JP5799532B2 - Semiconductor sealing resin composition, semiconductor device, and method for manufacturing semiconductor device - Google Patents

Description

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

  In recent years, instead of a package such as TSOP (Thin Small Outline Package), a method of manufacturing a package at a wafer level has been studied. As one of the methods, for example, there is a method of sealing on a silicon wafer. In this method, there are restrictions on the chip size and the like.

  Currently, a wafer level package using a plate-like pseudo wafer is being studied. Such a packaging technique is described in Patent Document 1, for example. The packaging method using the pseudo wafer described in Patent Document 1 includes the following steps. First, a releasable mount film is attached to a carrier, and a plurality of chips are mounted thereon. A plurality of chips are sealed with an epoxy resin composition. Thereafter, the pseudo wafer separated from the carrier is manufactured by peeling the film. This pseudo wafer is composed of a plurality of chips and a cured product of the epoxy resin composition. The connection surfaces of these chips are exposed. The pseudo wafer thus manufactured is divided for each element. And it is described that a package can be performed by disposing a divided body having the element on an interposer substrate.

U.S. Pat. No. 7,326,592

  However, as a result of investigations by the inventors, it has been found that in the prior art, when the pseudo wafer is separated from the carrier, the pseudo wafer is warped. When such warpage occurs, the yield of the semiconductor device may be reduced.

The present invention is as follows.
[1]
Forming a heat-peelable adhesive layer on the substrate;
A step of disposing a plurality of semiconductor elements on the main surface of the thermally peelable adhesive layer;
By forming a sealing material layer that seals a plurality of the semiconductor elements on the main surface of the thermally peelable adhesive layer using a resin composition for semiconductor sealing, the sealing material layer and the semiconductor Obtaining a structure composed of elements;
Separating the structure from the base material by peeling the heat-peelable adhesive layer, and the semiconductor sealing resin composition used in the method for manufacturing a semiconductor device,
An epoxy resin (A) having three or more epoxy groups in one molecule;
A curing agent (B) having three or more phenolic hydroxyl groups in one molecule;
A resin composition for encapsulating a semiconductor, comprising an inorganic filler (C).
[2]
The resin composition for semiconductor encapsulation according to [1], wherein the content of the inorganic filler (C) is 80% by mass or more and 93% by mass or less.
[3]
Using a dielectric analyzer, the time to reach the saturated ion viscosity of the resin composition for semiconductor encapsulation when measured under the conditions of a measurement temperature of 125 ° C. and a measurement frequency of 100 Hz is 100 seconds or more and 900 seconds from the start of measurement. The resin composition for semiconductor encapsulation according to [1] or [2], which is described below.
[4]
The minimum ion viscosity of the resin composition for semiconductor encapsulation is 6 or more and 8 or less when measured under the conditions of a measurement temperature of 125 ° C. and a measurement frequency of 100 Hz using a dielectric analyzer, and from the start of measurement. The resin composition for semiconductor encapsulation according to any one of [1] to [3], wherein an ionic viscosity after an elapsed time of 600 seconds is 9 or more and 11 or less.
[5]
The high viscosity of the resin composition for encapsulating a semiconductor is 20 Pa · s or more and 200 Pa · s or less when measured at a measurement temperature of 125 ° C. and a load of 40 kg using a high viscosity viscosity measuring device. The resin composition for semiconductor encapsulation according to any one of [1] to [4].
[6]
The resin composition for semiconductor encapsulation according to any one of [1] to [5], wherein a Shore D hardness of the encapsulant layer after being cured at 125 ° C. for 10 minutes is 70 or more. .
[7]
The resin composition for semiconductor encapsulation according to any one of [1] to [6], wherein a bending strength of the encapsulant layer at 260 ° C. is 10 MPa or more and 100 MPa or less.
[8]
The semiconductor sealing device according to any one of [1] to [7], wherein a bending elastic modulus of the sealing material layer at 260 ° C. is 5 × 10 ² MPa or more and 3 × 10 ³ MPa or less. Resin composition.
[9]
The resin composition for semiconductor encapsulation according to any one of [1] to [8], wherein the glass transition temperature (Tg) of the sealing material layer is 100 ° C. or higher and 250 ° C. or lower.
[10]
The linear expansion coefficient (α1) in the xy plane direction of the sealing material layer in the region of 25 ° C. or more and the glass transition temperature (Tg) or less is 3 ppm / ° C. or more and 15 ppm / ° C. or less. [9] The resin composition for semiconductor encapsulation according to any one of [9].
[11]
The storage elastic modulus (E ′) of the sealing material layer when measured with a dynamic viscoelasticity measuring device at a three-point bending mode, a frequency of 10 Hz, and a measurement temperature of 260 ° C. is 5 × 10 ² MPa or more, 5 The resin composition for semiconductor encapsulation according to any one of [1] to [10], which is × 10 ³ MPa or less.
[12]
After the step of peeling the heat-peelable adhesive layer, the contact angle of one surface of the sealing material layer from which the semiconductor element is exposed is 70 degrees or less at the time of measurement using formamide. The resin composition for semiconductor encapsulation according to any one of [1] to [11].
[13]
A semiconductor device comprising a semiconductor element sealed with a cured product of the semiconductor sealing resin composition according to any one of [1] to [12].

  According to the present invention, a structure of a semiconductor device excellent in yield and a manufacturing method thereof are provided.

It is sectional drawing which shows typically the semiconductor device in embodiment of this invention. It is process sectional drawing which shows the manufacturing procedure of the semiconductor device in embodiment of invention. It is process sectional drawing which shows the manufacturing procedure of the semiconductor device in embodiment of invention. It is process sectional drawing which shows the manufacturing procedure of the semiconductor device in embodiment of invention. It is process sectional drawing which shows the manufacturing procedure of the semiconductor device in embodiment of invention. Schematic of one Example from the melt-kneading of the semiconductor sealing resin composition to the collection of the granular resin composition to obtain the granular semiconductor sealing resin composition according to the embodiment of the invention It is. It is sectional drawing of one Example of the exciting coil for heating the rotor used for embodiment of invention and the cylindrical outer peripheral part of a rotor. It is sectional drawing of one Example of the double tube | pipe cylindrical body which supplies the resin composition for semiconductor sealing which was melt-kneaded to a rotor.

  Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, the same reference numerals are given to the same components, and the description will be omitted as appropriate.

  FIG. 1 is a cross-sectional view of a semiconductor device 100 in the present embodiment. 2 to 5 are process cross-sectional views illustrating the manufacturing procedure of the semiconductor device according to the present embodiment.

  As shown in FIG. 1, the semiconductor device 100 of the present embodiment includes a semiconductor element 106, a sealing material layer 108, a rewiring insulating resin layer 110, a via 114, a rewiring circuit 116, a solder resist layer 118, a solder ball. 120 and a pad 122 are provided. In FIG. 1, the semiconductor device 100 includes a single semiconductor element 106, but is not limited thereto, and may include a plurality of semiconductor elements 106. A plurality of pads 122 are formed on the lower surface 20 of the semiconductor element 106. The lower surface 20 of the semiconductor element 106 serves as a connection surface with the rewiring circuit 116.

  A rewiring insulating resin layer 110 is formed on the lower surface 20 (connection surface) of the semiconductor element 106. A solder resist layer 118 is formed on the insulating resin layer 110 for rewiring. A rewiring circuit 116 is formed on the solder resist layer 118. The rewiring insulating resin layer 110 is formed with a via 114 that electrically connects the rewiring circuit 116 and the pad 122. A solder ball 120 is formed on the rewiring circuit 116. Accordingly, the semiconductor device 100 is mounted on a mounting substrate such as an interposer via the solder balls 120 for external terminals.

  The semiconductor element 106 is sealed with a sealing material layer 108. In other words, the sealing material layer 108 is formed on the side wall surface and the upper surface of the semiconductor element 106. The lower surface 30 of the sealing material layer 108 and the lower surface 20 of the semiconductor element 106 constitute the same surface. In the semiconductor device 100, the rewiring circuit 116 can be formed on the lower surface 30 of the sealing material layer 108 in addition to the lower surface 20 of the semiconductor element 106. Therefore, since the rewiring circuit 116 can be formed also on the lower surface 30 of the sealing material layer 108 formed outside the region of the lower surface 20 of the semiconductor element 106 in a top view, wiring can be designed freely. Therefore, according to the semiconductor device 100 of the present embodiment, the degree of freedom of wiring is improved.

An outline of a method for manufacturing a semiconductor device in the present embodiment will be described. Moreover, the resin composition for semiconductor sealing used for the manufacturing method of this Embodiment is demonstrated.
The method for manufacturing a semiconductor device in the present embodiment includes the following steps.
(Chip mounting step): A step of forming a heat-peelable adhesive layer (mount film 104) on a substrate (carrier 102), and a plurality of surfaces on the main surface 10 of the heat-peelable adhesive layer (mount film 104). A step of disposing the semiconductor element 106;
(Sealing material layer 108 formation process): The process of forming the sealing material layer 108 which seals the several semiconductor element 106 on the main surface 10 of the mount film 104 using the resin composition for semiconductor sealing. By forming the sealing material layer 108, a structure (rewiring pseudo wafer 200) including the semiconductor element 106 and the sealing material layer 108 is formed.
(Rewiring pseudo wafer 200 forming step): A step of separating the rewiring pseudo wafer 200 from the carrier 102 by peeling the mount film 104. Thereby, the lower surface 30 of the sealing material layer 108 and the lower surface 20 of the semiconductor element 106 are exposed.
In addition, the method for manufacturing a semiconductor device in the present embodiment includes the following steps.
(Rewiring step): Step of forming the insulating resin layer 110 for rewiring on the lower surface of the sealing material layer 108 and the lower surface of the semiconductor element after the step of peeling the heat-peelable adhesive layer (mount film 104). And a step of forming the rewiring circuit 116 on the insulating resin layer 110 for rewiring.

  In the manufacturing method of the semiconductor device of the present embodiment, the following resin composition for semiconductor sealing of the present invention is used as the sealing material for the sealing material layer 108. The resin composition for semiconductor encapsulation of the present invention comprises an epoxy resin (A) having three or more epoxy groups in one molecule and a curing agent (B) having three or more phenolic hydroxyl groups in one molecule. And an inorganic filler (C).

  In the conventional packaging technology using a pseudo wafer, a releasable mount film is pasted on a carrier, and a plurality of chips are mounted thereon. A plurality of chips are sealed with an epoxy resin composition to obtain a structure. Thereafter, a pseudo wafer is formed by separating the carrier together with the film from the structure. The pseudo wafer includes a plurality of chips and a cured product of the epoxy resin composition.

  However, as a result of the study by the present inventors, the composition of the conventional epoxy resin composition is selected in view of the sealing characteristics of the final product without particularly intending the influence on the manufacturing process. It has been found that when the carrier is separated from the body, a difference in residual stress is generated between the upper surface and the lower surface of the pseudo wafer, causing the warp of the pseudo wafer.

