JP6627390B2 - Photosensitive sealing resin composition, method of manufacturing semiconductor device using the same, and semiconductor device - Google Patents

Description

  The present disclosure relates to a photosensitive sealing resin composition. In particular, a photosensitive encapsulating resin composition for manufacturing a semiconductor device for efficiently and inexpensively manufacturing a semiconductor device that requires high miniaturization and high density, a method for manufacturing a semiconductor device using the same, and a semiconductor Equipment related.

  For the purpose of increasing the density and performance of semiconductor packages, mounting forms in which chips with different performances are mixed in one package have been proposed. A package-on-package that is connected by stacking packages by flip-chip mounting has become important (for example, see Non-Patent Documents 1 and 2).

  In particular, when a semiconductor device is stacked on a semiconductor device such as a package-on-package, it is necessary to provide an external connection terminal for mounting the upper semiconductor device on the lower semiconductor device. Therefore, in order to connect the lower semiconductor device and the upper semiconductor device, a so-called TMV (Through Mold Via) structure semiconductor device in which an opening is provided in a sealing material of the lower semiconductor device and metal is filled, has been emerging. Was. In a semiconductor package having this TMV, a via for connection between devices is provided in a thermosetting resin by a laser in order to provide an opening (for example, see Patent Documents 1 to 7).

US Patent Application Publication No. 2012/0329249 U.S. Patent Application Publication No. 2015/0091182 US Patent Application Publication No. 2015/0145138 U.S. Pat. No. 7,671,457 U.S. Pat. No. 7,633,765 US Patent No. 8026587 US Patent No. 8018068

Susumu Honda "2D to 3D Packaging Technology Trends of Semiconductor Devices and Future Directions" Journal of Japan Institute of Electronics Packaging Vol. 18, No. 3, (2015), pp. 130 See SeungJae Lee, et al. , Electrical Characerization of Wafer Level Fan-Out (WLFO) Using Film Substrate for Low Cost Millimeter Enforcement Electronics Application, IEICE Electronics Co., Ltd.

  In the lower semiconductor package 100A obtained by the conventional manufacturing method using the sealing material shown in FIG. 12, the sealing opening 141 is formed at the corresponding position, so that the upper package is placed on the lower package and electrically connected. Can be secured. The opening for ensuring the connection of the sealing material shown here is generally formed by a carbon dioxide laser. However, in the opening of the sealing material by laser, it takes time because the opening operation cannot be performed at a time, and the diameter of the opening that can be opened for a thickness of 100 μm is limited to about 100 μm, which is smaller than this. It is difficult to form an opening with a diameter, the residue is likely to be generated after the opening operation due to laser opening, and it is necessary to introduce a compression device and a laser device for via opening to handle the sealing material. There were problems such as difficulty in reducing the manufacturing cost.

  SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and has been made in consideration of the above problem, and has been demanded to efficiently and inexpensively manufacture a three-dimensional semiconductor device that requires high miniaturization and high density. An object of the present invention is to provide a resin stopper composition, a method for manufacturing a semiconductor device using the same, and a semiconductor device.

The present invention relates to [1] a photosensitive sealing resin composition capable of forming a pattern by exposure and development, wherein the photosensitive sealing resin composition dissolves in an alkali developing solution at a speed of 3.0 μm / s or less. Things.
The present invention also provides [2] the photosensitive encapsulating resin composition according to [1], wherein the thickness of the encapsulant after encapsulating the semiconductor element is from 50 μm to 200 μm.
Further, the present invention provides the photosensitive sealing resin composition according to the above [1] or [2], wherein the minimum melting viscosity of the photosensitive sealing resin composition is from 10 Pa · s to 1000 Pa · s. is there.
Further, the present invention provides [4] a thermal expansion coefficient at 0 to 80 ° C. of the heat-cured material after the exposure and the heat-curing treatment in the range of 10 × 10 ⁻⁶ / K to 100 × 10 ⁻⁶ / K. The photosensitive sealing resin composition according to any one of the above [1] to [3].
The present invention also provides [5] the photosensitive sealing resin composition according to any one of [1] to [4], wherein the photosensitive sealing resin composition contains a polyimide resin.
Further, the present invention provides [6] (I) a step of sealing a semiconductor element with the photosensitive sealing resin composition according to any one of [1] to [5];
(II) a step of forming a pattern by a step of exposure treatment and an alkali development treatment of dissolving the photosensitive sealing resin composition in an alkali development solution at a speed of 3.0 μm / s or less;
(III) applying a conductive material to the formed pattern;
Is a method for manufacturing a semiconductor device comprising:
Further, the present invention is [7] a semiconductor device having a cured product of the photosensitive sealing resin composition according to any of [1] to [5].

  The photosensitive encapsulating resin composition of the present invention is used for producing a semiconductor device having a so-called TMV (Through Mold Via) structure in which an opening is provided in an encapsulating material of a semiconductor device to form a conductor. It does not require expensive equipment such as a compression device for sealing the material, can be sealed with a less expensive device such as a laminator, and does not require a laser device or the like for drilling. Since the connection is performed using the lithography technique, the density of the connection portion can be increased, and the connection can be efficiently manufactured at low cost. And since a semiconductor device is manufactured using this, a semiconductor device capable of high-density transmission can be manufactured efficiently and at low cost, and the obtained semiconductor device can perform high-density transmission at low cost. Excellent cost performance.

It is sectional drawing which shows typically the fixing member which stuck the metal on the surface. FIG. 4 is a cross-sectional view schematically illustrating a state where a semiconductor element is fixed on a fixing member. It is sectional drawing which shows the state which sealed the sealing material on the semiconductor element typically. It is sectional drawing which shows typically the state which provided the opening part in the sealing material after performing exposure processing and development processing. FIG. 3 is a cross-sectional view schematically illustrating a state in which a metal is applied (filled) to an opening of a sealing material. FIG. 9 is a cross-sectional view schematically showing a state in which the metal adhered to the fixing member and the surface is removed and the metal member is inverted. It is sectional drawing which shows typically the state which formed the rewiring insulating layer on the sealing material. It is sectional drawing which shows a wiring pattern typically. FIG. 4 is a cross-sectional view schematically showing a state in which a rewiring insulating layer is formed on a wiring pattern and bumps for mounting a package are mounted. FIG. 9 is a cross-sectional view schematically showing an operation of forming a rewiring insulating layer and singulating a state in which bumps are mounted. It is sectional drawing which shows typically the obtained semiconductor device after singulation. FIG. 11 is a cross-sectional view schematically showing a step of manufacturing a conventional semiconductor device.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings. In the following description, the same or corresponding parts will be denoted by the same reference characters, without redundant description. Unless otherwise specified, the positional relationship such as up, down, left, and right is based on the positional relationship shown in the drawings. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.
In this specification, the term "step" is included not only in an independent step but also in the case where the intended purpose of the step is achieved even if it cannot be clearly distinguished from other steps. . Further, in this specification, “sealing” means that it is only necessary to cover the semiconductor element, it may be a concave plate or a flat plate, and a concave plate-shaped resin composition and a flat fixing member (or , A rewiring insulating layer). In addition, transparency and electrical insulation are not particularly limited. Further, the resin composition, the rewiring insulating layer, and if necessary, the conductor pattern (wiring pattern) and the like, and the semiconductor element may be covered. Further, the term “layer” includes, in a plan view, a partially formed shape structure in addition to a partially formed shape structure.

  Here, a method for manufacturing the semiconductor device (semiconductor package) 100 shown in FIG. 11 will be described. The method for manufacturing a semiconductor device according to the present embodiment is particularly suitable for a mode that requires miniaturization and multi-pins. In particular, the manufacturing method of the present invention is suitable for a form in which a FO-WLP (Fan-out Wafer Level Package) is made three-dimensional.

