JP5884477B2 - Semiconductor device manufacturing method, semiconductor device obtained thereby, and thermosetting resin composition used therefor - Google Patents

Description

  The present invention relates to a semiconductor device, a manufacturing method thereof, and a thermosetting resin composition. More specifically, the present invention relates to a manufacturing method capable of performing connection between devices of a three-dimensional semiconductor device that is highly demanded for miniaturization and high density, and has a via in a thermosetting resin and excellent reliability. The present invention relates to a method for sufficiently efficiently manufacturing a semiconductor device having a property, a semiconductor device manufactured by the above method, and a thermosetting resin composition suitable for manufacturing the semiconductor device.

The semiconductor device includes a semiconductor element, a printed wiring board on which the semiconductor element is mounted, and an underfill material filled in a gap between the semiconductor element and the printed wiring board. This semiconductor device is mounted on a mounting substrate via solder balls, and exchanges electrical signals with other semiconductor devices.
2. Description of the Related Art In recent years, as semiconductor devices have become lighter, thinner, and smaller, semiconductor elements and printed wiring boards have been increased in density. In addition, mounting forms such as a package-on-package in which a semiconductor device is stacked on a semiconductor device are actively performed, and it is expected that the mounting density of the semiconductor device will increase further in the future.

  By the way, when a semiconductor device is stacked on a semiconductor device like a package-on-package, it is necessary to provide an external connection terminal for mounting the upper semiconductor device on the printed wiring board of the lower semiconductor device. . Therefore, if the number of external connection terminals of the upper semiconductor device increases, it is necessary to provide corresponding external connection terminals in the lower semiconductor device. However, the conventional semiconductor device has a low mounting density and is mounted. Since the number of external connection terminals of the semiconductor device is small, the external connection terminals can be easily provided.

  However, as miniaturization of semiconductor elements and semiconductor devices progresses and the number of external connection terminals increases, the semiconductor elements of the lower semiconductor device are sealed with a thermosetting resin, and the connection vias between the devices are heated with a laser. A so-called TMV (Through Mold Via) structure semiconductor device provided in a curable resin has emerged (see, for example, Patent Documents 1 to 4).

U.S. Pat. No. 7,671,457 U.S. Pat. No. 7,633,765 US Patent No. 8026587 US Patent No. 801068

  Since the semiconductor devices described in Patent Documents 1 to 4 are provided with vias in the thermosetting resin material using a laser, even when the solder ball diameter or pitch of the semiconductor device is reduced, the connection between the devices is good. Can be obtained.

  FIG. 8 shows a conventional method for manufacturing a semiconductor device. The semiconductor device 10A shown in FIG. 8E has vias for exchanging electrical signals with the outside. The semiconductor device 10A includes a semiconductor element, a printed wiring board on which the semiconductor element is mounted, an underfill material that fills a gap between the semiconductor element and the printed wiring board, a thermosetting resin that seals the semiconductor element, and the like. Can be obtained by appropriately forming vias.

  In the semiconductor device 10A, first, a semiconductor element is mounted on a printed wiring board (see FIG. 8A). Next, the gap between the semiconductor element and the printed wiring board is filled with an underfill material and cured as necessary (see FIG. 8B). Next, the semiconductor element is sealed with a thermosetting resin and cured as necessary (see FIG. 8C). Next, vias are formed using YAG laser, carbon dioxide laser, or excimer laser at the places that need to be electrically connected to the outside, and the electrodes on the printed wiring board are exposed (FIG. 8D). reference). Next, the semiconductor device 10A can be manufactured by filling the vias with solder by a printing method or ball mounting, melting as necessary, and uniformly filling the vias with the solder (FIG. 8E). reference). At this time, the solder may be supplied in advance on the electrodes of the printed wiring board.

