments, and the other processes (the individualizing process, the exposure process, the pick-up process, etc.) are the first. This is the same as the embodiment and the second embodiment. The pasting process will be described with reference to FIGS. The pasting step has a first pasting step and a second pasting step. In the attaching step, after the adhesive film 110 is attached to the semiconductor chip 27 in the first attaching step, the adhesive film 120 is attached to the adhesive film 110 in the second attaching step. Hereinafter, each step will be described.

  In a 1st affixing process, the laminated sheet 200 provided with the base film 140 and the adhesive film 110 affixed on the base film 140 first is prepared. Moreover, the laminated body 35 in 1st Embodiment or the laminated body 89 in 2nd Embodiment is prepared. Below, the process using the laminated body 35 is demonstrated as an example.

  Next, the laminated body 35 is fixed to the laminator 41 using the wafer ring 43 with the main surface 27b of the semiconductor chip 27 of the laminated body 35 facing upward. Subsequently, as shown in FIGS. 9A and 9B, the laminated sheet 200 is laminated on the semiconductor chip 27 so that the main surface 27 b of the semiconductor chip 27 and the adhesive film 110 of the laminated sheet 200 are in contact with each other. A body 91 is obtained. And as shown in FIG.9 (c), the laminated body 93 is obtained by peeling the base film 140 from the adhesive film 110. FIG.

  In the second attaching step, first, a laminated sheet 300 including a base film 130 and an adhesive film 120 attached to the base film 130 is prepared. Next, the laminate 93 is fixed to the laminator 41 with the adhesive film 110 of the laminate 93 facing upward. Subsequently, as illustrated in FIGS. 10A and 10B, the laminated sheet 300 is obtained by laminating the laminated sheet 300 on the adhesive film 110 so that the adhesive film 110 and the adhesive film 120 of the laminated sheet 300 are in contact with each other. . In the laminated body 95, the adhesive film 120 is attached to the adhesive film 110 on the opposite side of the semiconductor chip 27 with the adhesive film 110 interposed therebetween.

  Then, as shown in FIG. 10C, by peeling the dicing tape 23 from the semiconductor chip 27, a laminated body 55 having the same structure as that of the laminated body shown in FIG. 4 is obtained. The subsequent exposure process and pick-up process are the same as those in the first and second embodiments.

  In addition, the manufacturing method of the semiconductor chip with an adhesive layer is not limited to the above. For example, in the exposure process, the adhesive film 110 and the adhesive film 120 may be irradiated with the light L in a state where the dicing tape 23 or the back grind tape 81 is attached to the main surface of the semiconductor chip 27 on the light source 61 side. In this case, a tape that transmits light L may be used as the dicing tape 23 or the back grind tape 81.

[Method for Manufacturing Semiconductor Device]
The manufacturing method of the semiconductor device according to this embodiment includes a step of obtaining the semiconductor chip 75 with an adhesive layer by the method of manufacturing a semiconductor chip with an adhesive layer, and a mounting step. In the mounting process, as shown in FIG. 11, the semiconductor chip 27 of the semiconductor chip 75 with the adhesive layer is mounted on the mounting substrate (semiconductor mounting) via the unexposed portion 115b (adhesive layer) of the semiconductor chip 75 with the adhesive layer. The semiconductor device 99 is obtained by bonding to the supporting member 97. The mounting process is performed, for example, under the condition of heating at 50 to 150 ° C. for 0.1 to 10 seconds.

  Examples of the mounting substrate 97 include other semiconductor chips; lead frames such as 42 alloy lead frames and copper lead frames; resin films formed from epoxy resins, polyimide resins and maleimide resins; glass nonwoven fabrics or glass weaves Examples of the substrate include a substrate obtained by impregnating a cloth with a thermosetting resin such as an epoxy resin, a polyimide resin, and a maleimide resin and curing the resin; a glass substrate; and a ceramic substrate such as alumina.

  DESCRIPTION OF SYMBOLS 21 ... Semiconductor wafer, 21a, 21b ... Main surface of semiconductor wafer, 27 ... Semiconductor chip, 100 ... Laminated sheet for semiconductor, 110 ... Adhesive film, 115b ... Unexposed part (adhesive layer), 120 ... Adhesive film.

Claims (4)

A pasting step of attaching a plurality of semiconductor chips arranged at intervals to an adhesive film containing a photocurable component;
With the adhesive film containing a photocurable component disposed on the opposite side of the semiconductor chip across the adhesive film, the adhesive film and the adhesive film are irradiated with light using the semiconductor chip as a mask, and the adhesive film An exposure step of causing the reaction of the photocurable component to proceed in the exposed portion of the adhesive film and the exposed portion of the adhesive film to make it difficult to separate the exposed portion of the adhesive film and the exposed portion of the adhesive film ;
After the exposure step, the step of picking up the semiconductor chip to which the unexposed portion of the adhesive film is attached,
The manufacturing method of the semiconductor chip with an adhesive film which affixes the said semiconductor chip on the said adhesive film of the lamination sheet provided with the said adhesion film and the said adhesive film in the said sticking process.   The method further includes the step of obtaining the plurality of semiconductor chips by dicing the semiconductor wafer so that the semiconductor wafer is cut from one main surface to the other main surface of the semiconductor wafer before the attaching step. Item 2. The manufacturing method according to Item 1.   Before the attaching step, the semiconductor wafer is diced from one main surface side of the semiconductor wafer so that at least a part of the thickness direction of the semiconductor wafer remains without being cut, and then the semiconductor wafer is removed from the semiconductor wafer. The manufacturing method according to claim 1, further comprising a step of obtaining the plurality of semiconductor chips by grinding from the other main surface side of the wafer. The semiconductor chip of the adhesive film-attached semiconductor chips obtained by the method according to any one of claims 1 to 3, the step of attaching the mounting substrate via the adhesive film of the semiconductor chip with the adhesive film A method for manufacturing a semiconductor device.

Images