  The mechanism for causing such warpage is considered as follows. That is, a layer made of a cured resin composition (referred to as a sealing material layer) and a chip are formed on one surface of the pseudo wafer, and only the sealing material layer is formed on the other surface. The linear expansion coefficient of the chip is small. For this reason, when hardening a resin composition by heat processing, since the one surface side has a smaller linear expansion coefficient with respect to the other surface side, the other surface side heat contracts rather than the one surface side. Further, due to the heat history, heating loss occurred, and the sealing material layer on the other surface side was thermally deformed. However, when a difference in thermal shrinkage or thermal deformation occurs, the pseudo wafer is bonded to the carrier, so that residual stress remains on the pseudo wafer. When the carrier is separated, warpage occurs on one side of the pseudo wafer due to the difference in residual stress. When the rewiring material is applied on one surface of the pseudo wafer in which such warpage has occurred, the coating film characteristics of the rewiring material may be deteriorated. For this reason, in the conventional method for manufacturing a semiconductor device, the yield may be reduced.

  As a result of further investigation, the present inventors have found that as a resin composition for semiconductor encapsulation, an epoxy resin (A) having 3 or more epoxy groups in one molecule and 3 or more phenolic hydroxyl groups in one molecule. The present invention was completed by finding that warping on one side of the rewiring pseudo-wafer 200 (the side where the semiconductor element 106 is exposed) is reduced by adopting the one containing the curing agent (B) having I let you.

  The mechanism that can reduce the warpage of the rewiring pseudo-wafer 200 is not clear, but is presumed as follows. That is, the epoxy resin (A) and the curing agent (B) each have an epoxy group and a phenolic hydroxyl group as three or more functional groups (hereinafter sometimes referred to as polyfunctional groups) in one molecule. Yes. A cross-linked structure having a high density is constructed by the reaction of these polyfunctional groups. For this reason, a linear expansion coefficient falls. Moreover, since the reactivity becomes high, the reaction efficiency at a low temperature is improved. Moreover, since Tg improves by a crosslinked structure or low-temperature reaction characteristics, heat resistance is also improved. For this reason, the resin composition for semiconductor sealing which is excellent in the balance of a high temperature shrinkage characteristic, low temperature curability, and high temperature heat resistance is realizable. The cured product (encapsulant layer 108) of the resin composition for semiconductor encapsulation having an excellent balance of such properties may undergo thermal shrinkage due to thermal history during curing or removal of the heat-peelable adhesive layer, Thermal deformation is suppressed. Therefore, by using the encapsulant layer 108 obtained by curing the resin composition for semiconductor encapsulation, residual stress generated due to thermal shrinkage or thermal deformation in the rewiring pseudo-wafer 200 is obtained. The occurrence of differences can be reduced. Therefore, it is assumed that the warp of the rewiring pseudo wafer 200 can be reduced.

  Hereinafter, each manufacturing process of the semiconductor device 100 of the present invention will be described.

(Chip mounting process)
First, as shown in FIG. 2A, a heat-peelable adhesive layer (mount film 104) is disposed on a plate-like carrier 102. For example, a film-like mount film 104 can be placed on the surface of the carrier 102.
The shape and material of the carrier 102 are not particularly limited. For example, a circular or polygonal metal plate or silicon substrate can be used in a top view.
The mount film 104 preferably contains a main agent and a foaming agent. The main agent is not particularly limited and is, for example, an acrylic pressure-sensitive adhesive, a rubber-based pressure-sensitive adhesive, or a styrene / conjugated diene block copolymer, and preferably an acrylic pressure-sensitive adhesive. Moreover, there is no restriction | limiting in particular as a foaming agent, For example, they are various foaming agents, such as an inorganic type and an organic type. The heat peelability of the mount film 104 is obtained, for example, by making the pressure-sensitive adhesive foamable, and when heated to a temperature at which the pressure-sensitive adhesive foams, the adhesive strength of the pressure-sensitive adhesive is substantially lost. The film 104 can be easily peeled from the adherend.

  Subsequently, as illustrated in FIG. 2B, the plurality of semiconductor elements 106 are arranged apart from each other on the main surface 10 of the mount film 104 in a plan view. For example, the semiconductor elements 106 may have the same or different number of arrangement in the vertical and horizontal directions in plan view, and are point-symmetric or lattice-like from various viewpoints such as improvement in density and securing a terminal area per unit semiconductor chip. Etc. may be arranged. Further, the chip size of the semiconductor element 106 and the distance between the adjacent semiconductor elements 106 are not particularly limited, but are determined so as to efficiently use the mounting area of the mount film 104. The carrier 102 and the semiconductor element 106 are bonded and fixed via the mount film 104 so that the connection surface (the lower surface 20) of the semiconductor element 106 is in contact with the main surface 10 of the mount film 104.

(Encapsulant layer 108 forming step)
Subsequently, as shown in FIG. 3A, the plurality of semiconductor elements 106 placed on the main surface 10 of the mount film 104 are sealed with a sealing material layer 108. That is, the sealing material layer 108 is formed on the sidewall and the upper surface of the semiconductor element 106, and the sealing material layer 108 is formed so as to embed the separated portion of the semiconductor element 106. Therefore, the lower surface 20 (connection surface) of the semiconductor element 106 and the lower surface 30 (mount film 104 peeling surface) of the sealing material layer 108 constitute the same surface. In the present embodiment, the same surface refers to a continuous surface and an uneven height difference of preferably 1 mm or less, more preferably 100 μm or less. Such a sealing material layer 108 is formed by curing the semiconductor sealing resin composition according to the present invention. For example, the sealing material layer 108 can be formed by compression molding using a granular semiconductor sealing resin composition.

[Resin composition for semiconductor encapsulation]
Here, each component of the resin composition for semiconductor encapsulation according to the present invention will be described.
The resin composition for semiconductor encapsulation according to the present invention includes at least an epoxy resin (A), a curing agent (B), and an inorganic filler (C).

[Epoxy resin (A)]
First, the epoxy resin (A) will be described. The epoxy resin (A) is not particularly limited in molecular weight and structure as long as it has three or more epoxy groups in one molecule. For example, novolac epoxy resins such as phenol novolac type epoxy resin, cresol novolac type epoxy resin, aromatic glycidyl amine type epoxy resin such as aminophenol type glycidyl amine, triphenolmethane type epoxy resin, triphenolpropane type epoxy resin, Alkyl-modified triphenolmethane type epoxy resin, triazine nucleus-containing epoxy resin, dicyclopentadiene-modified phenol type epoxy resin, naphthols such as hydroxynaphthalene or dihydroxynaphthalene, and aldehyde compounds such as formaldehyde, acetaldehyde, benzaldehyde, salicylaldehyde, etc. A naphthol type epoxy such as a resin obtained by epoxidizing a novolak type naphthol resin obtained by reacting in an acid catalyst. Fatty, phenol aralkyl type epoxy resins having a phenylene and / or biphenylene skeleton, epoxy resins such as aralkyl type epoxy resins such as a naphthol aralkyl type epoxy resin having a phenylene and / or biphenylene skeleton, and aliphatic epoxy resins such as an alicyclic epoxy Is mentioned. Specifically, methoxynaphthalene / cresol / formaldehyde co-condensation type epoxy resin (for example, EXA-7320 manufactured by DIC Corporation), triphenylmethane type epoxy resin, tris (hydroxyphenyl) methane type epoxy resin, salicylaldehyde type epoxy. Naphthol type epoxy resin (for example, DIC Corporation, HP-4700) such as resin (for example, E-1032H60 manufactured by JER Corporation), 1,1-bis (2,7-diglycidyloxy-1-naphthyl) methane ), Biphenyl aralkyl type epoxy resin (for example, Nippon Kayaku Co., Ltd., NC-3000). These may be used alone or in combination of two or more.

Moreover, the epoxy resin (A) may further contain a compound (A-1) having one or two epoxy groups in one molecule in addition to the epoxy resin. As the compound (A-1), a compound having one epoxy group in one molecule such as glycidoxyphenyl ether and glycidoxynaphthyl ether, a biphenol type epoxy resin (for example, YL6677 manufactured by JER Corporation), Dihydroxyanthracene type epoxy resin (1,4-dihydro-9,10-anthracenediol / 1-chloro-2,3-epoxypropane polycondensate, manufactured by JER Corporation, YL-7310), (with tetramethyl) biphenyl type Epoxy (for example, YX-4000 series manufactured by JER Corporation), tetramethylbisphenol F type epoxy (for example, YTSLV-80XY manufactured by Toto Kasei Co., Ltd.), bisphenol A type epoxy (for example, YL6810 manufactured by JER Corporation), etc. Having two epoxy groups in one molecule of Thing, and the like.
The content of the compound (A-1) in the entire epoxy resin (A) is a content determined by the gel permeation chromatograph (GPC) area method, and is preferably 50 area% or less, more preferably 40 areas. % Or less. By setting the total amount of the 1-2 nuclei to the upper limit value or less, it is possible to suppress a decrease in heat resistance of the semiconductor sealing resin composition of the present invention.
Moreover, even if each of the epoxy resin (A) and the compound (A-1) is individually mixed at the time of compounding the resin composition for semiconductor encapsulation of the present invention, the epoxy resin (A) and the compound (A-1) are preliminarily mixed. ) May be blended by melt mixing, powder mixing, solvent mixing, or the like.
The gel permeation chromatography (GPC) measurement in the present invention is performed as follows. The GPC device is composed of a pump, an injector, a guard column, a column, and a detector, and tetrahydrofuran (THF) is used as a solvent. The pump flow rate is 0.5 ml / min. A flow rate higher than this is not preferable because the detection accuracy of the target molecular weight is lowered. In addition, in order to accurately measure at the above flow rate, it is necessary to use a pump with good flow rate accuracy, and the flow rate accuracy is preferably 0.10% or less. A commercially available guard column (for example, TSK GUARDCOLUMN HHR-L: diameter 6.0 mm, tube length 40 mm) manufactured by Tosoh Corporation, and a commercially available polystyrene gel column (TSK-GEL GMHHR- manufactured by Tosoh Corporation) are used for the guard column. L: diameter 7.8 mm, tube length 30 mm) are connected in series. A differential refractometer (RI detector, for example, a differential refractive index (RI) detector W2414 manufactured by WATERS) is used as the detector. Prior to the measurement, the guard column, the column and the inside of the detector are stabilized at 40 ° C. As a sample, a THF solution of an epoxy resin (A) adjusted to a concentration of 3 to 4 mg / ml is prepared, and this is injected from an about 50 to 150 μl injector to perform measurement. In analyzing the sample, a calibration curve prepared from a monodisperse polystyrene (hereinafter referred to as PS) standard sample is used. For the calibration curve, a logarithmic value of the molecular weight of PS and the peak detection time (retention time) of PS are plotted, and a regression of the cubic equation is used. As standard PS samples for preparing calibration curves, Shodex Standard SL-105 series product numbers S-1.0 (peak molecular weight 1060), S-1.3 (peak molecular weight 1310), S-2 manufactured by Showa Denko K.K. 0.0 (peak molecular weight 1990), S-3.0 (peak molecular weight 2970), S-4.5 (peak molecular weight 4490), S-5.0 (peak molecular weight 5030), S-6.9 (peak molecular weight 6930) ), S-11 (peak molecular weight 10700), S-20 (peak molecular weight 19900).

  Although the lower limit of content of an epoxy resin (A) is not specifically limited with respect to 100 mass% of the total value of the resin composition for semiconductor sealing, Preferably it is 1 to 30 mass%, More preferably, it is 5 The mass is 20% by mass or more.