  The semiconductor device 10A thus obtained can be mounted with another semiconductor device on the semiconductor device. However, the semiconductor device 10A manufactured by such a method requires introduction of a new facility such as a laser, and the thermosetting resin is oxidized by the heat of the laser, so that another semiconductor device is mounted on the semiconductor device. When mounting, flux activity is hindered, connection failure is likely to occur, it is necessary to use different lasers according to the aperture diameter, it is difficult to provide a relatively large aperture or special aperture, via As the number increases, there are problems such as the time required for via formation.

  The present invention has been made in view of the above problems, and an object thereof is to provide a method for sufficiently efficiently manufacturing a semiconductor device having vias in a thermosetting resin and having excellent reliability. And Another object of the present invention is to provide a semiconductor device manufactured by the above method and a thermosetting resin composition suitable for manufacturing the semiconductor device.

The present invention
(I) a step of forming a pattern of a photosensitive resin composition on a printed wiring board having a conductor circuit, and then subjecting the layer to exposure and development to form a pattern;
(II) mounting a semiconductor element on a printed wiring board;
(III) a step of thermosetting after forming a layer made of a thermosetting resin composition so as to cover at least part of the semiconductor element and the photosensitive resin composition;
(IV) a step of grinding a surface of a layer made of the thermosetting resin composition to expose a pattern of the photosensitive resin composition;
(V) removing the pattern of the photosensitive resin composition by alkali treatment, and forming an interlayer insulating layer made of a cured product of the thermosetting resin composition and having an opening reaching the surface of the printed wiring board;
(VI) A method of manufacturing a semiconductor device comprising: a printing method, an electrolytic plating method, or a step of forming a conductive metal or resin in an opening by ball mounting.

  The above method is characterized by combining alkali treatment with two types of resin compositions having different characteristics and functions, such as a photosensitive resin composition that functions as a resist and a thermosetting resin composition that functions as a sealing material. Thus, vias are formed in the sealing material at once after the alkali treatment. According to this method, the semiconductor device can be formed sufficiently efficiently as compared with the conventional method for manufacturing a semiconductor device as shown in FIG. Note that the thermosetting resin used for sealing the semiconductor element in the present invention can be any of powder, doublet, liquid and film, and should be selected according to the apparatus used for manufacturing the semiconductor device. Can do.

  In the said method, it is preferable that the hardening temperature in the process of said (III) is 150-250 degreeC, and heating time is 30-300 minutes.

  Moreover, it is preferable to perform the thermosetting in the process (III) in an atmosphere of an inert gas.

In the above method, the thickness T ₁ of the photosensitive resin composition on the conductor circuit of the printed wiring board is preferably 50 to 300 μm, and the thermosetting resin composition on the conductor circuit of the printed wiring board. the thickness _{T 2} of the layers is preferably 50 to 300 [mu] m. In addition, the ratio (T ₂ / T ₁ ) of the layer thickness T ₂ of the thermosetting resin composition to the layer thickness T ₁ of the photosensitive resin composition is 1.0 to 2.0. preferable.

It is preferable that the ratio (D / R _min ) of the depth D of the opening to the diameter R _min of the opening in the opening having the minimum diameter of the thermosetting resin composition is 0.1 to 1.0.
Moreover, this invention is a semiconductor device obtained by the manufacturing method of one of said semiconductor devices.

  Further, the present invention is a thermosetting resin composition used in the above method, wherein the resin composition contains at least one selected from the group consisting of an epoxy resin, a phenol resin, a polyamideimide resin, and a thermosetting polyimide resin. And a thermosetting resin composition containing an inorganic filler having a maximum particle size of 5 μm or less and an average particle size of 1 μm or less.

  The maximum particle size and the average particle size of the inorganic filler here are dynamic light scattering type nano track particle size distribution meter “UPA-EX150” (manufactured by Nikkiso Co., Ltd.) manufactured by Nikkiso Co., Ltd. or laser diffraction scattering type micro track particle size. It means a value measured using a distribution meter “MT-3100” (manufactured by Nikkiso Co., Ltd.).