A method for manufacturing the semiconductor device (semiconductor package) 100 will be described with reference to FIGS.
First, a support comprising a semiconductor element fixing base material 1 and a fixing member 2 is prepared (see FIG. 1). The substrate 1 for fixing a semiconductor element is not particularly limited, and examples thereof include a glass cloth-impregnated substrate in which a glass cloth is impregnated with a resin, a silicon wafer, glass, and a SUS (stainless steel) plate. Materials having an elastic modulus of 1 GPa or more (also referred to as “high-rigidity materials”) are suitable.
The thickness of the semiconductor element fixing substrate 1 is preferably 0.2 to 0.8 mm. If it is 0.2 mm or more, warpage during the assembly process can be suppressed, and handling tends to be easy. On the other hand, when the thickness is 0.8 mm or less, the semiconductor element fixing base material 1 is easily removed, and the material cost tends to be reduced. The average coefficient of thermal expansion from room temperature (25 ° C.) to 150 ° C. of the semiconductor element fixing substrate 1 is preferably 1 × 10 ⁻⁶ to 15 × 10 ⁻⁶ / K. If it is 1 × 10 ⁻⁶ / K or more, the material cost tends to be reduced. On the other hand, in the case of 15 × 10 ⁻⁶ / K or less, the warpage after chip mounting tends to be suppressed.

  Next, the semiconductor element 3 is fixed on the fixing member 2 (see FIG. 2). The semiconductor element 3 is bonded via the fixing member 2. The fixing member 2 can be used by previously setting it on the back surface of the wafer-shaped semiconductor element 3 by laminating or the like and dividing the semiconductor element 3 into individual pieces. Although the fixing member 2 is not particularly limited, it is preferable to select a film-shaped fixing member. This is because, when the film is in the form of a film, the operability of sticking on the semiconductor element fixing base material 1 and peeling operation at the time of removing the support are good. The semiconductor element 3 is fixed by using a mounting machine such as a die bonder. When a heat-peelable sheet is used as the fixing member 2, the heat-peelable sheet can be peeled off by, for example, placing it on a hot plate set at a predetermined temperature and heating. The heating temperature may be appropriately determined according to the heat release sheet to be used.

Next, the semiconductor element 3 is sealed so as to cover the semiconductor element 3 using the photosensitive sealing resin composition 4 (see FIG. 3).
The photosensitive sealing resin composition 4 of the present embodiment preferably contains (A) an alkali-soluble resin, (B) a radiation-polymerizable compound, and (C) a photoinitiator. In the present specification, these components may be simply referred to as component (A), component (B), component (C), and the like. Further, the photosensitive sealing resin composition of the present embodiment can be suitably used for sealing a semiconductor element.

  In the photosensitive sealing resin composition 4 of the present embodiment, as the component (A), a polymer having an alkali-soluble group is preferable, and a polymer having an alkali-soluble group at a terminal or a side chain is more preferable. Examples of the alkali-soluble group include an ethylene glycol group, a carboxyl group, a hydroxyl group, a sulfonyl group, and a phenolic hydroxyl group. The polymer having an alkali-soluble group may have one of the above functional groups alone or may have two or more of the above functional groups.

  As the component (A), for example, polyester resin, polyether resin, polyimide resin, polyamide resin, polyamideimide resin, polyetherimide resin, polyurethane resin, polyurethaneimide resin, polyurethaneamideimide resin, siloxane polyimide resin, polyesterimide resin , These copolymers, their precursors (polyamic acid, etc.), polybenzoxazole resin, phenoxy resin, polysulfone resin, polyethersulfone resin, polyphenylene sulfide resin, polyester resin, polyether resin, polycarbonate resin, poly Examples thereof include an ether ketone resin, a (meth) acrylic copolymer having a weight average molecular weight of 10,000 to 1,000,000, a novolak resin, and a phenol resin. These can be used alone or in combination of two or more. Further, these resins may have a main chain and / or a side chain to which a glycol group such as ethylene glycol or propylene glycol, a carboxyl group and / or a hydroxyl group is provided.

  Among these, the component (A) is preferably a polyimide resin from the viewpoints of high-temperature adhesion, heat resistance, and film formability. The polyimide resin can be obtained, for example, by subjecting a tetracarboxylic dianhydride and a diamine to a condensation reaction by a known method.

  In the above condensation reaction, the mixing molar ratio of the tetracarboxylic dianhydride and the diamine is such that the total of the diamine is 0.5 to 2.0 mol with respect to the total of 1.0 mol of the tetracarboxylic dianhydride. More preferably, it is 0.8 to 1.0 mol. The order of addition of the tetracarboxylic anhydride and the diamine may be arbitrary.

  The component (B) can be used without particular limitation as long as it is a photopolymerizable compound or a photocrosslinkable compound. For example, a compound having at least one ethylenically unsaturated bond in the molecule may be used. it can. The component (C) is not particularly limited as long as the component (B) can be polymerized, and can be appropriately selected from commonly used photopolymerization initiators.

The sealing with the photosensitive sealing resin composition 4 may be performed by a lamination method or a compression method. The productivity is improved by laminating using the film-shaped photosensitive sealing resin composition. The opening 5 is opened by exposure processing and development processing (see FIG. 4). In the exposure treatment, a predetermined portion of the photosensitive encapsulating resin composition 4 is exposed to light by irradiating an actinic ray through a mask pattern, and photocured. As a light source for the actinic ray, a known light source can be used, and a light source that effectively emits ultraviolet rays such as a carbon arc lamp, a mercury vapor arc lamp, an ultra-high pressure mercury lamp, a high pressure mercury lamp, and a xenon lamp can be used. Further, a direct drawing type direct laser exposure may be used. The exposure dose varies depending on the device used and the composition of the photosensitive sealing resin composition 4, but is preferably 100 to 1000 mJ / cm ² , more preferably 600 to 800 mJ / cm ² . Tend to exposure is likely to be molded with sufficient photocuring if 100 mJ / cm ² or more, while the opening 5 from the upper surface of the photosensitive sealing resin composition 4 if 1000 mJ / cm ² or less, It is advantageous to form the fixing member 2 so as to penetrate it. Next, the fixing member 2 is exposed from the coated photosensitive sealing resin composition 4 by removing the photosensitive sealing resin composition 4 other than the exposed portions by development. As a developing solution used in the developing treatment, for example, an alkali developing solution such as an aqueous solution of tetramethylammonium hydroxide (1 to 5% by mass aqueous solution) at 20 to 50 ° C. is used, and spraying, rocking immersion, brushing, scraping and the like are used. Developed by the known method. Thereby, a predetermined pattern is formed. The dissolution rate of the photosensitive sealing resin composition 4 in a developing solution is 3.0 μm / s or less, and more preferably 1.0 to 2.5 μm / s. If it is 3.0 μm / s or less, the pattern shape formed by the exposure operation can be held relatively well. On the other hand, when it is larger than 3.0 μm / s, the solubility in not only the unexposed portion but also the exposed portion is increased, and there is a tendency that a defect such as a defective formation of the opening occurs. The dissolution rate in the developer can be adjusted depending on the photosensitive sealing resin composition to be used, the developer (type, temperature), and the like. After the opening 5 is provided by the developing process, a thermosetting process at about 150 ° C. for about 1 hour may be performed. The thickness of the photosensitive sealing resin composition 4 is preferably 50 to 200 μm. The thickness of the photosensitive sealing resin composition 4 is the height from the photosensitive sealing resin composition surface in contact with the upper surface of the fixing member 2 in FIG. When the thickness is 50 μm or more, the semiconductor element 3 tends to be easily sealed. On the other hand, if it is 200 μm or less, the occurrence of warpage after sealing tends to be suppressed, and the opening 5 tends to be easily formed.
The minimum melt viscosity of the photosensitive sealing resin composition may be 10 to 500 Pa · s. The minimum melt viscosity is a value obtained by measuring the melt viscosity in the range of 25 to 200 ° C. by using the photosensitive sealing resin composition before exposure, setting the temperature to 10 ° C./min, the frequency to 1 Hz.
The cured product of the photosensitive sealing resin composition 4 after the exposure treatment and the heat curing treatment preferably has a coefficient of thermal expansion at 0 to 80 ° C. of 20 × 10 ⁻⁶ to 80 × 10 ⁻⁶ / K. If it is 20 × 10 ⁻⁶ / K or more, the amount of filler does not need to be increased, and there is less concern that the resolution of the photosensitive encapsulating resin composition 4 is reduced. On the other hand, when it is 80 × 10 ⁻⁶ / K or less, the warpage of the package tends to be easily suppressed. The heat curing treatment is preferably performed at about 150 ° C. for about 1 hour. Preferably it is 100-230 degreeC, More preferably, it is 120-220 degreeC, More preferably, it is 140-210 degreeC, Although it does not specifically limit about a curing time, Preferably, it is 30-300 minutes, More preferably, it is 40-240. Minutes, more preferably 50 to 200 minutes.