[Curing agent (B)]
Next, the curing agent (B) will be described. The curing agent (B) is not particularly limited, but is a monomer, oligomer, or polymer in general having 3 or more phenolic hydroxyl groups in one molecule, and its molecular weight and molecular structure are not particularly limited. Novolak type resins such as phenol novolak resin, cresol novolak resin, naphthol novolak resin, etc .; polyfunctional phenol resins such as triphenolmethane type phenol resin; modified phenol resins such as terpene modified phenol resin and dicyclopentadiene modified phenol resin; phenylene skeleton And / or aralkyl resins such as a phenol aralkyl resin having a biphenylene skeleton and a naphthol aralkyl resin having a phenylene and / or biphenylene skeleton. These may be used alone or in combination of two or more. Specifically, a reaction product of 2-hydroxybenzaldehyde, formaldehyde and phenol (for example, HE910-20 manufactured by Air Water Co., Ltd.), a triphenylmethane type curing agent (for example, MEH-7500 manufactured by Meiwa Kasei Co., Ltd.) Series), polycondensate of 1-naphthol · 1,4-benzenedimethanol (or 1,4-bis (methoxymethyl) benzene) (for example, SN-485 manufactured by Nippon Steel Chemical Co., Ltd.), biphenylene skeleton phenol Aralkyl type curing agents, biphenyl aralkyl type curing agents (for example, Meiwa Kasei Co., Ltd., MEH-7851 series / or Nippon Kayaku Co., Ltd., GPH-65), phenol novolac type curing agents (for example, Sumitomo Bakelite Co., Ltd.) Manufactured, PR series: PR-HF-3). Such a phenol resin curing agent provides a good balance of flame resistance, moisture resistance, electrical properties, curability, storage stability, and the like. In particular, from the viewpoint of curability, for example, the hydroxyl group equivalent of the phenol resin-based curing agent can be 90 g / eq or more and 250 g / eq or less.

  Furthermore, examples of the curing agent that can be used in combination include a polyaddition type curing agent, a catalyst type curing agent, and a condensation type curing agent.

  Examples of the polyaddition type curing agent include aliphatic polyamines such as diethylenetriamine (DETA), triethylenetetramine (TETA), and metaxylenediamine (MXDA), diaminodiphenylmethane (DDM), m-phenylenediamine (MPDA), and diamino. In addition to aromatic polyamines such as diphenylsulfone (DDS), polyamine compounds including dicyandiamide (DICY), organic acid dihydralazide, and the like; alicyclic acid anhydrides such as hexahydrophthalic anhydride (HHPA) and methyltetrahydrophthalic anhydride (MTHPA) , Acid anhydrides including aromatic anhydrides such as trimellitic anhydride (TMA), pyromellitic anhydride (PMDA), benzophenone tetracarboxylic acid (BTDA); polysulfide, thioester, thioate Polymercaptan compounds, such as isocyanate prepolymers, isocyanate compounds such as blocked isocyanate; and organic acids such as carboxylic acid-containing polyester resins.

  Examples of the catalyst-type curing agent include tertiary amine compounds such as benzyldimethylamine (BDMA) and 2,4,6-trisdimethylaminomethylphenol (DMP-30); 2-methylimidazole, 2-ethyl-4 -Imidazole compounds such as methylimidazole (EMI24); Lewis acids such as BF3 complexes.

  Examples of the condensation type curing agent include urea resins such as methylol group-containing urea resins; melamine resins such as methylol group-containing melamine resins.

  In the case where such other curing agents are used in combination, the lower limit of the content of the phenol resin curing agent is preferably 20% by mass or more, and 30% by mass with respect to the total curing agent (B). More preferably, it is more preferably 50% by mass or more. When the blending ratio is within the above range, good fluidity can be exhibited while maintaining flame resistance and solder resistance. The upper limit of the content of the phenol resin curing agent is not particularly limited, but is preferably 100% by mass or less with respect to the total curing agent (B).

  Although it does not specifically limit about the lower limit of the total value of the hardening | curing agent (B) content with respect to the resin composition for semiconductor sealing of this invention, The total value of the resin composition for semiconductor sealing is 100 mass%. Is preferably 0.8% by mass or more, and more preferably 1.5% by mass or more. When the lower limit value of the blending ratio is within the above range, good curability can be obtained. Moreover, although it does not specifically limit about the upper limit of the total value of content of the hardening | curing agent (B) with respect to the resin composition for semiconductor sealing of this invention, It is the total value of the resin composition for all semiconductor sealing. It is preferable that it is 12 mass% or less with respect to 100 mass%, and it is more preferable that it is 10 mass% or less. When the upper limit value of the content of the curing agent (B) is within the above range, good solder resistance can be obtained.

  The phenol resin as the curing agent (B) and the epoxy resin (A) are equivalent ratios of the number of epoxy groups (EP) of all epoxy resins (A) and the number of phenolic hydroxyl groups (OH) of all phenol resins. It is preferable to blend so that (EP) / (OH) is 0.8 or more and 1.3 or less. When the equivalent ratio is within the above range, sufficient curing characteristics can be obtained when the resulting resin composition for encapsulating a semiconductor is molded.

[Inorganic filler (C)]
As the inorganic filler (C) used for the semiconductor sealing resin composition of the present invention, inorganic fillers generally used in the technical field of semiconductor sealing resin compositions can be used. Examples thereof include fused silica, spherical silica, crystalline silica, alumina, silicon nitride, and aluminum nitride. The particle size of the inorganic filler is desirably 0.01 μm or more and 150 μm or less from the viewpoint of filling properties in the mold cavity.

  The content of the inorganic filler (C) is preferably 80% by mass or more, more preferably 83% by mass or more, and still more preferably with respect to 100% by mass of the total value of the resin composition for semiconductor encapsulation. It is 86 mass% or more. When the lower limit value is within the above range, an increase in moisture absorption and a decrease in strength due to the curing of the obtained resin composition for encapsulating a semiconductor can be reduced. Thereby, the hardened | cured material which has favorable solder crack-proof property can be obtained. The amount of the inorganic filler (C) is preferably 95% by mass or less, more preferably 93% by mass or less, and still more preferably with respect to 100% by mass of the total value of the resin composition for semiconductor encapsulation. Is 91 mass% or less. When the upper limit is within the above range, the obtained resin composition for encapsulating a semiconductor has good fluidity and good moldability.

  In addition, when using an inorganic filler and a metal hydroxide such as aluminum hydroxide and magnesium hydroxide as described later, and an inorganic flame retardant such as zinc borate, zinc molybdate, and antimony trioxide, The total amount of these inorganic flame retardants and the inorganic filler is desirably within the range of the content of the inorganic filler (C).

[Other ingredients]
The semiconductor sealing resin composition of the present invention may contain a curing accelerator (D). The curing accelerator (D) only needs to accelerate the reaction between the epoxy group of the epoxy resin and the hydroxyl group of the phenol resin curing agent (B), and a generally used curing accelerator (D) is used. it can.

  Specific examples of the curing accelerator (D) include phosphorus atom-containing compounds such as organic phosphines, tetra-substituted phosphonium compounds, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds, adducts of phosphonium compounds and silane compounds; Examples thereof include nitrogen atom-containing compounds such as 1,8-diazabicyclo (5,4,0) undecene-7, benzyldimethylamine, and 2-methylimidazole. Among these, a phosphorus atom-containing compound is preferable from the viewpoint of curability, and from the viewpoint of balance between fluidity and curability, a tetra-substituted phosphonium compound, a phosphobetaine compound, an adduct of a phosphine compound and a quinone compound, a phosphonium compound A catalyst having latency such as an adduct of silane compound and silane compound is more preferable. In view of fluidity, tetra-substituted phosphonium compounds are particularly preferable. From the viewpoint of solder resistance, phosphobetaine compounds, adducts of phosphine compounds and quinone compounds are particularly preferable, and in view of latent curability. An adduct of a phosphonium compound and a silane compound is particularly preferable. Further, from the viewpoint of continuous moldability, a tetra-substituted phosphonium compound is preferable. Among these, phosphorus atom-containing compounds such as organic phosphines, phosphobetaine compounds, and adducts of phosphine compounds and quinone compounds are particularly preferable from the viewpoint of reducing residue.

  Examples of the organic phosphine that can be used in the semiconductor sealing resin composition of the present invention include a third phosphine such as triphenylphosphine.

  Examples of the phosphobetaine compound that can be used in the semiconductor sealing resin composition of the present invention include compounds represented by the following general formula (9).

  In General formula (9), X1 represents a C1-C3 alkyl group, Y1 represents a hydroxyl group, f is an integer of 0-5, g is an integer of 0-4.

  The compound represented by the general formula (9) is obtained, for example, as follows. First, it is obtained through a step of bringing a triaromatic substituted phosphine, which is a third phosphine, into contact with a diazonium salt and replacing the triaromatic substituted phosphine with a diazonium group of the diazonium salt. However, the present invention is not limited to this.

  Examples of the adduct of a phosphine compound and a quinone compound that can be used in the resin composition for semiconductor encapsulation of the present invention include compounds represented by the following general formula (10).

  In General Formula (10), P represents a phosphorus atom, R21, R22, and R23 each independently represent an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms, and R24, R25, and R26 independently represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and R24 and R25 may be bonded to each other to form a ring.

  Examples of the phosphine compound used as an adduct of a phosphine compound and a quinone compound include an aromatic ring such as triphenylphosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, trinaphthylphosphine, and tris (benzyl) phosphine. Those having a substituent such as a substituent or an alkyl group or an alkoxyl group are preferred, and examples of the substituent such as an alkyl group and an alkoxyl group include those having 1 to 6 carbon atoms. From the viewpoint of availability, triphenylphosphine is preferable.

  In addition, examples of the quinone compound used for the adduct of the phosphine compound and the quinone compound include o-benzoquinone, p-benzoquinone, and anthraquinones. Among them, p-benzoquinone is preferable from the viewpoint of storage stability.

  As a method for producing an adduct of a phosphine compound and a quinone compound, the adduct can be obtained by contacting and mixing in a solvent capable of dissolving both organic tertiary phosphine and benzoquinone. The solvent is preferably a ketone such as acetone or methyl ethyl ketone, which has low solubility in the adduct. However, the present invention is not limited to this.

  In the compound represented by the general formula (10), R21, R22 and R23 bonded to the phosphorus atom are phenyl groups, and R24, R25 and R26 are hydrogen atoms, that is, 1,4-benzoquinone and triphenyl A compound to which phosphine has been added is preferable in that it reduces the thermal elastic modulus of the cured product of the resin composition for semiconductor encapsulation.

  The lower limit of the content of the curing accelerator (D) that can be used in the resin composition for semiconductor encapsulation of the present invention is 0.1% with respect to 100% by mass of the total value of the resin composition for semiconductor encapsulation. It is preferable that it is mass% or more. When the lower limit value of the content of the curing accelerator (D) is within the above range, sufficient curability can be obtained. Moreover, it is preferable that the upper limit of content of a hardening accelerator (D) is 1 mass% or less with respect to 100 mass% of total values of the resin composition for whole semiconductor sealing. Sufficient fluidity | liquidity can be obtained as the upper limit of content of a hardening accelerator (D) is in the said range.