  According to the present invention, a semiconductor device having vias in a thermosetting resin and having excellent reliability can be manufactured sufficiently efficiently.

It is an end elevation which shows typically the state where the layer of photosensitive resin was formed in the surface of a printed wiring board. It is an end view which shows typically the state in which the pattern of the photosensitive resin was formed in the surface of a printed wiring board. FIG. 3 is an end view schematically showing a state in which a semiconductor element is mounted on a printed wiring board and a gap between the semiconductor element and the printed wiring board is filled with an underfill material. It is an end view which shows typically the state in which the layer of the thermosetting resin was formed so that at least one part of the pattern of a semiconductor element and photosensitive resin might be covered. FIG. 5 is an end view schematically showing a state after the semiconductor device shown in FIG. 4 is ground. FIG. 6 is an end view schematically showing a state in which the semiconductor device shown in FIG. 5 is subjected to an alkali treatment to form an opening in a thermosetting resin. FIG. 7 is an end view schematically showing a state in which a conductive material is formed in the opening of the semiconductor device shown in FIG. 6. It is a figure which shows the manufacturing method ((a)-(e)) of the 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 are denoted by the same reference numerals, and redundant description is omitted. Further, the positional relationship such as up, down, left and right is based on the positional relationship shown in the drawings unless otherwise specified. Further, the dimensional ratios in the drawings are not limited to the illustrated ratios.

  Here, a method of manufacturing the semiconductor device 10 in which vias are provided in the thermosetting resin shown in FIG. 7 will be described from the mode shown in FIG. Note that the method for manufacturing a semiconductor device of the present invention is particularly suitable in the form of mounting a flip chip type semiconductor element that is becoming thinner. Further, it is particularly suitable for a semiconductor device that requires many electrical connections.

  A method for manufacturing a semiconductor device of the present invention will be described with reference to the drawings.

A layer 3 made of a photosensitive resin composition, which will be described later, is formed on the surface of the printed wiring board 2, and a predetermined portion of the layer 3 made of the photosensitive resin composition is exposed by irradiating actinic rays through a mask pattern. The layer made of the photosensitive resin composition is photocured (exposure treatment in step (I)). A known light source can be used as the actinic ray light source. For example, a light source that effectively emits ultraviolet rays, such as a carbon arc lamp, a mercury vapor arc lamp, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, and a xenon lamp can be used. Further, direct drawing direct laser exposure may be used. Although an exposure amount changes with compositions of the apparatus to be used and the photosensitive resin composition, Preferably it is 10-600 mJ / cm < ² >, More preferably, it is 20-400 mJ / cm < ² >. When the exposure amount is less than 10 mJ / cm ² , the photocuring tends to be insufficient, and when it exceeds 600 mJ / cm ² , the photocuring becomes excessive and the shape of the layer 3 made of the photosensitive resin composition can be stably obtained. Tends to be difficult.

  Next, by removing the layer 3 made of the photosensitive resin composition other than the exposed portion by development, a pattern 3a made of the photosensitive resin composition is formed on the surface of the printed wiring board as shown in FIG. 2 ((I ) Process development process). The pattern 3a made of the photosensitive resin composition is removed by an alkali treatment described later, and becomes an opening in the thermosetting resin composition layer 5 (see FIG. 6). As the developer used at this time, for example, an alkaline developer such as a dilute solution of sodium carbonate (1 to 5% by mass aqueous solution) at 20 to 50 ° C. is used, and spraying, rocking immersion, brushing, scraping, etc. Development is performed by a known method. Thereby, the pattern 3a which consists of a predetermined photosensitive resin composition is formed.