  Next, a conductive material is applied to the openings 5 of the photosensitive sealing resin composition 4 (see FIG. 5). As the conductive material, besides Al, Cu, Sn, Ni, Au, Ag, or the like, a conductive material or alloy can be given. Examples of the applying method include sputtering, PVD, CVD, electrolytic plating, and electroless plating. In particular, when electrolytic plating is performed, a metal seed layer is formed in advance by sputtering or the like, and then the metal can be applied (filled) to the openings by a method such as electrolytic plating. Before the metal plating is formed, pickling treatment or plasma treatment may be performed in order to remove the residue on the fixing member 2.

  Next, the semiconductor element fixing base material 1 and the fixing member 2 are removed (FIG. 6 shows an inverted state). Although there is no particular limitation on the removing method, the semiconductor element fixing base material 1 and the fixing member 2 can be removed by using a heat-peelable fixing member 2 and heating the fixing member 2.

  The material used for the rewiring insulating layers 7 and 9 formed on the photosensitive sealing resin composition 4 may be a photosensitive resin or a thermosetting resin (see FIGS. 7, 8 and 9). Further, it may be liquid or film. In the case of using a liquid photosensitive material, a layer having a predetermined thickness is formed by a spin coater, and then a predetermined pattern is formed by exposure and development, followed by thermosetting in a nitrogen atmosphere. Thereafter, if necessary, a seed layer is formed by electroless plating or sputtering (not shown). Thereafter, a wiring forming resist is formed, and a pattern is formed by exposure and development. Next, a wiring pattern 8 is formed by electrolytic plating or the like (see FIG. 8). Next, the resist is stripped, and the seed layer is removed (not shown). Thereafter, the rewiring insulating layer 9 is formed of a photosensitive material (see FIG. 9). If multiple layers are required, these cycles can be repeated again. When the seed layer is formed by the electroless copper plating method, the thickness of the seed layer is not particularly limited, but usually 0.1 to 1.0 μm is preferably used. By forming the seed layer before forming the wiring pattern 8, the electrolytic copper plating method becomes possible, and the wiring pattern 8 can be selectively formed. The seed layer can be formed not only by electroless copper plating but also by sputtering. The target can be appropriately selected, but Ti / Cu is generally used. The thickness of the Ti or Cu layer is not particularly limited, but is preferably about 20 to 100 nm for Ti and about 100 to 500 nm for Cu. For the formation of solder balls, the outermost layer electrode can be plated using a commercially available electroless nickel / gold plating solution or the like. The thickness of the nickel plating is preferably 1 to 10 μm, and the thickness of the gold plating is preferably 0.01 to 1.0 μm, more preferably 0.05 to 0.15 μm.

Next, as shown in FIG. 9, the solder balls 10 are mounted on the electrodes. Mounting the solder balls 10 can be easily performed by using a commercially available N ₂ reflow apparatus. The timing for mounting the solder balls 10 is not particularly limited, and may be after the individual pieces as needed.
Finally, as shown in FIG. 10, the semiconductor device 100 can be obtained by singulation.

  The above-described semiconductor package 100 is particularly suitable in a mode in which miniaturization and increase in the number of pins are required. In particular, the manufacturing method of the present invention is suitable for a form in which a FO-WLP (Fan-out Wafer Level Package) is made three-dimensional.

  As described above, the method for manufacturing a semiconductor device (semiconductor package) and the material for a semiconductor package according to the present invention have been described. However, the present invention is not necessarily limited to the above-described embodiment, and may be appropriately changed without departing from the gist of the present invention. Changes may be made.

  The objects and advantages of the present disclosure will be further illustrated by the following examples, which should not be unduly limited by the specific materials and amounts thereof, as well as other conditions and details, recited in these examples. Should not be interpreted.

  First, an SUS plate (SUS304 processed to a diameter of 220 mm and a thickness of 1.5 mm) was prepared as a substrate for fixing a semiconductor element. On the surface of the SUS plate, a fixing member (manufactured by Nitto Denko Corporation, trade name: Riba Alpha; heat release sheet) having a thickness of 18 μm is roll-laminated (trade name: HOTDOG 12DX, manufactured by Ramie Corporation, temperature: 60 ° C., wire) It was attached using a pressure of 4 kgf / cm (39.2 N / cm) and a feed rate of 0.5 m / min (FIG. 1). At that time, the side opposite to the surface (foamed surface) of the fixing member (river alpha) film that was foamed by heating was bonded to the SUS plate.

<Preparation of silicon wafer for semiconductor device>
An 8-inch wafer semiconductor element (Waltz Co., Ltd., trade name: WALTS-TEG CC80-0101JY_ (PI) _ModelI) was prepared (not shown). The wafer was processed to a thickness of 40 μm by back grinding.

<Attaching dicing tape to silicon wafer for semiconductor device>
A dicing tape (manufactured by Hitachi Chemical Co., Ltd., trade name: HAE-1504) was prepared. The method of forming the dicing tape will be described below. The dicing tape is peeled off from the surface opposite to the active surface of the semiconductor element wafer, and the polyethylene film as the protective film is peeled off, and a press-type vacuum laminator (manufactured by Meiki Seisakusho Co., Ltd., trade name: MVLP-500) is used. Attached. The pressing was performed at a hot plate temperature of 40 ° C., a vacuum evacuation time of 30 seconds, a lamination press time of 60 seconds, an air pressure of 4 kPa or less, and a pressure of 0.5 MPa.

<Preparation of semiconductor device>
The above-mentioned silicon wafer for semiconductor elements to which the dicing tape was attached was diced into a size of 10 mm in length and 10 mm in width. For dicing, a dicing saw for silicon wafers (trade name: DAD-3350, manufactured by Disco Corporation) was used. A 27 HEFF dicing blade was used, and the number of revolutions per minute was 30,000 revolutions / minute and the cutting speed was 20 mm / sec.

<Semiconductor device mounting>
The singulated semiconductor element was mounted such that the active surface was bonded to the fixing member (see FIG. 2). A flip chip bonder (manufactured by Panasonic Corporation, trade name: FCB3 NM-SB50A) was used for mounting. The SUS plate with the fixing member attached to the stage was fixed by suction. The stage was mounted at a setting temperature of 50 ° C., a head temperature of the flip chip bonder was 50 ° C., and a pressure bonding time was 1 second. The load at the time of press bonding was 10 N.

<Synthesis of photosensitive sealing resin composition: alkali-soluble resin PI-1>
In a 300 mL round bottom flask equipped with a stirrer, a thermometer, a nitrogen purge device (nitrogen inflow tube), and a reflux condenser with a water receiver, 2,2-bis (3-amino-4-hydroxy) as a diamine was placed. 39 g (0.11 mol) of phenyl) hexafluoropropane (manufactured by Central Glass Co., Ltd., trade name: BIS-AP-AF, molecular weight: 366), D-400 (polyoxyalkylene diamine, manufactured by BASF), trade name: D-400, molecular weight: 433) was 46 g (0.11 mol), and BY16-871EG (siloxane diamine, manufactured by Dow Corning Toray Co., Ltd., trade name: BY16-871EG, molecular weight: 248.5) was 6.6 g (0). .027 mol) and 13.1 g (0.12 mol) of m-AP (metaaminophenol, manufactured by Wako Pure Chemical Industries, Ltd., special grade) And a solvent in which NMP (N-methylpyrrolidone, manufactured by Wako Pure Chemical Industries, Ltd., dehydrated) were charged 200 g, was stirred to a diamine is dissolved in a solvent.