  In the present invention, a compound (E) in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring (hereinafter sometimes simply referred to as “compound (E)”) can be used. The compound (E) in which a hydroxyl group is bonded to each of two or more adjacent carbon atoms constituting an aromatic ring can be used to cause a crosslinking reaction between the epoxy resin (A) and the phenol resin-based curing agent (B). Even when a phosphorus atom-containing curing accelerator having no latent property is used as the curing accelerator to be promoted (D), the reaction in the melt-kneading of the semiconductor sealing resin composition can be suppressed, A semiconductor sealing resin composition can be obtained stably. The compound (E) also has an effect of lowering the melt viscosity of the resin composition for semiconductor encapsulation and improving the fluidity. As the compound (E), a monocyclic compound represented by the following general formula (12) or a polycyclic compound represented by the following general formula (13) can be used. You may have the substituent of.

  In General Formula (12), one of R31 and R35 is a hydroxyl group, the other is a hydrogen atom, a hydroxyl group, or a substituent other than a hydroxyl group, and R32, R33, and R34 are substitutions other than a hydrogen atom, a hydroxyl group, or a hydroxyl group. It is a group.

  In General Formula (13), one of R36 and R42 is a hydroxyl group, the other is a hydrogen atom, a hydroxyl group or a substituent other than a hydroxyl group, and R37, R38, R39, R40, and R41 are a hydrogen atom, a hydroxyl group, A substituent other than a hydroxyl group.

  Specific examples of the monocyclic compound represented by the general formula (12) include catechol, pyrogallol, gallic acid, gallic acid ester, and derivatives thereof. Specific examples of the polycyclic compound represented by the general formula (13) include 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, and derivatives thereof. Among these, a compound in which a hydroxyl group is bonded to each of two adjacent carbon atoms constituting an aromatic ring is preferable because of easy control of fluidity and curability. In consideration of volatilization in the kneading step, it is more preferable that the mother nucleus is a compound having a low volatility and a highly stable weighing naphthalene ring. In this case, specifically, the compound (E) can be a compound having a naphthalene ring such as 1,2-dihydroxynaphthalene, 2,3-dihydroxynaphthalene and derivatives thereof. These compounds (E) may be used individually by 1 type, or may use 2 or more types together.

  The lower limit of the content of the compound (E) is preferably 0.01% by mass or more, more preferably 0.03% by mass with respect to 100% by mass of the total value of the resin composition for encapsulating all semiconductors. Above, especially preferably 0.05% by mass or more. When the lower limit value of the content of the compound (E) is within the above range, a sufficient viscosity reduction and fluidity improvement effect of the resin composition for semiconductor encapsulation can be obtained. Moreover, it is preferable that the upper limit of content of a compound (E) is 1 mass% or less with respect to the total value of 100 mass% of the resin composition for all semiconductor sealing, More preferably, it is 0.8 mass%. Hereinafter, it is particularly preferably 0.5% by mass or less. When the upper limit value of the content of the compound (E) is within the above range, there is little possibility of causing a decrease in the curability of the resin composition for semiconductor encapsulation and a decrease in the physical properties of the cured product.

  In the resin composition for semiconductor encapsulation of the present invention, a coupling agent (F) such as a silane coupling agent is added to improve the adhesion between the epoxy resin (A) and the inorganic filler (C). Can do. As a coupling agent (F), if it reacts between an epoxy resin (A) and an inorganic filler (C) and improves the interface strength of an epoxy resin (A) and an inorganic filler (C). Well, not particularly limited, for example, epoxy silane, amino silane, ureido silane, mercapto silane and the like. Moreover, a coupling agent (F) raises the effect of the compound (E) of reducing the melt viscosity of the resin composition for semiconductor sealing, and improving fluidity | liquidity by using together with the above-mentioned compound (E). It is also possible.

  Examples of the epoxy silane include γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4 epoxycyclohexyl) ethyltrimethoxysilane. Etc. Examples of the aminosilane include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, and N-β (aminoethyl) γ-aminopropyl. Methyldimethoxysilane, N-phenylγ-aminopropyltriethoxysilane, N-phenylγ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-6- (aminohexyl) 3 -Aminopropyltrimethoxysilane, N- (3- (trimethoxysilylpropyl) -1,3-benzenedimethanane, etc. In addition, examples of ureidosilane include γ-ureidopropyltriethoxysilane, hexa Methyl disilazane, etc. of aminosilane The primary amino moiety may be used as a latent aminosilane coupling agent protected by reacting with a ketone or an aldehyde, and the aminosilane may have a secondary amino group. For example, by pyrolysis such as γ-mercaptopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, bis (3-triethoxysilylpropyl) tetrasulfide, bis (3-triethoxysilylpropyl) disulfide Examples include silane coupling agents that exhibit the same function as mercaptosilane coupling agents, etc. These silane coupling agents may be pre-hydrolyzed, and these silane coupling agents. Can be used alone or two or more It may be used in combination.

  Mercaptosilane is preferred in terms of the balance between solder resistance and continuous moldability, aminosilane is preferred in terms of fluidity, and in terms of adhesion to organic components such as polyimide on the silicon chip surface and solder resist on the substrate surface. Epoxysilane is preferred.

  As a lower limit of the content of the coupling agent (F) such as a silane coupling agent that can be used in the semiconductor sealing resin composition of the present invention, the total value of all the semiconductor sealing resin compositions is 100% by mass. Is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more. If the lower limit of the content of the coupling agent (F) such as a silane coupling agent is within the above range, the interface strength between the epoxy resin (A) and the inorganic filler (C) does not decrease, and the semiconductor Good solder crack resistance in the apparatus can be obtained. Moreover, as an upper limit of content of coupling agents (F), such as a silane coupling agent, 1 mass% or less is preferable with respect to the total value of 100 mass% of the resin composition for whole semiconductor sealing, More preferably Is 0.8% by mass or less, particularly preferably 0.6% by mass or less. If the upper limit of the content of the coupling agent (F) such as a silane coupling agent is within the above range, the interface strength between the epoxy resin (A) and the inorganic filler (C) does not decrease, and the semiconductor Good solder crack resistance in the apparatus can be obtained. Moreover, if content of coupling agents (F), such as a silane coupling agent, exists in the said range, the water absorption of the hardened | cured material of the resin composition for semiconductor sealing will not increase, and it is favorable in a semiconductor device. Solder crack resistance can be obtained.

  In the resin composition for semiconductor encapsulation of the present invention, an inorganic flame retardant (G) can be added in order to improve flame retardancy. Among these, a metal hydroxide or a composite metal hydroxide that inhibits the combustion reaction by dehydrating and absorbing heat during combustion is preferable in that the combustion time can be shortened. Examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, calcium hydroxide, barium hydroxide, and zirconia hydroxide. The composite metal hydroxide is a hydrotalcite compound containing two or more metal elements, wherein at least one metal element is magnesium, and the other metal elements are calcium, aluminum, tin, titanium, iron Any metal element selected from cobalt, nickel, copper, or zinc may be used, and as such a composite metal hydroxide, a magnesium hydroxide / zinc solid solution is easily available on the market. Of these, aluminum hydroxide and magnesium hydroxide / zinc solid solution are preferable from the viewpoint of the balance between solder resistance and continuous moldability. An inorganic flame retardant (G) may be used independently or may be used 2 or more types. Further, for the purpose of reducing the influence on the continuous moldability, a surface treatment may be performed with a silicon compound such as a silane coupling agent or an aliphatic compound such as wax.

  In the semiconductor sealing resin composition of the present invention, in addition to the components described above, colorants such as carbon black, bengara and titanium oxide; natural waxes such as carnauba wax; synthetic waxes such as polyethylene wax; stearic acid and zinc stearate Release agents such as higher fatty acids and their metal salts or paraffin; low-stress additives such as silicone oil and silicone rubber may be appropriately blended.

  The resin composition for encapsulating a semiconductor of the present invention comprises an epoxy resin (A), a curing agent (B), an inorganic filler (C), and other additives described above at room temperature using, for example, a mixer. Mix uniformly and then melt and knead using a kneader such as a heating roll, kneader, or extruder, if necessary, and then cool and pulverize as necessary to achieve the desired degree of dispersion and fluidity. Etc. can be adjusted.

  Moreover, in the resin composition for semiconductor encapsulation according to the present invention, the saturated ion viscosity of the resin composition for semiconductor encapsulation when measured under the conditions of a measurement temperature of 125 ° C. and a measurement frequency of 100 Hz using a dielectric analyzer. Is preferably 100 seconds or more, more preferably 180 seconds or more, and even more preferably 300 seconds or more from the start of measurement, while preferably 900 seconds or less, more preferably 800 seconds or less, still more preferably 700 seconds or less. The time when the saturated ion viscosity is reached means, for example, the time when the increase in the ion viscosity is stopped. By setting the time at which the saturated ion viscosity of the resin composition for semiconductor encapsulation reaches within the above range, a resin composition for semiconductor encapsulation excellent in low-temperature moldability can be obtained.

  Moreover, in the resin composition for semiconductor encapsulation according to the present invention, the minimum ionic viscosity of the resin composition for semiconductor encapsulation when measured under the conditions of a measurement temperature of 125 ° C. and a measurement frequency of 100 Hz using a dielectric analyzer. (Log Ion Viscosity) is preferably 6 or more and 8 or less, and the ionic viscosity after 600 seconds from the start of measurement is preferably 9 or more and 11 or less. The time of appearance of the lowest ionic viscosity represents the ease of dissolution as a resin system, and the value of the lowest ionic viscosity represents the lowest viscosity as a resin system. By setting the minimum ionic viscosity of the resin composition for semiconductor encapsulation within the above range, a resin composition for semiconductor encapsulation excellent in low-temperature moldability can be obtained.

  In addition, in the resin composition for semiconductor encapsulation according to the present invention, a nozzle having a nozzle diameter of 0.5 mmφ and a length of 1 mm is used by using a Koka type viscosity measuring apparatus (manufactured by Shimadzu Corporation, CFT500). Thus, the high viscosity of the resin composition for semiconductor encapsulation when measured at a measurement temperature of 125 ° C. and a load of 40 kg is preferably 20 Pa · s to 200 Pa · s, more preferably 30 Pa · s to 180 Pa. -S or less. By setting the high viscosity of the resin composition for semiconductor encapsulation within the above range, a resin composition for semiconductor encapsulation excellent in low-temperature moldability can be obtained.

  Thus, in the present embodiment, for example, the curing accelerator (D) is appropriately selected, or a triphenolmethane type epoxy resin, a triphenolpropane type epoxy resin, an alkyl-modified triphenolmethane type epoxy resin, etc. Semiconductors with excellent low-temperature moldability by using polyfunctional epoxy resins and trifunctional phenolic resins such as triphenolmethane type phenolic resin, triphenolpropane type phenolic resin, and alkyl-modified triphenolmethane type phenolic resin A sealing resin composition is obtained.

  By using such a resin composition for encapsulating a semiconductor excellent in low-temperature moldability, the step of forming the encapsulant layer 108 (compression molding step) is preferably 100 ° C. or higher and 150 ° C. or lower, more preferably 115. The curing treatment can be performed under a temperature condition of not lower than 135 ° C. and more preferably not lower than 120 ° C. and not higher than 130 ° C.