The thickness T ₁ of the layer 3 made of the photosensitive resin composition is preferably 50 to 300 μm. When the thickness T _{1 of the} layer 3 made of the photosensitive resin composition is thicker than 300 μm, it tends to be difficult to form a fine pattern. On the other hand, when the thickness of the layer 3 made of the photosensitive resin composition is less than 50 μm, it is necessary to make the semiconductor element thin and to narrow the gap between the semiconductor element and the printed wiring board, and it is difficult to manufacture the semiconductor device. There are circumstances that become. As shown in FIG. 2, the thickness T ₁ of the layer 3 made of the photosensitive resin composition refers to the thickness of the layer 3 made of the photosensitive resin composition on the electrode 4 (conductor circuit of the printed wiring board).

  Next, as shown in FIG. 3, the semiconductor element 1 is mounted at a predetermined location and mounted (step (II)). The semiconductor element is not particularly limited to face-up or face-down, but a face-down flip chip type is preferable from the viewpoint of recent high density and thinning. Flip chip mounting is performed using a flip chip bonder. If necessary, the flux is transferred and mounted at a predetermined load and temperature. There are cases where the connection is made by a flip chip bonder, and cases where the connection is made by subsequent reflow. After mounting the semiconductor element, flux cleaning is performed as necessary. A drying process is performed as necessary, and a gap between the semiconductor element and the printed wiring board is filled with an underfill material, and is cured by heat.

  Next, as shown in FIG. 4, a layer 5 made of a thermosetting resin composition, which will be described later, is formed so as to cover the surface of the semiconductor element and the printed wiring board (electrode 4 and pattern 3 a of the photosensitive resin composition). (Step (III)). In the step of forming the layer 5 made of the thermosetting resin composition, in the case of powder or tablet, molding by transfer press, in the case of liquid, known screen printing, application by roll coater, in the case of film, vacuum lamination The layer 5 made of the thermosetting resin composition is formed on the printed wiring board by passing through the step of attaching by, for example. Next, the formed layer 5 made of the thermosetting resin composition is thermoset (step (III)). As the thermosetting resin composition, any of powder, tablet, liquid and film can be applied, and can be selected according to the apparatus used for manufacturing the semiconductor device.

The layer 5T ₂ made of the thermosetting resin composition is preferably 50 to 300 μm. When the thickness T ₂ of the layer 5 made of a thermosetting resin composition is thick beyond 300 [mu] m, they tend to be difficult to form a fine pattern. On the other hand, when the thickness of the layer made of the thermosetting resin composition is less than 50 μm, it is necessary to make the semiconductor element thin and to narrow the gap between the semiconductor element and the printed wiring board, and to manufacture the semiconductor device. There are circumstances that make it difficult. The thickness T ₂ of the layer 5 made of a thermosetting resin composition, as shown in FIG. 4, refer to the thickness of the layer 5 of the electrode 4 (the conductor circuit of the printed wiring board) The thermosetting resin composition on. Further, it is preferable that the thickness T ₂ of the layer 5 having a thickness of T ₁ and a thermosetting resin composition layer 3 made of a photosensitive resin composition are the same thickness.

In the above production method, the ratio (T ₂ / T ₁ ) of the thickness T ₂ of the layer 5 of the thermosetting resin composition to the thickness T ₁ of the layer 3 of the photosensitive resin composition is 1.0 to 2.0. Preferably, it is 1.0-1.5. This is because when T ₂ / T ₁ is less than 1.0, the pattern 3a of the photosensitive resin composition cannot be embedded in the layer 5 made of the thermosetting resin composition. Conversely, when T ₂ / T ₁ is larger than 2.0, the layer 5 made of the thermosetting resin composition on the layer 3 of the photosensitive resin composition becomes thick, and as a result, the thermosetting resin composition Not only does the alkali treatment or the grinding process by polishing ((IV) step) take a long time for the layer 5 formed by thermal curing of the layer 5 but also tends to cause deterioration of the alkaline liquid.