  While cooling the flask in an ice bath, 93 g (0.30 mol) of ODPA (4,4'-oxydiphthalic dianhydride, manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little to the solution in the flask. After the addition was completed, the temperature of the solution was raised to 180 ° C. while blowing nitrogen gas, and the temperature was maintained for 3 hours to obtain a polyimide resin PI-1 as an alkali-soluble resin. The obtained polyimide resin was thinly applied on an aluminum cup, and was dried at 180 ° C. for 3 hours using a hot air convection dryer (trade name: MSO-80TPS, manufactured by Futaba Kagaku Co., Ltd.). The heating residue of the polyimide was measured to be 75% by mass.

<Preparation of photosensitive sealing resin composition solution (S-1)>
Using the alkali-soluble resin obtained above and the other compounds shown below, the respective components were blended at the following composition ratio (unit: parts by mass), and a photosensitive sealing resin composition solution (S -1) was obtained.

(I) Isocyanuric acid EO-modified di and triacrylate (manufactured by Toagosei Co., Ltd., trade name: M-313): 29.8% by mass.
(II) bisphenol F type bisglycidyl ether (manufactured by Toto Kasei Kogyo Co., Ltd., trade name: YDF-870GS): 18.24% by mass.
(III) Trisphenol compound (α, α, α′-tris (4-hydroxyphenol) -1-ethyl-4-isopropylbenzene) (trade name: TrisP-PA, manufactured by Honshu Chemical Industry Co., Ltd.): 4. 3% by mass.
(IV) Hydrophobic fumed silica (average particle size: about 16 nm) (manufactured by Nippon Aerosil Co., Ltd., trade name: R-972) (N-methyl-2-pyrrolidone (Kanto Chemical Co., Ltd., special grade)) % By mass): 4.3% by mass.
(V) The alkali-soluble resin (polyimide resin PI-1): 42.5% by mass.
(VI) Photoinitiator (bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by BASF, trade name: I-819)): 1.24% by mass.
(VII) Dicumyl peroxide (manufactured by NOF CORPORATION, trade name: Parkmill D) 0.43% by mass.
(VIII) Curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name: 2P4MHZ) (10% by mass dissolved in N-methyl-2-pyrrolidone (Kanto Chemical Co., Ltd., special grade)): 0.43% by mass.
(IX) Solvent (N-methyl-2-pyrrolidone) (Kanto Chemical Co., Ltd., special grade): 10 mL.

<Synthesis of photosensitive sealing resin composition: alkali-soluble resin PI-2>
In a 300 mL round bottom flask equipped with a stirrer, a thermometer, a nitrogen purge device (nitrogen inflow tube), and a reflux condenser with a water receiver, 2,2-bis (3-amino-4-hydroxy) as a diamine was placed. 54 g (0.15 mol) of phenyl) hexafluoropropane (manufactured by Central Glass Co., Ltd., trade name: BIS-AP-AF, molecular weight: 366), D-400 (polyoxyalkylene diamine, manufactured by BASF), trade name: D-400, molecular weight: 433) 22 g (0.051 mol), BY16-871EG (siloxane diamine, manufactured by Dow Corning Toray, trade name: BY16-871EG, molecular weight: 248.5) 6.6 g (0) .027 mol) and 13.1 g (0.12 mol) of m-AP (metaaminophenol, manufactured by Wako Pure Chemical Industries, Ltd., special grade) , And the solvent is a NMP (N-methylpyrrolidone, manufactured by Wako Pure Chemical Industries, Ltd., dehydrated) were charged 200 g, was stirred to a diamine is dissolved in a solvent.

  While cooling the flask in an ice bath, 93 g (0.30 mol) of ODPA (4,4'-oxydiphthalic dianhydride, manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little to the solution in the flask. After completion of the addition, the solution was heated to 180 ° C. while blowing nitrogen gas, and kept warm for 3 hours to obtain a polyimide resin PI-2, which is an alkali-soluble resin. The obtained polyimide resin was thinly applied on an aluminum cup, and was dried at 180 ° C. for 3 hours using a hot air convection dryer (trade name: MSO-80TPS, manufactured by Futaba Kagaku Co., Ltd.). The heating residue of the polyimide was measured to be 75% by mass.

<Preparation of photosensitive sealing resin composition solution (S-2)>
Except for using the alkali-soluble resin (PI-2) instead of the alkali-soluble resin (PI-1), the photosensitive sealing resin is prepared in the same manner as the photosensitive sealing resin composition solution (S-1). A composition solution (S-2) was obtained.

<Synthesis of photosensitive sealing resin composition: alkali-soluble resin PI-3>
In a 300 mL round bottom flask equipped with a stirrer, a thermometer, a nitrogen purge device (nitrogen inflow tube), and a reflux condenser with a water receiver, 2,2-bis (3-amino-4-hydroxy) as a diamine was placed. 77.5 g (0.21 mol) of phenyl) hexafluoropropane (manufactured by Central Glass Co., Ltd., trade name: BIS-AP-AF, molecular weight: 366), BY16-871EG (siloxane diamine, manufactured by Dow Corning Toray Co., Ltd.) 6.6 g (0.027 mol) of trade name: BY16-871EG, molecular weight: 248.5), and 13.1 g (0.12 mol) of m-AP (metaaminophenol, manufactured by Wako Pure Chemical Industries, Ltd., special grade) ) And 200 g of NMP (N-methylpyrrolidone, manufactured by Wako Pure Chemical Industries, Ltd., dehydrated) as a solvent, and stirred to dissolve the diamine in the solvent. It was.

  While the flask was cooled in an ice bath, 93 g (0.30 mol) of ODPA (4,4'-oxydiphthalic dianhydride, manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little to the solution in the flask. After the addition was completed, the temperature of the solution was raised to 180 ° C. while blowing nitrogen gas, and the temperature was maintained for 3 hours to obtain a polyimide resin PI-3 as an alkali-soluble resin. The obtained polyimide resin was thinly applied on an aluminum cup, and was dried at 180 ° C. for 3 hours using a hot air convection dryer (trade name: MSO-80TPS, manufactured by Futaba Kagaku Co., Ltd.). The heating residue of the polyimide was measured to be 75% by mass.

<Preparation of photosensitive sealing resin composition solution (S-3)>
Except for using the alkali-soluble resin (PI-3) instead of the alkali-soluble resin (PI-1), the photosensitive encapsulating resin is prepared in the same manner as the photosensitive encapsulating resin composition solution (S-1). A composition solution (S-3) was obtained.

<Synthesis of photosensitive sealing resin composition: alkali-soluble resin PI-4>
In a 300 mL round bottom flask equipped with a stirrer, a thermometer, a nitrogen purge device (nitrogen inflow tube), and a reflux condenser with a water receiver, 2,2-bis (3-amino-4-hydroxy) as a diamine was placed. 43.8 g (0.12 mol) of phenyl) hexafluoropropane (manufactured by Central Glass Co., Ltd., trade name: BIS-AP-AF, molecular weight: 366), D-400 (polyoxyalkylenediamine, manufactured by BASF), product 51.9 g (0.12 mol) of name: D-400, molecular weight: 433), and 7 of BY16-871EG (siloxane diamine, manufactured by Dow Corning Toray, trade name: BY16-871EG, molecular weight: 248.5) 7 6.5 g (0.030 mol), 6.54 g (0.03 g) of m-AP (metaaminophenol, manufactured by Wako Pure Chemical Industries, Ltd.) 0 mol), and the solvent is a NMP (N-methylpyrrolidone, manufactured by Wako Pure Chemical Industries, Ltd., dehydrated) were charged 200 g, was stirred to a diamine is dissolved in a solvent.

  While the flask was cooled in an ice bath, 93 g (0.30 mol) of ODPA (4,4'-oxydiphthalic dianhydride, manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little to the solution in the flask. After the addition was completed, the temperature of the solution was raised to 180 ° C. while blowing nitrogen gas, and the temperature was maintained for 3 hours to obtain a polyimide resin PI-4, which is an alkali-soluble resin. The obtained polyimide resin was thinly applied on an aluminum cup, and was dried at 180 ° C. for 3 hours using a hot air convection dryer (trade name: MSO-80TPS, manufactured by Futaba Kagaku Co., Ltd.). The heating residue of the polyimide was measured to be 75% by mass.