  Here, although the mechanism is unknown, the present inventors have found that if the molding temperature of the resin composition for semiconductor encapsulation is lowered, the remaining area of the paste is reduced. Therefore, by setting the curing process of the semiconductor sealing resin composition within the above temperature range, that is, by reducing the curing temperature, the remaining area of the mounting film 104 can be reduced. Accordingly, by setting the molding temperature in the step of forming the sealing material layer 108 to be equal to or lower than the above upper limit value, the residue can be reduced. On the other hand, the moldability of the sealing material layer 108 can be improved by setting the molding temperature to the above lower limit value or more. In particular, by setting the molding temperature within a more preferable range, it is possible to realize a semiconductor device that is excellent in the balance between the reduction of residue and the moldability of the sealing material layer 108.

  The remaining area is obtained by the following method, for example. First, the groove area remaining on the molded product (the lower surface 30 of the sealing material layer 108) is measured with a digital microscope. The ratio (%) is calculated by dividing the groove area by the area of the lower surface 30 of the sealing material layer 108 (excluding the area of the lower surface 20 of the semiconductor element 106). It should be noted that the measurement can be difficult when the glue remains on almost the entire surface. In this case, for example, the remaining area of the glue may be determined to be 80% or more without performing detailed calculation.

  Examples of the conditions for creating a molded product sample are as follows. First, a heat peelable adhesive layer (for example, Riva Alpha (registered trademark)) is attached to a metal plate (aluminum plate or the like) (the area of the heat peelable adhesive layer is 50 × 50 mm). The semiconductor sealing resin composition is filled into a mold and compression molded (cured at 125 ° C. for 7 minutes). Then, post-cure (150 ° C., 1 hour). After cooling to room temperature, the cured product is peeled off from the metal plate on a hot plate at 180 ° C. Thereafter, Riva Alpha is peeled off from the cured product of the semiconductor sealing resin composition at 180 ° C. to obtain a sample of a molded product.

  The laver remaining area is preferably 0% or more and 10% or less, more preferably 8% or less, and further preferably 5% or less. By setting the remaining area of the glue to the upper limit value or less, the coating film characteristics of the rewiring material on the lower surface 30 of the encapsulant layer 108 can be improved, so that a semiconductor device with excellent yield can be obtained.

[Method for Producing Granular Semiconductor Encapsulating Resin Composition According to the Present Invention]
Next, a method for obtaining the granular semiconductor sealing resin composition of the present invention will be described.
The method for obtaining a granular semiconductor sealing resin composition according to the present invention is not particularly limited as long as the particle size distribution and granule density of the present invention are satisfied. For example, a cylinder having a plurality of small holes The melt-kneaded resin composition is supplied to the inside of the rotor composed of the outer periphery of the disk and the disk-shaped bottom surface, and the semiconductor sealing resin composition is subjected to centrifugal force obtained by rotating the rotor. A method obtained by passing through small holes (hereinafter also referred to as “centrifugal milling method”); after each raw material component is premixed by a mixer, heated and kneaded by a kneader such as a roll, kneader or extruder, and then cooled and pulverized Obtained by removing coarse particles and fine powder using a sieve (hereinafter, also referred to as “pulverization sieving method”); Die with multiple small diameters installed at the tip A method of obtaining by cutting with a cutter that slides and rotates substantially parallel to the die surface, and the molten resin extruded in a strand form from a small hole arranged in the die while performing heat-kneading using an unloader (hereinafter, Also referred to as “hot cut method”). In any method, the particle size distribution and granule density of the present invention can be obtained by selecting kneading conditions, centrifugal conditions, sieving conditions, cutting conditions and the like. A particularly preferred production method is centrifugal milling, and the granular semiconductor sealing resin composition obtained thereby can stably express the particle size distribution and granule density of the present invention. It is preferable for transportability and prevention of sticking. In addition, in the centrifugal milling method, the particle surface can be smoothed to some extent, so that the particles are not caught and the frictional resistance with the surface of the conveying path does not increase, and the bridge ( This is also preferable for prevention of clogging) and prevention of retention on the conveyance path. Further, the centrifugal milling method is advantageous in terms of transportability in compression molding because the particles are formed using a centrifugal force from a melted state, so that the voids are included in the particles to some extent and the granule density can be lowered to some extent.

  On the other hand, in the pulverization sieving method, it is necessary to examine a method for treating a large amount of fine powder and coarse particles generated by sieving, but the sieving device and the like are used in existing production lines for semiconductor sealing resin compositions. Therefore, it is preferable in that a conventional production line can be used as it is. The pulverization sieving method expresses the particle size distribution of the present invention, such as selection of sheet thickness when forming a molten resin sheet before pulverization, selection of pulverization conditions and screen during pulverization, selection of sieving during sieving, etc. Since there are many factors that can be controlled independently, it is preferable in that there are many choices of means for adjusting to a desired particle size distribution. The hot cut method is also preferable in that a conventional production line can be used as it is, for example, by adding a hot cut mechanism to the tip of the extruder.

  Next, a centrifugal milling method, which is an example of a production method for obtaining a granular resin composition for encapsulating a semiconductor according to the present invention, will be described in more detail with reference to the drawings. FIG. 6 is a schematic view of an example from the melt kneading of the semiconductor sealing resin composition to the collection of the granular semiconductor sealing resin composition to obtain the granular semiconductor sealing resin composition. FIG. 7 is a cross-sectional view of an embodiment of an exciting coil for heating the rotor and the cylindrical outer peripheral portion of the rotor, and FIG. 8 is a melt-kneaded resin composition for semiconductor encapsulation supplied to the rotor. Sectional drawing of one Example of the double tube | pipe type cylindrical body to perform is shown, respectively.

  The semiconductor sealing resin composition melt-kneaded by the twin screw extruder 309 is supplied to the inside of the rotor 301 through a double-pipe cylindrical body 305 cooled by passing a refrigerant between the inner wall and the outer wall. At this time, the double-pipe cylinder 305 is preferably cooled using a refrigerant so that the melt-kneaded resin composition for semiconductor sealing does not adhere to the wall of the double-pipe cylinder 305. By supplying the semiconductor sealing resin composition to the rotor 301 through the double-pipe cylindrical body 305, the rotor 301 can be supplied even if the semiconductor sealing resin composition is supplied in a continuous thread form. Since the resin composition for semiconductor encapsulation does not overflow from the rotor 301, it can be stably supplied. The particle shape and particle size distribution of the granular semiconductor sealing resin composition can be adjusted by controlling the molten resin discharge temperature and the like according to the kneading conditions in the twin screw extruder 309. Further, by incorporating a degassing device in the twin-screw extruder 309, the entrainment of bubbles in the particles can be controlled.

  The rotor 301 is connected to the motor 310 and can be rotated at an arbitrary rotation number, and the particle shape and particle size distribution of the granular semiconductor sealing resin composition are adjusted by appropriately selecting the rotation number. can do. A cylindrical outer peripheral portion 302 having a plurality of small holes installed on the outer periphery of the rotor 301 includes a magnetic material 303, and an AC power source generated by an AC power generator 306 in an excitation coil 304 provided in the vicinity thereof. Is heated by eddy current loss and hysteresis loss accompanying the passage of the alternating magnetic flux generated by energizing. In addition, as this magnetic material 303, iron material, silicon steel, etc. are mentioned, for example, 1 type or 2 or more types of magnetic materials 303 can be combined and used. The vicinity of the small holes in the cylindrical outer peripheral portion 302 having a plurality of small holes may not be formed of the same material as that of the magnetic material 303. For example, it is formed of a nonmagnetic material having high thermal conductivity, and magnetically above and below it. By providing the material 303, the vicinity of the small hole of the cylindrical outer peripheral portion 302 can be heated by heat conduction using the heated magnetic material 303 as a heat source. Examples of the nonmagnetic material include copper and aluminum, and one type or two or more types of nonmagnetic materials can be used in combination. After the semiconductor sealing resin composition is supplied to the inside of the rotor 301, the semiconductor sealing resin composition flies to the heated cylindrical outer peripheral portion 302 by centrifugal force obtained by rotating the rotor 301 by the motor 310.

  The resin composition for encapsulating a semiconductor in contact with the heated cylindrical outer peripheral portion 302 having a plurality of small holes easily passes through the small holes in the cylindrical outer peripheral portion 302 and is discharged without increasing the melt viscosity. . The temperature to heat can be arbitrarily set with the characteristic of the resin composition for semiconductor sealing to apply. By appropriately selecting the heating temperature, it is possible to adjust the particle shape and particle size distribution of the granular semiconductor sealing resin composition. In general, if the heating temperature is raised too much, the resin composition hardens and the fluidity may decrease or the small holes in the cylindrical outer peripheral portion 302 may be clogged. Since the contact time between the semiconductor sealing resin composition and the cylindrical outer peripheral portion 302 is extremely short, the influence on the fluidity is extremely small. Further, since the cylindrical outer peripheral portion 302 having a plurality of small holes is uniformly heated, there is very little local change in fluidity. The plurality of small holes in the cylindrical outer peripheral portion 302 can adjust the particle shape and particle size distribution of the granular semiconductor sealing resin composition by appropriately selecting the hole diameter.

  The granular semiconductor sealing resin composition discharged through the small holes in the cylindrical outer peripheral portion 302 is collected, for example, in an outer tank 308 installed around the rotor 301. The outer tank 308 passes through a small hole in the cylindrical outer peripheral portion 302 in order to prevent adhesion of the granular semiconductor sealing resin composition to the inner wall and fusion between the granular semiconductor sealing resin compositions. The collision surface with which the flying granular resin composition for semiconductor encapsulation collides is 10 to 80 degrees, preferably 25 to 65 degrees with respect to the flight direction of the granular semiconductor sealing resin composition. It is preferable that they are installed with an inclination of. When the slope of the collision surface with respect to the flight direction of the resin composition for semiconductor encapsulation is not more than the above upper limit value, the collision energy of the granular resin composition for semiconductor encapsulation can be sufficiently dispersed, and adhesion to the wall surface is prevented. Less likely to occur. Further, if the slope of the collision surface with respect to the flight direction of the resin composition is equal to or higher than the lower limit value, the flight speed of the granular semiconductor sealing resin composition can be sufficiently reduced. Even in the event of a next collision, there is little risk of adhering to the exterior wall surface.

  In addition, when the temperature of the collision surface where the granular semiconductor sealing resin composition collides increases, the granular semiconductor sealing resin composition tends to adhere, so a cooling jacket 307 is provided on the outer periphery of the collision surface. Thus, it is preferable to cool the collision surface. The inner diameter of the outer tank 308 is such that the granular semiconductor sealing resin composition is sufficiently cooled to adhere to the inner wall of the granular semiconductor sealing resin composition, or the granular semiconductor sealing resin composition. It is desirable to have a size that does not cause mutual fusion. In general, an air flow is generated by the rotation of the rotor 301 and a cooling effect is obtained, but cold air may be introduced as necessary. Although the size of the outer tank 308 depends on the amount of resin to be processed, for example, when the diameter of the rotor 301 is 20 cm, adhesion and fusion can be prevented if the inner diameter of the outer tank 308 is about 100 cm.