  In the heat curing treatment, the heat curing temperature is preferably 150 to 250 ° C., and the heating time (curing time) is preferably 30 to 300 minutes. More preferably, the curing temperature is 160 to 200 ° C., and the curing time is 30 to 120 minutes. If the curing temperature is less than 150 ° C. and the curing time is as short as less than 30 minutes, thermal curing will be insufficient, and subsequent grinding treatment (desmear treatment, etc.) will cause overgrinding and peeling, which may cause peeling of the thermosetting resin. Become. On the other hand, if the curing temperature is higher than 250 ° C. and the curing time is longer than 300 minutes, the oxidation progresses, and the deterioration of the resin is likely to occur at the copper interface that is the material of the conductor circuit. is there. A clean oven is generally used for thermosetting, and it is preferable to perform curing in an atmosphere of an inert gas such as nitrogen in order to suppress copper oxidation.

  Next, as shown in FIG. 5, the surface of the layer 5 of the thermosetting resin composition after the thermosetting treatment is ground to expose the pattern 3a of the photosensitive resin composition (step (IV)). The exposure of the pattern 3a of the photosensitive resin composition may be carried out by an alkali treatment described later. When the layer 5 of the thermosetting resin composition is thick, polishing (mechanical polishing, chemical mechanical polishing (CMP), etc. ). When carrying out the polishing treatment, specifically, grinding is performed with abrasive cloth paper or sandpaper obtained by adhering an abrasive to paper or cloth using an apparatus such as a grinder or a back grinder. In particular, the abrasive is not limited, but artificial abrasives such as fused alumina and silicon carbide, and natural abrasives such as garnet and emery are used. In particular, the grain size of the abrasive grains is not limited, but it is desirable to grind with # 1500 or more at the end so as not to leave scratches on the surface. Further, the polishing step and the alkali treatment described later may be performed by individual apparatuses, or may be performed by an apparatus in which these steps are incorporated as a series of steps. Moreover, grinding may not only expose the pattern 3a of the photosensitive resin composition but also expose the surface of the semiconductor element. This is because when the surface of the semiconductor element is exposed, the heat dissipation characteristics are improved.

After the pattern 3a of the photosensitive resin composition is exposed by the grinding process, the pattern 3a of the photosensitive resin composition is peeled and removed by the alkali process, and the opening reaching the surface of the printed wiring board as shown in FIG. A thermosetting resin composition having 5 h is formed (step (V)). The alkali treatment can be performed, for example, by immersing the substrate to be treated in a mixed solution of sodium permanganate solution, sodium hydroxide solution, potassium permanganate solution, chromium solution, sulfuric acid, or the like. Specifically, after the substrate to be treated is swelled with hot water or a predetermined swelling liquid, residues, etc. are removed with sodium permanganate liquid, etc., and reduction (neutralization) is performed, followed by washing with water and washing with hot water. , Dry. If a sufficient opening is not formed even after a single process, the process may be performed multiple times. The alkali treatment is not limited to the above. Further, after the alkali treatment, thermosetting of the thermosetting resin may be performed again. Although the effect varies depending on the thermosetting resin to be used, not only can the glass transition temperature be raised by thermosetting, but also low thermal expansion can be achieved.
Grinding the surface of the layer made of the thermosetting resin composition of (IV) to expose the pattern of the photosensitive resin composition, and removing the pattern of the photosensitive resin composition by the alkali treatment of (V), The step of forming an interlayer insulating layer having an opening can also be performed continuously. The surface of the layer made of the thermosetting resin composition can be ground (etched) with an alkaline chemical solution, and the exposed pattern of the photosensitive resin composition can be removed with the same chemical solution. Since efficiency can be achieved, it is preferable.

  Next, as shown in FIG. 7, a conductive material is formed in the opening of the thermosetting resin by printing, electrolytic plating, ball mounting, or the like (step (VI)). The conductive material is not particularly limited, but usually eutectic solder or lead-free solder is used. The semiconductor device 10 can be obtained by melting the solder as necessary.