<Preparation of photosensitive sealing resin composition solution (S-4)>
Except for using the alkali-soluble resin (PI-4) instead of the alkali-soluble resin (PI-1), the photosensitive sealing resin is prepared in the same manner as the photosensitive sealing resin composition solution (S-1). A composition solution (S-4) was obtained.

<Synthesis of photosensitive sealing resin composition: alkali-soluble resin PI-5>
In a 300 mL round bottom flask equipped with a stirrer, a thermometer, a nitrogen purge device (nitrogen inflow tube), and a reflux condenser with a water receiver, 2,2-bis (3-amino-4-hydroxy) as a diamine was placed. 18 g (0.049 mol) of phenyl) hexafluoropropane (manufactured by Central Glass Co., Ltd., trade name: BIS-AP-AF, molecular weight: 366), D-400 (polyoxyalkylene diamine, manufactured by BASF), trade name: D-400, molecular weight: 433) was 65 g (0.15 mol), and BY16-871EG (siloxane diamine, manufactured by Dow Corning Toray, trade name: BY16-871EG, molecular weight: 248.5) was 6.6 g (0). .027 mol) and 13.1 g (0.12 mol) of m-AP (metaaminophenol, manufactured by Wako Pure Chemical Industries, Ltd., special grade) , And the solvent is a NMP (N-methylpyrrolidone, manufactured by Wako Pure Chemical Industries, Ltd., dehydrated) were charged 200 g, was stirred to a diamine is dissolved in a solvent.

<Preparation of photosensitive sealing resin composition solution>
While cooling the flask in an ice bath, 93 g (0.30 mol) of ODPA (4,4'-oxydiphthalic dianhydride, manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little to the solution in the flask. After the addition was completed, the temperature of the solution was raised to 180 ° C. while blowing nitrogen gas, and the temperature was maintained for 3 hours to obtain a polyimide resin PI-5, which is an alkali-soluble resin. The obtained polyimide resin was thinly applied on an aluminum cup, and was dried at 180 ° C. for 3 hours using a hot air convection dryer (trade name: MSO-80TPS, manufactured by Futaba Kagaku Co., Ltd.). The heating residue of the polyimide was measured to be 75% by mass.

<Preparation of photosensitive sealing resin composition solution (S-5)>
Except for using the alkali-soluble resin (PI-5) instead of the alkali-soluble resin (PI-1), the photosensitive sealing resin is prepared in the same manner as the photosensitive sealing resin composition solution (S-1). A composition solution (S-5) was obtained.

<Synthesis of photosensitive sealing resin composition: alkali-soluble resin PI-6>
In a 300 mL round bottom flask equipped with a stirrer, a thermometer, a nitrogen purge device (nitrogen inflow tube), and a reflux condenser with a water receiver, 2,2-bis (3-amino-4-hydroxy) as a diamine was placed. 39 g (0.11 mol) of phenyl) hexafluoropropane (manufactured by Central Glass Co., Ltd., trade name: BIS-AP-AF, molecular weight: 366), D-400 (polyoxyalkylene diamine, manufactured by BASF), trade name: D-400, molecular weight: 433) was 46 g (0.11 mol), and BY16-871EG (siloxane diamine, manufactured by Dow Corning Toray Co., Ltd., trade name: BY16-871EG, molecular weight: 248.5) was 6.6 g (0). .027 mol) and 13.1 g (0.12 mol) of m-AP (metaaminophenol, manufactured by Wako Pure Chemical Industries, Ltd., special grade) And a solvent in which NMP (N-methylpyrrolidone, manufactured by Wako Pure Chemical Industries, Ltd., dehydrated) were charged 200 g, was stirred to a diamine is dissolved in a solvent.

  While the flask was cooled in an ice bath, 93 g (0.30 mol) of ODPA (4,4'-oxydiphthalic dianhydride, manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little to the solution in the flask. After the addition was completed, the temperature of the solution was raised to 180 ° C. while blowing nitrogen gas, and the temperature was maintained for 3 hours to obtain a polyimide resin PI-6, which is an alkali-soluble resin. The obtained polyimide resin was thinly applied on an aluminum cup, and was dried at 180 ° C. for 3 hours using a hot air convection dryer (trade name: MSO-80TPS, manufactured by Futaba Kagaku Co., Ltd.). The heating residue of the polyimide was measured to be 75% by mass.

<Preparation of photosensitive sealing resin composition solution (S-6)>
Using the alkali-soluble resin obtained above and the other compounds shown below, the respective components were blended at the following composition ratio (unit: parts by mass), and a photosensitive sealing resin composition solution (S -6) was obtained.

(I) Isocyanuric acid EO-modified di- and triacrylate (manufactured by Toagosei Co., Ltd., trade name: M-313): 33.4% by mass.
(II) bisphenol F-type bisglycidyl ether (manufactured by Toto Kasei Kogyo Co., Ltd., trade name: YDF-870GS): 9.5% by mass.
(III) Trisphenol compound (α, α, α'-tris (4-hydroxyphenol) -1-ethyl-4-isopropylbenzene) (trade name: TrisP-PA, manufactured by Honshu Chemical Industry Co., Ltd.): 39% by mass.
(IV) Hydrophobic fumed silica (average particle size: about 16 nm) (manufactured by Nippon Aerosil Co., Ltd., trade name: R-972) (N-methyl-2-pyrrolidone (Kanto Chemical Co., Ltd., special grade)) % By mass): 4.77% by mass.
(V) The alkali-soluble resin (polyimide resin PI-6): 47.7% by mass
(VI) Photoinitiator (bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by BASF, trade name: I-819)): 1.43% by mass.
(VII) Dicumyl peroxide (manufactured by NOF CORPORATION, trade name: Parkmill D) 0.48% by mass.
(VIII) Curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd., trade name: 2P4MHZ) (dissolved in N-methyl-2-pyrrolidone (Kanto Chemical Co., Ltd., special grade) at 10% by mass): 0.24% by mass.
(IX) Solvent (N-methyl-2-pyrrolidone) (Kanto Chemical Co., Ltd., special grade): 10 mL.

<Preparation of photosensitive sealing resin composition solution (SE-1)>
Each component was blended at the composition ratio (unit: parts by mass) shown below to obtain a photosensitive sealing resin composition solution (SE-1).
(I) Acid-modified cresol novolak type epoxy acrylate (manufactured by DIC, trade name: EXP-2810): 39.2% by mass.
(II) Photoreactive compound (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA): 6.9% by mass.
(III) As photoinitiator, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, manufactured by BASF, trade name: DAROCURE-TPO): 1.4% by mass, and 2,4-diethylthioxanthone (Nippon Kagaku) Product name: Kayacure DETX-S, manufactured by Yakuhin Co., Ltd .: 0.1% by mass.
(IV) Thermosetting resin (biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: NC-3000H): 4.6% by mass, bisphenol F type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Name: YSLV-80): 9.2% by mass.
(V) Inorganic filler component: Barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., trade name: B30): 14% by mass, silica (manufactured by Admatex Co., Ltd., sample name: MEK slurry (1)): 23% by mass. The average particle size and the maximum particle size in a state where the inorganic filler is dispersed in the photosensitive resin composition are measured using a laser diffraction scattering microtrack particle size distribution meter (manufactured by Nikkiso Co., Ltd., trade name: MT-3100). did. The average particle size of B30 was 0.3 μm, and the average particle size of MEK slurry (1) was 0.5 μm. The maximum particle size of the inorganic filler containing B30 and MEK slurry was 3 μm or less. The particle size of the inorganic filler after forming the film was confirmed by observing a cross section of the inorganic filler after curing the film with an electron microscope (manufactured by Hitachi High-Technologies Corporation, trade name: SU-1510). It was confirmed that the maximum particle size of the inorganic filler dispersed in the film was 5 μm or less.
(VI) The following were used as other components. Butadiene-based elastomer (manufactured by Daicel Corporation, trade name: Eporide PB3600): 1.4% by mass, polymerization inhibitor (manufactured by Kawaguchi Chemical Industry Co., Ltd., trade name: Antage 500): 0.2% by mass.