(Rewiring pseudo wafer 200 forming step)
Subsequently, as shown in FIG. 3B, the mount film 104 is peeled from the lower surface 30 of the sealing material layer 108 and the lower surface 20 of the semiconductor element 106. For example, the mount film 104 can be separated by thermally decomposing the mount film 104 by heat treatment. In addition to the heat treatment, an irradiation treatment such as electron beam or ultraviolet light may be performed. In this manner, the mount film 104 and the carrier 102 can be separated from the structure including the carrier 102, the mount film 104, the semiconductor element 106, and the sealing material layer 108. Thereby, the rewiring pseudo wafer 200 shown in FIG. 3B is obtained. The rewiring pseudo-wafer 200 includes a semiconductor element 106 and a sealing material layer 108. On the same surface as the lower surface 30 of the sealing material layer 108, the lower surfaces 20 (connection surfaces) of the plurality of semiconductor elements 106 are exposed. On the other hand, a sealing material layer 108 is formed so as to continuously cover the upper surfaces of the plurality of semiconductor elements 106. In other words, in a cross-sectional view, the sealing material layer 108 and the semiconductor element 106 are formed on one surface (rewiring forming surface) side of the rewiring pseudo-wafer 200, while on the other surface (sealing surface) side. Only the sealing material layer 108 is formed. The rewiring pseudo wafer 200 has, for example, a plate shape. The rewiring pseudo wafer 200 may have a circular shape or a rectangular shape in plan view.

  The rewiring pseudo-wafer 200 includes a plurality of semiconductor elements 106 and a sealing material layer 108. The lower surface 20 of the semiconductor element 106 and the lower surface 30 of the sealing material layer 108 are exposed on the one surface 50 of the rewiring pseudo-wafer 200. That is, the one surface 50 is constituted by the lower surface 20 and the lower surface 30. On the other hand, only the upper surface 40 of the sealing material layer 108 is exposed on the other surface 60 of the rewiring pseudo-wafer 200. In such a rewiring pseudo-wafer 200, the encapsulant layer 108 is obtained by curing a resin composition for encapsulating a semiconductor that has an excellent balance of high temperature shrinkage characteristics, low temperature curability, and high temperature heat resistance. is there. Such a sealing material layer 108 is prevented from thermal contraction or thermal deformation due to thermal history during curing or removal of the heat-peelable adhesive layer. By using this sealing material layer 108, the difference in residual stress generated between the one surface 50 and the other surface 60 in the rewiring pseudo-wafer 200 can be reduced. For this reason, the curvature of the one surface 50 of the rewiring pseudo-wafer 200 can be reduced. Thereby, on the one surface 50, while improving the coating-film characteristic of the insulating resin layer 110 for rewiring, connection reliability can be improved. Therefore, the semiconductor device 100 excellent in yield can be obtained.

In the step of peeling the mount film 104 according to the present embodiment, the sealing material layer 108, the mount film 104, and the peel strength under the following measurement conditions are preferably 1 N / m or more and 10 N / m or less, and more Preferably they are 2 N / m or more and 9 N / m or less.
The measurement conditions for peel strength are a measurement temperature of 180 ° C. and a peeling speed of 50 mm / min. By setting the peel strength within the above range, the residue of the mount film 104 can be reduced. For this reason, it can suppress that a liquid rewiring material becomes difficult to form on the sealing material layer 108 surface. The reduction of the peel strength can be realized, for example, by appropriately selecting the material and the curing temperature of the semiconductor sealing resin composition.

  In the manufacturing method of the semiconductor device of the present embodiment, the contact angle of the lower surface of the sealing material layer 108 after the process of peeling the mount film 104 and before the rewiring process is measured at the time of measurement using formamide. , Specified below 70 degrees.

As a result of the study by the inventors, the residue on the lower surface 30 was reduced on the lower surface 30 of the sealing material layer 108 due to the contact angle measured with the rewiring material on the lower surface 30 (the peeled surface from which the mount film 104 was peeled off). It was found that can be evaluated. That is, it has been found that by reducing the contact angle of the lower surface 30, the residue can be reduced. As a result of improving the wettability of the rewiring material on the lower surface 30 of the sealing material layer 108, it was considered that the coating film characteristics of the rewiring material were improved.
Based on the above experimental facts, the following hypothesis was established.
(I) There is a measurement standard substance for measuring the contact angle that shows the tendency of the wettability of the rewiring material.
(Ii) The wettability of the rewiring material can be qualitatively evaluated with the measurement standard substance of (i).
(Iii) The wettability of the rewiring material can be improved by appropriately controlling the contact angle measured with the measurement standard substance of (i).
Based on these hypotheses, the present inventors have found a measurement standard substance that exhibits a tendency to wettability of the rewiring material, and studied to control the contact angle by the measurement standard substance to an appropriate value.

  From various experimental results, it was concluded that it is preferable to use formamide as a measurement standard substance. That is, it has been found that by controlling the lower surface 30 of the encapsulant layer 108 measured using formamide to 70 degrees or less, the residue on the lower surface 30 can be reduced, and the present invention has been completed. This formamide is a measurement standard substance generally used in the field of contact angles.

  As described above, in the present embodiment, by reducing the contact angle of the lower surface 30 of the sealing material layer 108 specified by formamide, the residue on the lower surface 30 is reduced. For this reason, the lower surface 30 of the sealing material layer 108 has high wettability with respect to the material constituting the insulating resin layer 110 for rewiring. Thereby, since the material which comprises the insulating resin layer 110 for rewiring becomes easy to spread uniformly, the coating-film characteristic of the insulating resin layer 110 for rewiring improves. Therefore, the semiconductor device 100 excellent in yield can be obtained.

In the manufacturing method of the semiconductor device of the present embodiment, the upper limit value of the contact angle of the lower surface of the sealing material layer 108 after the step of peeling the mount film 104 is preferably 70 at the time of measurement using formamide. It is not more than 65 degrees, more preferably not more than 65 degrees, and further preferably not more than 60 degrees. On the other hand, the lower limit value of the contact angle is not particularly limited, but is, for example, 0 degree, preferably 5 degrees or more, and more preferably 10 degrees or more.
Here, in the present embodiment, the contact angle may be, for example, an average value, a minimum value, or a maximum value after a predetermined measurement time from the start of measurement, but the average value is more preferable. Although it does not specifically limit as predetermined time, For example, it shall be 10 seconds. Specifically, after the mount film 104 is peeled off, a method of taking the average value by repeating the measurement of the value after 10 seconds by allowing the droplet to stand at 25 ° C. and measuring the value after 10 seconds can be mentioned.

This formamide is used as a standard solution in general contact angle measurement.
In the present embodiment, the measurement is performed at a measurement temperature of 25 ° C. and a measurement apparatus: Dropmaster 500 (manufactured by Kyowa Science Co., Ltd.).

  In the present embodiment, for example, the contact angle can be reduced by appropriately selecting the main agent and the curing agent or appropriately selecting the curing accelerator (D). A reduction in the contact angle measured using formamide indicates that the contact angle of the rewiring material is reduced. For this reason, by setting the contact angle according to the present embodiment within the above range, the residue of the mount film 104 is reduced, so that the liquid rewiring material spreads on the surface of the rewiring pseudo wafer 200. It is suppressed that it becomes difficult. Therefore, in the present embodiment, the semiconductor device 100 with excellent yield can be obtained.

(Post cure)
Post-cure may be performed on the sealing material layer 108 in the rewiring pseudo-wafer 200 before and / or after the mount film 104 is peeled off. Post-curing is performed, for example, in a temperature range of 150 ° C. to 200 ° C., more preferably 160 ° C. to 190 ° C., for 10 minutes to 8 hours. By performing the post cure after the mount film 104 is peeled off, the residue of the mount film 104 can be suppressed.

(Rewiring process)
Subsequently, after the step of peeling the mount film 104, as shown in FIG. 4A, a rewiring insulating resin layer 110 is formed on the lower surface 30 of the sealing material layer 108 and on the lower surface 20 of the semiconductor element 106. . In other words, the rewiring insulating resin layer 110 is formed on one surface of the rewiring pseudo wafer 200 (the surface having the connection surface of the semiconductor element 106).

  Subsequently, as shown in FIG. 4B, an opening 112 that exposes the surface of the pad 122 on the connection surface of the semiconductor element 106 is formed in the insulating resin layer 110 for rewiring. For example, a pattern is formed in the insulating resin layer 110 for rewiring using a photolithography method or the like, and a curing process is performed. As the conditions for the curing treatment, for example, the curing is performed in a temperature range of 150 ° C. to 300 ° C. for 10 minutes to 5 hours. In addition, the rewiring insulating resin layer 110 may be directly formed on the rewiring pseudo-wafer 200, but a passivation layer (not shown) may be formed therebetween.

  Moreover, the insulating resin layer 110 for rewiring is not particularly limited, but polyimide resin, polybenzooxide resin, benzocyclobutene resin, and the like are used from the viewpoint of heat resistance and reliability.

  Subsequently, as shown in FIG. 5A, after a power feeding layer is formed on the entire surface of the rewiring pseudo wafer 200 by a method such as sputtering, a resist layer is formed on the power feeding layer and exposed to a predetermined pattern. After the development, the via 114 and the rewiring circuit 116 are formed by electrolytic copper plating. After the rewiring circuit 116 is formed, the resist layer is peeled off and the power feeding layer is etched.

  In the rewiring pseudo-wafer 200 according to the present embodiment, the Shore D hardness of the sealing material layer 108 after being cured at 125 ° C. for 10 minutes is preferably 70 or more and 100 or less. Preferably they are 80 or more and 95 or less. By setting the Shore D hardness within the above range, a sample having a stable shape can be created in the sealing material layer 108 around the semiconductor element 106, and the occurrence of deformation of the surface shape such as a dent can be suppressed. The insulating resin layer 110 and the rewiring circuit 116 can be formed with high accuracy.

  In the rewiring pseudo-wafer 200 according to the present embodiment, the bending strength of the sealing material layer 108 at 260 ° C. is preferably 10 MPa or more and 100 MPa or less, and more preferably 20 MPa or more and 80 MPa or less. . By setting the bending strength within the above range, a sample having a stable shape can be prepared in the sealing material layer 108 around the semiconductor element 106, and the occurrence of deformation of the surface shape such as a dent can be suppressed. The resin layer 110 and the rewiring circuit 116 can be formed with high accuracy.

In the rewiring pseudo-wafer 200 according to the present embodiment, the flexural modulus of the sealing material layer 108 at 260 ° C. is preferably 5 × 10 ² MPa or more and 3 × 10 ³ MPa or less, more preferably. Is 7 × 10 ² MPa or more and 2.8 × 10 ³ MPa or less. By setting the flexural modulus within the above range, it is possible to create a sample with a stable shape in the sealing material layer 108 around the semiconductor element 106 and to suppress the occurrence of deformation of the surface shape such as a dent. The insulating resin layer 110 for use and the rewiring circuit 116 can be formed with high accuracy.

Further, in the rewiring pseudo-wafer 200 according to the present embodiment, the encapsulant layer 108 is stored when measured using a dynamic viscoelasticity measuring device at a three-point bending mode, a frequency of 10 Hz, and a measurement temperature of 260 ° C. The elastic modulus (E ′) is preferably 5 × 10 ² MPa or more and 5 × 10 ³ MPa or less, more preferably 8 × 10 ² MPa or more and 4 × 10 ³ MPa or less. By setting the storage elastic modulus (E ′) within the above range, a sample with a stable shape can be created in the sealing material layer 108 around the semiconductor element 106, and the occurrence of deformation of the surface shape such as a dent can be suppressed. The rewiring insulating resin layer 110 and the rewiring circuit 116 can be formed with high accuracy.