<Preparation of photosensitive sealing resin composition solution (SE-2)>
Each component was blended at the composition ratio (unit: parts by mass) shown below to obtain a photosensitive sealing resin composition solution (SE-2).
(I) Acid-modified cresol novolak type epoxy acrylate (manufactured by DIC Corporation, trade name: EXP-2810): 48.4% by mass.
(II) Photoreactive compound (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd., trade name: KAYARAD DPHA): 8.5% by mass.
(III) As a photoinitiator, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, manufactured by BASF, trade name: DAROCURE-TPO): 1.7% by mass, and 2,4-diethylthioxanthone (Nippon Kagaku) Product name: Kayacure DETX-S, manufactured by Yakuhin Co., Ltd .: 0.2% by mass.
(IV) Thermosetting resin (biphenyl aralkyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd., trade name: NC-3000H): 5.7% by mass, bisphenol F type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Name: YSLV-80): 11% by mass.
(V) Inorganic filler component: Barium sulfate (manufactured by Sakai Chemical Industry Co., Ltd., trade name: B30): 8.5% by mass, silica (manufactured by Admatechs, sample name: MEK slurry (1)): 14% by mass %. The average particle size and the maximum particle size in a state where the inorganic filler is dispersed in the photosensitive resin composition are measured using a laser diffraction scattering microtrack particle size distribution meter (manufactured by Nikkiso Co., Ltd., trade name: MT-3100). did. The average particle size of B30 was 0.3 μm, and the average particle size of MEK slurry (1) was 0.5 μm. The maximum particle size of the inorganic filler containing B30 and MEK slurry was 3 μm or less. The particle size of the inorganic filler after forming the film was confirmed by observing a cross section of the inorganic filler after curing the film with an electron microscope (manufactured by Hitachi High-Technologies Corporation, trade name: SU-1510). It was confirmed that the maximum particle size of the inorganic filler dispersed in the film was 5 μm or less.
(VI) The following were used as other components. Butadiene-based elastomer (manufactured by Daicel Corporation, trade name: Eporide PB3600): 1.7% by mass, polymerization inhibitor (manufactured by Kawaguchi Chemical Industry Co., Ltd., trade name: Antage 500): 0.3% by mass.

<Film molding of photosensitive sealing resin composition solution>
Using the photosensitive sealing resin composition solution obtained above, it was formed into a film by the following operation, and the photosensitive sealing resins of Examples 1 to 6, Reference Examples 1 to 3 and Comparative Examples 1 to 3 were formed. A composition (a film-shaped photosensitive sealing resin material) was obtained. The photosensitive sealing resin composition solution obtained above was coated on a 50 μm-thick polyethylene terephthalate film (manufactured by Teijin Limited, trade name: G2-16) as a support layer using a coater (manufactured by Yasui Seiki Co., Ltd. (Trade name: β coater SNC280) to form a photosensitive sealing resin composition layer by uniform application. The coating speed was 3.0 mm / min. Subsequently, the resultant was dried at 80 ° C for 20 minutes using a hot air convection dryer (trade name: MSO-80TPS, manufactured by Futaba Kagaku Co., Ltd.), and further dried at 120 ° C for 20 minutes. For the thickness at the time of coating, after sealing the semiconductor element by the following procedure, set the distance between the knife of the coater and the coating surface so that a predetermined thickness is obtained when measured by the following measuring method. Was adjusted.

  Subsequently, a roll laminator was formed as a polyethylene film (trade name: NF-15) (protective film) on the surface of the photosensitive sealing resin composition layer opposite to the side in contact with the support layer as a protective film. (Trade name: HOTDOG 12DX, temperature 60 ° C., linear pressure 4 kgf / cm (39.2 N / cm), feed rate 0.5 m / min, manufactured by Ramie Corporation) to obtain a photosensitive sealing resin composition Was.

<Seal of semiconductor element using photosensitive sealing resin composition>
Using this photosensitive sealing resin composition, it was stuck on the semiconductor element fixed on the fixing member. The method for forming the photosensitive sealing resin composition is described below. The photosensitive encapsulating resin composition was adhered on the semiconductor element using a press-type vacuum laminator (trade name: V130, manufactured by Nikko Materials Co., Ltd.) after peeling off the polyethylene film of the protective film (FIG. 3). reference). Laminating conditions were as follows: a hot plate temperature for pressing was 100 ° C., a vacuuming time was 18 seconds, a laminating press time was 60 seconds, an air pressure was 4 kPa or less, and a pressure for bonding was 0.4MP.

<Method for measuring thickness of photosensitive sealing resin composition after semiconductor element sealing>
A method for measuring the thickness of the photosensitive sealing resin composition after sealing will be described.
After sealing the semiconductor element with the photosensitive sealing resin composition, the thickness of a portion where no semiconductor element was present was measured with a film thickness meter (manufactured by Mitutoyo Corporation, trade name: Digimatic Indicator ID-H). .

<Evaluation test>
The following evaluation tests were performed on the photosensitive sealing resin composition obtained above.

<Measurement method of developer dissolution rate of photosensitive sealing resin composition>
A method for measuring the developer dissolution rate of the photosensitive sealing resin composition will be described. The above photosensitive encapsulating resin composition, coated to a thickness of 300 μm, is pressed on a mirror surface of an 8-inch silicon wafer (manufactured by Enatec Co., Ltd.) having a thickness of 725 μm, and a press-type vacuum laminator (manufactured by Nikko Materials Co., Ltd.) (Trade name: V130). Laminating conditions were as follows: a hot plate temperature for pressing was 100 ° C., a vacuuming time was 18 seconds, a laminating press time was 60 seconds, an air pressure was 4 kPa or less, and a pressure for bonding was 0.4MP. After sticking, the film thickness was measured with a film thickness meter (manufactured by Mitutoyo Corporation, trade name: Digimatic Indicator ID-H), and this was used as an initial value. 2.38% by mass of tetramethylammonium at 26 ° C. using a spin developing machine (manufactured by Mikasa Corporation, trade name: AD-3000, spray pressure: 0.2 MPa, scan width: 4.0 cm, scan speed: 5.0 cm / sec) An aqueous hydroxide solution (manufactured by Tama Chemical Industry Co., Ltd.) was sprayed for 20 seconds, then washed with pure water for 20 seconds, and further air-dried for 10 seconds. After the development, the film thickness was measured by the above film thickness meter. By repeating the above, the residual film amount with respect to the developing time was plotted, and a linear approximation was performed to calculate the developing speed from the slope value.

<Measurement method of melt viscosity of photosensitive sealing resin composition>
A method for measuring the melt viscosity of the photosensitive sealing resin composition will be described.
The melt viscosity was measured using a low viscosity viscoelasticity measuring device (trade name: MCR-301, manufactured by Anton Paar Japan, Inc.). A photosensitive film formed into a film having a length of 30 mm, a width of 30 mm, and a thickness of 300 μm in the center of the bottom of an aluminum circular plate having a diameter of 4 cm and a depth of 5 mm (trade name: Disposable Plate EMS / CTD600, manufactured by Anton Paar Japan). The sealing resin composition was attached, and the circular plate was fixed on the stage of the device. After a measuring cell (manufactured by Anton Paar Japan, Inc., trade name: Messkoperachse D-CP / PP7) was attached to the apparatus, a jig (manufactured by Anton Paar Japan, Inc., trade name: SPPYU08-07) was attached to the tip of the cell. ). The measurement cell was lowered so that the tip of the jig was at a height of 200 μm from the bottom of the circular plate, and the tip of the jig was buried in the photosensitive sealing resin composition. The measurement conditions were set to a temperature rise of 10 ° C./min and a frequency of 1 Hz, and the melt viscosity was measured in the range of 25 to 200 ° C. The lowest value of the melt viscosity in the temperature range was defined as the lowest melt viscosity.

<Method of measuring storage elastic modulus of photosensitive sealing resin measurement object>
A method for measuring the storage elastic modulus of the photosensitive sealing resin composition after exposure and development will be described. First, a layer of a photosensitive encapsulating resin composition having a thickness of 40 μm was prepared, and this layer was subjected to 1000 mJ / cm using a high-precision parallel exposure machine (manufactured by Oak Co., Ltd., trade name: EXM-1172-B-∞). Exposure is carried out for ² seconds, and then heated on a hot plate at 80 ° C. for about 30 seconds. Thereafter, the above layer was treated at a temperature of 26 ° C. using a developing machine (manufactured by Mikasa Corporation, trade name: AD-3000, spray pressure: 0.2 MPa, scan width: 4.0 cm, scan speed: 5.0 cm / sec). A 38% by mass aqueous solution of tetramethylammonium hydroxide (manufactured by Tama Chemical Industry Co., Ltd.) was sprayed for 180 seconds, then washed with pure water for 20 seconds, and further air-dried for 10 seconds. Two films thus obtained were prepared, dried by heating at 120 ° C. for 10 minutes, and then roll laminator (trade name: HOTDOG 12DX, manufactured by Ramie Corporation, temperature: 60 ° C., linear pressure: 4 kgf / cm (39.2 N) / Cm) at a feed rate of 0.5 m / min) to obtain a laminate having a thickness of 80 μm. Next, the obtained laminate is heated in an oven at 180 ° C. for 3 hours. A sample obtained by cutting the heat-cured laminate into a strip having a width of 5 mm and a length of 30 mm was used as a sample, and the temperature was raised at a rate of 5 ° C. using a viscoelastic analyzer (trade name: RSA-2, manufactured by Rheometrics). / Min, a frequency of 1 Hz, and a measurement temperature of −50 to 300 ° C., and the storage elastic modulus at 110 ° C. is determined.

<Method of measuring thermal expansion coefficient of photosensitive sealing resin composition>
A method for measuring the thermal expansion coefficient of the photosensitive sealing resin composition will be described. First, a layer of a photosensitive encapsulating resin composition having a thickness of 100 μm was prepared, and this layer was 1600 mJ / cm ² using a parallel exposure machine (manufactured by Oak Manufacturing Co., Ltd., trade name: EXM-1201). Exposure was performed with the amount of energy. Next, it was placed on a hot plate (trade name: Triplet Hotplate TH-900, manufactured by AS-ONE Corporation) and heated at 80 ° C. for 1 minute. The polyethylene terephthalate on the photosensitive sealing resin composition is peeled off, and a developing machine (trade name: AD-3000, manufactured by Mikasa Corporation, spray pressure 0.2 MPa, scan width 4.0 cm, scan speed 5.0 cm / sec) Was sprayed with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (manufactured by Tama Chemical Industry Co., Ltd.) for 180 seconds, washed with pure water for 20 seconds, and air-dried for 10 seconds. Two films thus obtained were prepared, dried by heating at 120 ° C. for 10 minutes, and then roll laminator (trade name: HOTDOG 12DX, manufactured by Ramie Corporation, temperature: 60 ° C., linear pressure: 4 kgf / cm (39.2 N) / Cm) at a feed rate of 0.5 m / min) to obtain a laminate having a thickness of 200 μm. Next, the obtained laminate is heated at 175 ° C. for 2 hours in an oven (trade name: PVC-212, manufactured by Espec Corporation). This heat-cured laminate was cut into a strip having a width of 5 mm and a length of 30 mm to obtain a strip-shaped sample. Fix both ends of this strip-shaped sample with a jig, fix it to a thermal analyzer (trade name: TMA / SS6000, manufactured by Seiko Instruments Inc.), and pull both ends so that the load becomes constant. The temperature was raised, and the strain at each temperature was measured. The load was 19.6 mN, the temperature was raised at a rate of 5 ° C./min, and the measurement temperature was -20 to 250 ° C., and the coefficient of thermal expansion was obtained from the linear gradient of the temperature and strain from 0 ° C. to 80 ° C.

<Formation of opening>
A photomask on which a pattern is formed is brought into close contact with the applied photosensitive sealing resin composition, and an energy of 800 mJ / cm ² is applied using a parallel exposure machine (trade name: EXM-1201 manufactured by Oak Manufacturing Co., Ltd.). Exposure was performed in quantity. Then, it was placed on a hot plate (trade name: Triplet Hotplate TH-900, manufactured by As One Corporation) and heated at 80 ° C. for 1 minute. The polyethylene terephthalate on the photosensitive sealing resin composition is peeled off, and a developing machine (trade name: AD-3000, manufactured by Mikasa Corporation, spray pressure 0.2 MPa, scan width 4.0 cm, scan speed 5.0 cm / sec) Is sprayed with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (manufactured by Tama Chemical Industry Co., Ltd.) at 26 ° C. for 180 seconds, then washed with pure water for 20 seconds, and further air-dried for 10 seconds to obtain a photosensitive solution. An opening was provided in the sealing resin composition. Subsequently, ultraviolet irradiation was performed using a parallel exposure machine (manufactured by Oak Manufacturing Co., Ltd., trade name: EXM-1201) at an energy amount of 2000 mJ / cm ² , and an oven (manufactured by Espec Corporation, trade name: PVC-212) was used. ) At 175 ° C. for 2 hours (see FIG. 4).

<Formation of electrolytic copper plating>
A seed layer was formed in the opening of the photosensitive sealing resin composition by a sputtering apparatus (trade name: CFS-12P-100, manufactured by Shibaura Precision Co., Ltd.). In the sputtering, first, a Ti film was formed to a thickness of 100 nm as an adhesive layer, and then Cu was laminated to a thickness of 300 nm. The pressure during sputtering was 10 ⁻⁵ Pa, and the voltage application time was 10 minutes for Ti and 30 minutes for Cu, respectively.
Next, a metal material (copper) was applied (filled) to the opening by electrolytic copper plating (see FIG. 5). The plating solution composition for electrolytic plating is shown below.
(Electroplating solution composition)
5.0 g of copper sulfate (manufactured by Wako Pure Chemical Industries, Ltd., special grade)
120 g of concentrated sulfuric acid (special grade, manufactured by Wako Pure Chemical Industries, Ltd.)
Hydrochloric acid (Wako Pure Chemical Industries, Ltd., special grade) 0.2 g
Was dissolved in pure water to make the whole 1 L. The procedure of electrolytic plating is shown below. First, the anode was connected to a copper plate, and the cathode was connected to the sputtered copper formed on the photosensitive sealing resin composition, so as to be immersed in the plating solution. The current density was set to 1.0 A / dm ^2, and treatment was carried out for 4 hours to give (fill) plated copper in the openings.

<Removal of semiconductor element fixing substrate and fixing member>
Next, the surface of the semiconductor element fixing base material is vacuum-adsorbed to a tape remover (manufactured by AS ONE Corporation, trade name: NEO HOTPLATE HI-1000), and heated to 150 ° C., thereby foaming the fixing member. The photosensitive sealing resin composition containing plated copper was peeled off (see FIG. 6).

<Formation of rewiring insulating layer>
A rewiring insulating layer was formed on the photosensitive sealing resin composition (see FIGS. 7, 8, and 9). Specifically, a photosensitive insulating material (manufactured by Hitachi Chemical Co., Ltd., trade name: AH-1170T) is applied by a spin coater, and a mask is attached and exposed (Mikasa Corporation, trade name: mask aligner MA-200, After performing 300 mJ / cm ² ), using a developing machine (manufactured by Mikasa Corporation, trade name: AD-3000), dip-developing (35) with a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (manufactured by Tama Chemical Industry Co., Ltd.). After infiltration for 2 seconds, a waste liquid was performed by spinning.
Next, heat curing was performed at 200 ° C. for 1 hour in an oven (manufactured by Espec Corporation, trade name: PVC-212) under a nitrogen atmosphere (oxygen concentration: 50 ppm by volume or less). Next, Ti was deposited to a thickness of 100 nm by a sputtering apparatus (trade name: CFS-12P-100, manufactured by Shibaura Precision Co., Ltd.), and Cu was continuously deposited to a thickness of 300 nm to form a seed layer. Next, a dry film resist (manufactured by Hitachi Chemical Co., Ltd., trade name: Phototec RY-3525) was roll-laminated (trade name: HOTDOG 12DX, manufactured by Ramie Corporation, temperature: 60 ° C., linear pressure: 4 kgf / cm (39.2 N / cm) at a feed rate of 0.5 m / min), and a photomask on which a pattern is formed is brought into close contact with each other, and exposed with an exposure machine (manufactured by Oak Manufacturing Co., Ltd., trade name: EXM-1201, 100 mJ / cm ² ). went. Next, spray development was performed for 90 seconds with a 1% by mass aqueous solution of sodium carbonate at 30 ° C. to open the dry film resist. Next, copper plating having a thickness of 5 μm was formed on the seed layer by an electrolytic copper plating method. Next, the dry film resist was peeled off by peeling liquid. Next, the seed layer was removed from the etching solution. Next, a photosensitive insulating material (trade name: AH-1170T, manufactured by Hitachi Chemical Co., Ltd.) was applied again by a spin coater, and exposed and developed. Subsequently, thermal curing was performed at a predetermined temperature of 200 ° C. in a nitrogen atmosphere (oxygen concentration: 50 ppm by volume or less) for one hour (not shown).