  Further, in the rewiring pseudo-wafer 200 according to the present embodiment, the linear expansion coefficient (α1) in the xy plane direction of the sealing material layer 108 in the region of 25 ° C. or more and the glass transition temperature (Tg) or less is preferably Is from 3 ppm / ° C. to 15 ppm / ° C., more preferably from 4 ppm / ° C. to 11 ppm / ° C. For example, by using a polyfunctional epoxy resin (A) or a polyfunctional curing agent (B), the linear expansion coefficient (α1) can be within the above range. By setting the linear expansion coefficient (α1) within the above range, the sealing material layer 108 around the semiconductor element 106 can be prevented from warping the opposing surface side with respect to the arrangement surface side of the semiconductor element 106. The insulating resin layer 110 for wiring and the rewiring circuit 116 can be formed with high accuracy.

  Thus, in the present embodiment, for example, a polyfunctional epoxy resin such as a triphenolmethane type epoxy resin, a triphenolpropane type epoxy resin, an alkyl-modified triphenolmethane type epoxy resin, and a triphenolmethane type phenol resin. By appropriately selecting and using a polyfunctional phenolic resin such as a triphenolpropane type phenolic resin or an alkyl-modified triphenolmethane type phenolic resin, or by promoting curing during molding or by post curing after molding, The resin can be further cured, and a cured product (encapsulant layer 108) of the resin composition for semiconductor encapsulation having a stable shape can be obtained. Therefore, the yield of the semiconductor device 100 of this embodiment is improved.

  In the rewiring pseudo-wafer 200 according to the present embodiment, the glass transition temperature (Tg) of the sealing material layer 108 is preferably 100 ° C. or higher and 250 ° C. or lower, more preferably 110 ° C. or higher and 220 ° C. or lower. It is. For example, the glass transition temperature (Tg) can be within the above range by using a polyfunctional epoxy resin (A) or a polyfunctional curing agent (B) or by promoting a curing reaction. By setting the glass transition temperature (Tg) within the above range, when the insulating resin layer 110 for rewiring is cured, the heat loss of the sealing material layer 108 is reduced, and the surface of the insulating resin layer 110 for rewiring is reduced. It can be suppressed that a void resulting from the generated gas is generated and the rewiring circuit 116 is hardly formed.

  In the rewiring pseudo-wafer 200 according to the present embodiment, when the rewiring insulating resin layer 110 is cured at 250 ° C. for 90 minutes, the rewiring insulating resin layer 110 is cured before and after the curing process. The mass difference of the sealing material layer 108 is preferably within 5% by mass. Thereby, as described above, it is possible to suppress the occurrence of a void due to the generated gas on the surface of the insulating resin layer 110 for rewiring and the difficulty of forming the rewiring circuit 116.

Subsequently, flux is applied to lands provided on the wiring pattern (rewiring circuit 116). Next, the solder ball 120 is mounted on the land by mounting the solder ball 120 and then melting by heating. Further, a solder resist layer 118 is formed so as to cover a part of the rewiring circuit 116 and the solder balls 120. The applied flux can be resin-based or water-based. As the heating and melting method, reflow, hot plate (hot plate) or the like can be used. Thereby, the wafer level package 210 is obtained.
Thereafter, the wafer level package 210 is singulated, for example, for each semiconductor element 106 by a method such as dicing. Thereby, the semiconductor device 100 of the present embodiment can be obtained. Note that the semiconductor element 106 having a plurality of functions can be arranged in one semiconductor device 100 by dividing the semiconductor chip 108 into units. The semiconductor device 100 obtained in this way may be mounted on a substrate (interposer 132). For mounting, for example, the solder ball 120 of the semiconductor device 100 is electrically connected to a wiring circuit formed on the interposer via bumps. A stacked package is obtained.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail with reference to an Example, this invention is not limited to description of these Examples at all.

  Each component used for the resin composition for semiconductor sealing obtained in the Example mentioned later, a reference example, and a comparative example is demonstrated. Unless otherwise specified, the amount of each component is part by mass.

フェノール樹脂系硬化剤１：下記式（２）で表されるトリフェニルメタン骨格を有するフェノール樹脂（エア・ウオーター（株）製、商品名ＨＥ９１０−２０、軟化点８８℃、水酸基当量１０１）
４．３０質量部

溶融球状シリカ１：（平均粒径２４μｍ、比表面積３．５ｍ^２／ｇ） ７３質量部
溶融球状シリカ２：（平均粒径０．５μｍ、比表面積５．９ｍ^２／ｇ） １５質量部
硬化促進剤１：トリフェニルホスフィン（ケイ・アイ化成（株）製、商品名ＰＰ−３６０）
０．１質量部
着色剤：カーボンブラック（比表面積２９ｍ^２／ｇ、ＤＢＰ吸収量７１ｃｍ^３／１００ｇ）
０．３質量部
カップリング剤：Ｎ−フェニルγ−アミノプロピルトリメトキシシラン（信越化学（株）製、商品名ＫＢＭ−５７３）
０．２質量部
離型剤：モンタン酸エステル系ワックス（クラリアントジャパン（株）製、商品名リコルブＷＥ−４）
０．１５質量部 (Example 1)
<Composition (part by mass) of resin composition for semiconductor encapsulation>
Epoxy resin 1: an epoxy resin mainly composed of an epoxy resin having a triphenylmethane skeleton represented by the following formula (1) (product name: YL6677, epoxy equivalent 163)
6.95 parts by mass

Phenol resin-based curing agent 1: phenol resin having a triphenylmethane skeleton represented by the following formula (2) (produced by Air Water Co., Ltd., trade name HE910-20, softening point 88 ° C., hydroxyl group equivalent 101)
4.30 parts by mass

Fused spherical silica 1: (average particle size 24 μm, specific surface area 3.5 m ² / g) 73 parts by mass Fused spherical silica 2: (average particle size 0.5 μm, specific surface area 5.9 m ² / g) 15 parts by mass Agent 1: Triphenylphosphine (manufactured by K.I. Kasei Co., Ltd., trade name PP-360)
0.1 parts by weight Colorant: carbon black (specific surface area ^29m 2 / g, DBP absorption 71cm ^3/100 g)
0.3 parts by mass Coupling agent: N-phenyl γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-573)
0.2 part by weight Release agent: Montanate ester wax (manufactured by Clariant Japan Co., Ltd., trade name Recolve WE-4)
0.15 parts by mass

<Preparation of master batch>
After the raw materials of the resin composition having the above composition were pulverized and mixed for 5 minutes by a super mixer, this mixed raw material was prepared.

<Manufacture of granular resin composition>
An iron punched wire net having a small hole with a hole diameter of 2.5 mm was used as the material of the cylindrical outer peripheral portion 302 shown in FIG. A punched wire net having a height of 25 mm and a thickness of 1.5 mm processed into a cylindrical shape was attached to the outer periphery of a rotor 301 having a diameter of 20 cm, thereby forming a cylindrical outer peripheral portion 302. The rotor 301 was rotated at 3000 RPM, and the cylindrical outer peripheral portion 302 was heated to 115 ° C. with an exciting coil. After the rotation speed of the rotor 301 and the temperature of the cylindrical outer peripheral portion 302 are in a steady state, the melt obtained by melting and kneading the master batch with the twin-screw extruder 309 while degassing with a degassing device Is supplied to the inside of the rotor 301 from the upper side of the rotor 301 through the double tube cylindrical body 305 at a rate of 2 kg / hr, and the centrifugal outer force of the cylindrical outer peripheral portion 302 is obtained by the centrifugal force obtained by rotating the rotor 301. By allowing a plurality of small holes to pass through, a granular semiconductor sealing resin composition was obtained.

<Manufacture of semiconductor devices>
On the mount film (Nitto Denko Co., Ltd .: Riva Alpha (registered trademark)), 25 semiconductor elements (manufactured by Artex, product number AS8R, 10 mm long × 10 mm wide, 0.725 mm thick) are parallel to each other. And they were placed 0.5 cm apart. These square semiconductor elements are arranged five vertically and five horizontally in plan view. Subsequently, compression molding was performed using the granular semiconductor sealing resin composition to seal the semiconductor element on the mount film. The compression molding conditions were a molding temperature of 125 ° C. and a curing time of 7 minutes. Thereafter, post-curing was performed at 150 ° C. for 1 hour, the mount film was peeled off, and further post-curing was performed at 175 ° C. for 4 hours. In this way, a square rewiring pseudo-wafer (length 10 cm × width 10 cm, thickness 0.15 cm) was obtained.

  Subsequently, a rewiring material (manufactured by Sumitomo Bakelite Co., Ltd., CRC-8902) was applied to one surface of the sealing material layer on the connection surface side of the semiconductor element, and a curing process was performed at 250 ° C. for 90 minutes. Subsequently, a rewiring circuit was formed on the insulating resin layer for rewiring to obtain a semiconductor device.

エポキシ樹脂３：一般名 ビスフェノールＡ型エポキシ樹脂（化学品名：４，４'−イソプロピリデンジフェノールと１−クロロ−２，３−エポキシプロパンの重縮合物、ＪＥＲ（株）製、商品名ＹＬ６８１０、エポキシ当量１７２）
フェノール樹脂系硬化剤２：下記式（４）で表されるビフェニレン骨格を有するフェノールアラルキル樹脂（明和化成（株）製、商品名ＭＥＨ−７８５１ＳＳ、軟化点１０７℃、水酸基当量２０４）

硬化促進剤２：４−ヒドロキシ−２−（トリフェニルホスホニウム）フェノラート（ケイ・アイ化成（株）製、商品名ＴＰＰ−ＢＱ）
硬化促進剤３：テトラフェニルホスホニウム・ビス（ナフタレン−２，３−ジオキシ）フェニルシリケート（住友ベークライト（株）製）
硬化促進剤４：テトラフェニルホスホニウム・４，４'−スルフォニルジフェノラート（住友ベークライト（株）製）
硬化促進剤５：テトラフェニルホスホニウム・２，３'−ジヒドロキシナフタレート（住友ベークライト（株）製）
硬化促進剤６：２−（トリフェニルホスホニウム）フェノラート（エア・ウオーター（株）製、商品名ＰＢ−７）
硬化促進剤７：２−メチルイミダゾール（四国化成工業（株）製、キュアゾール２ＭＺ−Ｐ） (Examples 2-6, Reference Examples 1-4, Comparative Example 1)
A granular resin composition was produced in the same manner as in Example 1 according to the formulation in Tables 1 and 2, and then a semiconductor device was produced in the same manner as in Example 1.
The raw materials used other than Example 1 are shown below.
Epoxy resin 2: phenol aralkyl type epoxy resin having a biphenylene skeleton represented by the following formula (3) (manufactured by Nippon Kayaku Co., Ltd., trade name NC3000P, softening point 58 ° C., epoxy equivalent 273)

Epoxy resin 3: general name bisphenol A type epoxy resin (chemical name: polycondensate of 4,4′-isopropylidenediphenol and 1-chloro-2,3-epoxypropane, manufactured by JER Corporation, trade name YL6810, Epoxy equivalent 172)
Phenol resin-based curing agent 2: Phenol aralkyl resin having a biphenylene skeleton represented by the following formula (4) (Maywa Kasei Co., Ltd., trade name MEH-7851SS, softening point 107 ° C., hydroxyl equivalent 204)

Curing accelerator 2: 4-hydroxy-2- (triphenylphosphonium) phenolate (manufactured by Kay Kasei Co., Ltd., trade name TPP-BQ)
Curing accelerator 3: Tetraphenylphosphonium bis (naphthalene-2,3-dioxy) phenyl silicate (manufactured by Sumitomo Bakelite Co., Ltd.)
Curing accelerator 4: Tetraphenylphosphonium • 4,4′-sulfonyldiphenolate (manufactured by Sumitomo Bakelite Co., Ltd.)
Curing accelerator 5: tetraphenylphosphonium 2,3′-dihydroxynaphthalate (manufactured by Sumitomo Bakelite Co., Ltd.)
Curing accelerator 6: 2- (triphenylphosphonium) phenolate (trade name PB-7, manufactured by Air Water Co., Ltd.)
Curing accelerator 7: 2-methylimidazole (manufactured by Shikoku Chemicals Co., Ltd., Curesol 2MZ-P)

(Evaluation method)
Each evaluation was performed according to the following conditions.

-Warpage (μm)
In the manufacturing process of the semiconductor device of the example and the reference example, after peeling the mount film and before the post cure, using a contact surface roughness meter (Surfcom-480A manufactured by Tokyo Seimitsu Co., Ltd.) The amount of warpage was measured. The results are shown in Table 1.
The conditions are listed below.
Measurement length: 90mm
Measurement position: In plan view, the square structure has two orthogonal center lines. The measurement was made along each of the vertical center line (first place) and the horizontal center line (second place).
Measurement surface: surface on which the semiconductor element is exposed Note that the value of warpage (μm) is the average value of two locations (the total value of the amount of warpage in the vertical direction and the amount of warpage in the horizontal direction is divided by 2 measurement points) ). Moreover, the measurement of the amount of warpage was performed on the structure that was at room temperature after the mount film was peeled off.

-Ion viscosity Using DEA231 / 1 cure analyzer manufactured by NETZSCH as the dielectric analyzer main unit, MP235 Mini-Press manufactured by NETZSCH as the press, measuring temperature 125 ° C, measuring frequency according to ASTM E2039 Under a condition of 100 Hz, about 3 g of a powdered granular resin composition obtained in Examples and Reference Examples was introduced into the upper surface of the electrode part in the press, and then pressed and measured. From the obtained viscosity profile, the minimum ionic viscosity, the ionic viscosity after 600 seconds, and the time to reach the saturated ionic viscosity were determined. Minimum ion viscosity, no unit of ion viscosity after 600 seconds, unit of time to reach saturated ion viscosity is second (sec.). Table 3 shows the measurement results.

・ High viscosity (40kg)
For the granular resin compositions obtained in the examples and reference examples, 125 ° C., pressure 40 kgf / cm ² , capillary diameter 0 using a Koka type flow tester (CFT-500 manufactured by Shimadzu Corporation) The Koka type viscosity was measured under the condition of 0.5 mm. The unit is Pa · s. Table 3 shows the measurement results.

-Shore D hardness Transfer molding was performed using the granular resin compositions obtained in Examples and Reference Examples, and test pieces having a length of 800 mm, a width of 10 mm, and a thickness of 4 mm were molded. The conditions for transfer molding were a molding temperature of 125 ° C. and a curing time of 10 minutes. At the time of molding, 10 seconds after opening the mold, the Shore D hardness of the test piece was measured using a Shore D hardness meter. Table 3 shows the measurement results.

・ Bending strength and flexural modulus (molded at 125 ℃)
Transfer molding was performed using the granular resin compositions obtained in Examples and Reference Examples to obtain JIS bending test pieces. The conditions for transfer molding were a molding temperature of 125 ° C. and a curing time of 7 minutes. The bending strength and bending elastic modulus at 260 ° C. of the obtained test piece were measured according to JIS K 6911. The unit is ppm / ° C. Table 3 shows the measurement results.

-Glass transition temperature (Tg) and linear expansion coefficient (α1) by TMA measurement (molded product at 125 ° C)
Transfer molding was performed using the granular resin compositions obtained in Examples and Reference Examples to obtain test pieces having a length of 15 mm, a width of 4 mm, and a thickness of 3 mm. The conditions for transfer molding were a molding temperature of 125 ° C. and a curing time of 7 minutes. Using the thermal dilatometer (TMA-120 manufactured by Seiko Instruments Inc.), the obtained test piece was heated from room temperature (25 ° C.) at a rate of temperature increase of 5 ° C./min. The rapidly changing temperature was determined as the glass transition temperature. The unit is ° C. Moreover, the average linear expansion coefficient between room temperature (25 degreeC) and Tg-30 degreeC was calculated | required, and it was set as (alpha) 1. The unit is MPa. Table 3 shows the measurement results.

-Storage elastic modulus (E ') by DMA measurement (molded product at 125 ° C)
Transfer molding was performed using the granular resin compositions obtained in Examples and Reference Examples to obtain test pieces having a width of 4 mm, a length of 20 mm, and a thickness of 0.1 mm. The conditions for transfer molding were a molding temperature of 125 ° C. and a curing time of 7 minutes. Storage elastic modulus at 260 ° C. when the obtained test piece was measured using DMA (Dynamic mechanical analysis / dynamic viscoelasticity measuring device) under the conditions of a three-point bending mode, a frequency of 10 Hz, and a measurement temperature of 260 ° C. (E ′) was determined. The unit is MPa. Table 3 shows the measurement results.

-Peel strength In the manufacturing process of the semiconductor device of the examples and reference examples, when the mount film is peeled off, the sealing material layer and the mount film are peeled off at a measurement temperature of 180 ° C. and a peeling speed of 50 mm / min. The peel strength was determined. The unit is N / m. Table 3 shows the measurement results.

Contact angle measured using formamide In the manufacturing process of the semiconductor device of the example and the reference example, the contact angle between the bottom surface of the sealing material layer after peeling the mount and formamide was measured by Dropmaster 500 (manufactured by Kyowa Kagaku Co., Ltd.) Then, the droplet was allowed to stand at 25 ° C., and the value after 10 seconds was measured three times, and the average value was taken. The unit is ° (degrees). The results are shown in Table 3.

Contact angle measured using rewiring material In the manufacturing process of the semiconductor device of Example and Reference Example, the bottom surface of the encapsulant layer after peeling the mount film and the rewiring material (Sumitomo Bakelite Co., Ltd., CRC- 8902) using Dropmaster 500 (manufactured by Kyowa Kagaku Co., Ltd.), the droplet was allowed to stand at 25 ° C., and the value after 10 seconds was measured three times to obtain the average value. It was. The unit is ° (degrees). The results are shown in Table 3.

In Examples 1 to 5, it was found that the warpage was reduced as compared with Comparative Example 1.
About Examples 1-6, since the contact angle of formamide was reducing rather than the reference examples 1-4, it turned out that a paste residue is suppressed. For this reason, about Examples 1-6, it turned out that the contact angle of rewiring material is also reduced from the reference example, and it can apply | coat without a problem.

  Needless to say, the above-described embodiment and a plurality of modifications can be combined within a range in which the contents do not conflict. Further, in the above-described embodiments and modifications, the structure of each part has been specifically described, but the structure and the like can be changed in various ways within a range that satisfies the present invention.

DESCRIPTION OF SYMBOLS 10 Main surface 20 Lower surface 30 Lower surface 40 Upper surface 50 One surface 60 Other surface 100 Semiconductor device 102 Carrier 104 Mount film 106 Semiconductor element 108 Sealing material layer 110 Insulating resin layer 112 for rewiring 114 Opening 114 Via 116 Rewiring circuit 118 Solder resist layer 120 Solder ball 122 Pad 200 Rewiring pseudo wafer 210 Wafer level package 301 Rotor 302 Cylindrical outer peripheral portion 303 Magnetic material 304 Excitation coil 305 Double tube cylindrical body 306 AC power source generator 307 Cooling jacket 308 Outer tank 309 Biaxial Extruder 310 motor

Claims (9)

Forming a heat-peelable adhesive layer on the substrate;
A step of disposing a plurality of semiconductor elements on the main surface of the thermally peelable adhesive layer;
Using a resin composition for semiconductor sealing, a sealing material layer for sealing a plurality of the semiconductor elements on the main surface of the thermally peelable adhesive layer is formed by compression molding at a temperature condition of 100 ° C. or higher and 150 ° C. or lower. To obtain a structure composed of the sealing material layer and the semiconductor element;
Separating the structure from the substrate by peeling the thermally peelable adhesive layer;
Including
The semiconductor sealing resin composition is:
An epoxy resin (A) having three or more epoxy groups in one molecule;
A curing agent (B) having three or more phenolic hydroxyl groups in one molecule;
An inorganic filler (C);
A method of manufacturing a semiconductor device including:   The manufacturing method of the semiconductor device of Claim 1 whose content of the said inorganic filler (C) with respect to the said whole resin composition for semiconductor sealing is 80 mass% or more and 93 mass% or less.   The manufacturing method of the semiconductor device of Claim 1 whose Shore D hardness of the hardened | cured material obtained by hardening the said resin composition for semiconductor sealing on 125 degreeC and the conditions for 10 minutes is 70 or more.   2. The semiconductor device according to claim 1, wherein a bending strength at 260 ° C. of a cured product obtained by curing the resin composition for sealing semiconductor at 125 ° C. for 7 minutes is 10 MPa or more and 100 MPa or less. Production method. The flexural modulus at 260 ° C. of a cured product obtained by curing the resin composition for semiconductor encapsulation at 125 ° C. for 7 minutes is 5 × 10 ² MPa or more and 3 × 10 ³ MPa or less. A method for manufacturing a semiconductor device according to claim 1.   The semiconductor of Claim 1 whose glass transition temperature (Tg) of the hardened | cured material obtained by hardening the said resin composition for semiconductor sealing on 125 degreeC and the conditions for 7 minutes is 100 degreeC or more and 250 degrees C or less. Device manufacturing method.   The linear expansion coefficient (α1) in the xy plane direction in a region of 25 ° C. or more and glass transition temperature (Tg) or less of a cured product obtained by curing the resin composition for semiconductor encapsulation at 125 ° C. for 7 minutes. The method for manufacturing a semiconductor device according to claim 1, wherein the ratio is 3 ppm / ° C. or more and 15 ppm / ° C. or less. A cured product obtained by curing the resin composition for semiconductor encapsulation at 125 ° C. for 7 minutes was measured using a dynamic viscoelasticity measuring device at a three-point bending mode, a frequency of 10 Hz, and a measurement temperature of 260 ° C. The manufacturing method of the semiconductor device of Claim 1 whose storage elastic modulus (E ') at the time is 5 * 10 < ² > MPa or more and 5 * 10 < ³ > MPa or less.   The contact angle of one surface of the sealing material layer from which the semiconductor element is exposed after the step of peeling the heat-peelable pressure-sensitive adhesive layer is 70 degrees or less at the time of measurement using formamide. Item 14. A method for manufacturing a semiconductor device according to Item 1.

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