<Mounting solder balls>
Using a reflow apparatus (trade name: TNP25-337EM, manufactured by Tamura Corporation), the solder balls were mounted in a nitrogen atmosphere (oxygen concentration: 100 ppm by volume or less) (see FIG. 9).
Finally, the semiconductor device 100 having a package size of 15 mm in length and 15 mm in width was obtained by singulating using Dicer (trade name: DAD-3350, manufactured by Disco Corporation) (see FIGS. 10 and 11). 27 HEFF (manufactured by Disco Corporation) was used as a dicing blade (the number of revolutions per minute was 30,000 revolutions / minute, and the cutting speed was 20 mm / sec) to singulate.

<Evaluation Method of Flatness after Sealing Semiconductor Element of Photosensitive Encapsulating Resin Composition>
The flatness of the photosensitive sealing resin composition after sealing the semiconductor element was evaluated based on the step after sealing the upper part of the semiconductor element and the part without the semiconductor element. The step was measured with a film thickness meter (trade name: Digimatic Indicator ID-H, manufactured by Mitutoyo Corporation).
“◎”: The photosensitive sealing resin composition at the upper portion of the semiconductor element and the portion where the semiconductor element is not present has a step of 0 μm. “○”: The photosensitive sealing resin at the upper portion of the semiconductor element and the portion where the semiconductor element is not present. When the step of the composition exceeds 0 μm and is less than 5 μm “△”: When the step of the photosensitive sealing resin composition in the upper part of the semiconductor element and the portion where the semiconductor element does not exist is 5 μm or more and less than 10 μm “X”: Not applicable to the above (10μm or more)

<How to measure the amount of warpage after package singulation>
The amount of warpage of the package was measured at room temperature (25 ° C.) using a laser displacement meter (manufactured by KEYENCE CORPORATION, LKG80, step 100 μm, measurement range: 15 mm long, 15 mm wide) at room temperature (25 ° C.). A three-dimensional average plane was calculated from the obtained displacement of each point, and the one having the largest difference between the obtained average plane and the displacement obtained by the measurement was defined as the amount of warpage, and evaluated as follows.
“◎”: The amount of warpage is less than 3 μm “○”: The amount of warpage is 3 μm or more and less than 5 μm “△”: The amount of warpage is 5 μm or more and less than 10 μm “×”: The above does not apply (10 μm) Above)

<Evaluation method of the aspect ratio that allows opening of the photosensitive sealing resin composition>
The openable aspect ratio (film thickness / opening diameter) of the photosensitive sealing resin composition was evaluated based on the following criteria.
“◎”: Aspect ratio of 2.0 or more “○”: Aspect ratio of 1.0 or more and less than 2.0 “×”: Aspect ratio of less than 1.0

<Evaluation method of thermal shock test after package singulation>
In the thermal shock test, five pieces of the same singulated package were allowed to stand in a thermal shock tester (NT-1010, manufactured by Espec Corporation), and the temperature was changed from a minimum temperature of −55 ° C. to a maximum temperature of 125 ° C. once. The cycle was subjected to 1000 temperature cycles. Thereafter, 100 openings were randomly extracted from each package, and the number of defects such as cracks and peeling was counted using a metallographic microscope (Erecting Metals Microscope BX51, manufactured by Onlimpus Corporation). This was performed for five packages, the average value was obtained, and the evaluation was performed based on the following criteria.
“A”: Out of 100 openings, the average number of openings with defects was 10 or less “B”: Out of 100 openings, the average number of openings with defects exceeded 10 , 50 or less “C”: Of 100 openings, the average number of openings having defects exceeds 50

Measurement of the photosensitive sealing resin compositions of Examples 1 to 6 and Reference Examples 1 to 3 performed on the dissolution rate, the thickness of the photosensitive sealing resin composition after sealing, the minimum melt viscosity, and the coefficient of thermal expansion ( Evaluation) The results are shown in Table 1.

  Table 2 shows the measurement (evaluation) results of the photosensitive sealing resin compositions of Comparative Examples 1 to 3.

As shown in Tables 1 and 2, according to the resin composition for photosensitive encapsulation and the method for manufacturing a semiconductor device of the present invention, if the dissolution rate is 3.0 μm / s or less, the fine opening formed by the exposure operation. It was confirmed that a semiconductor device (package) having a portion as a sealing material could be manufactured. On the other hand, in Comparative Examples 1, 2, and 3 in which the dissolution rate is higher than 3.0 μm / s, the aspect ratio is adversely affected, and a high aspect shape tends to be hardly obtained. In Example 4 in which the thickness of the encapsulant after encapsulation of the semiconductor element is larger than 200 μm, the amount of package warpage after encapsulation tends to slightly deteriorate, and in Example 5 in which the encapsulation material is smaller than 50 μm, flatness after encapsulation is obtained. Was slightly inferior. In Reference Example 2 in which the minimum melt viscosity exceeds 500 Pa · s, the flatness after sealing tends to be inferior, and in Reference Examples 2 and 3 in which the coefficient of thermal expansion is larger than 80 × 10 ⁻⁶ / K, sealing is performed. It tends to be inferior in the amount of package warpage later.

  DESCRIPTION OF SYMBOLS 1 ... Substrate for fixing a semiconductor element, 2 ... Fixing member, 3 ... Semiconductor element, 4 ... Photosensitive sealing resin composition, 5 ... Opening, 6 ... Reference numeral 7 Rewiring insulating layer 8 Wiring pattern 9 Rewiring insulating layer 10 Solder ball 100 Semiconductor device (semiconductor package) 100A Lower semiconductor package 111 Core substrate 112 Wiring pattern Reference numerals 113, interlayer insulating layer, 114, via opening, 110, printed wiring board for lower package, 120, semiconductor element with bump, 130, underfill material, 140, sealing material, 141, sealing opening, 142, connection material .

Claims (5)

A photosensitive sealing resin composition capable of forming a pattern by exposure and development,
Dissolving in an alkali developing solution at a speed of 1.3 to 3.0 μm / s ,
The minimum melt viscosity of the photosensitive sealing resin composition is 10 Pa · s to 500 Pa · s,
A photosensitive sealing resin composition, wherein the photosensitive sealing resin composition contains a polyimide resin .   The photosensitive sealing resin composition according to claim 1, wherein the thickness of the sealing material after sealing the semiconductor element is 50 µm to 200 µm. After exposure, further claim 1 or 2 thermal expansion coefficient at 0 to 80 ° C. of thermoset after being heat-cured is in the range of 20 × ^{10 -6} / K from 80 × ^{10 -6} / K Photosensitive sealing resin composition. (I) a step of sealing a semiconductor element with the photosensitive sealing resin composition according to any one of claims 1 to 3 ,
(II) a step of forming a pattern by subjecting the photosensitive encapsulating resin composition to an exposure treatment and an alkali development treatment for dissolving the photosensitive sealing resin composition in an alkali development solution at a rate of 1.3 to 3.0 μm / s; ,
(III) applying a conductive material to the formed pattern;
A method for manufacturing a semiconductor device comprising: The semiconductor device having a cured product of the photosensitive sealing resin composition according to any one of claims 1-3.

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