Although the diameter of the via opening (R shown in FIG. 5) of the thermosetting resin composition layer 5 is not particularly limited, the opening relative to the diameter R _min of the minimum diameter opening of the thermosetting resin composition layer 5 is not limited. The depth ratio (D / R _min ) is preferably 0.1 to 1.0, more preferably 0.2 to 0.8. This is because when D / R _min is less than 0.1, the thermosetting resin composition layer 5 cannot be thinned when an opening having a small diameter is provided. On the other hand, when D / R _min exceeds 1.0, the layer 3 made of the photosensitive resin composition does not peel off when an opening having a small diameter is provided, and it is difficult to provide a predetermined opening. It is. The shape of the opening is circular, but may be elliptical or the like. When the opening is formed other than a circle, the diameter R may be a circle equivalent diameter.

  The semiconductor device 10 described above is particularly suitable in the form of mounting flip chip type semiconductor elements that are becoming finer, higher density, and thinner. Further, it is particularly suitable for a semiconductor device that requires many electrical connections.

  Next, although the photosensitive resin composition and thermosetting resin composition used for manufacture of the above-mentioned semiconductor device 10 will be described in detail, the present invention is not limited to these resin compositions.

Although the photosensitive resin composition used for manufacture of the semiconductor device 10 is not specifically limited, The following are suitable. That is, the photosensitive resin composition suitable for forming the photosensitive resin layer is
(A) a binder polymer;
(B) a photopolymerizable compound having at least one ethylenically unsaturated bond;
(C) a photopolymerization initiator;
It is preferable to contain.

  It is preferable that the photosensitive resin composition does not contain (d) an inorganic filler. In this case, the resolution after development is improved, a fine pattern can be formed, and the side surface of the opening after peeling by alkali treatment (desmear treatment) tends to be smooth.

  Examples of the (a) binder polymer (hereinafter sometimes referred to as “component (a)” for the sake of convenience) include, for example, acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyds. Resin, phenol resin and the like. An acrylic resin is preferable from the viewpoint of alkali developability. These can be used alone or in combination of two or more. (A) The binder polymer can be produced, for example, by radical polymerization of a polymerizable monomer.

  Examples of the polymerizable monomer include polymerizable styrene derivatives substituted at the α-position or aromatic ring such as styrene, vinyltoluene, and α-methylstyrene, acrylamide such as diacetone acrylamide, acrylonitrile, and the like. Vinyl alcohol ethers such as vinyl-n-butyl ether, (meth) acrylic acid alkyl ester, (meth) acrylic acid benzyl ester, (meth) acrylic acid tetrahydrofurfuryl ester, (meth) acrylic acid dimethylaminoethyl ester, ( (Meth) acrylic acid diethylaminoethyl ester, (meth) acrylic acid glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (meth) acrylic acid, α-Bromo (meth) acrylic acid, α-chloro (meth) acrylic acid, β-furyl (meth) acrylic acid, β-styryl (meth) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, maleic acid Examples thereof include maleic acid monoesters such as monoethyl and monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, crotonic acid and propiolic acid. These can be used alone or in combination of two or more. In addition, (meth) acryl means acryl or methacryl corresponding to it, for example, (meth) acrylic acid shows acrylic acid or methacrylic acid corresponding to it.

  Further, (a) the binder polymer preferably contains a carboxyl group from the viewpoint of alkali developability, for example, by radical polymerization of a polymerizable monomer having a carboxyl group and another polymerizable monomer. Can be manufactured. As the polymerizable monomer having a carboxyl group, (meth) acrylic acid is preferable, and methacrylic acid is more preferable.

  The carboxyl group content (a) of the binder polymer (the ratio of the polymerizable monomer having a carboxyl group to the total polymerizable monomer used) is preferably 12 from the viewpoint of the balance between alkali developability and alkali resistance. It is -50 mass%, More preferably, it is 12-40 mass%, More preferably, it is 15-30 mass%, Most preferably, it is 15-25 mass%. When the carboxyl group content is less than 12% by mass, alkali developability tends to be inferior, and when it exceeds 50% by mass, alkali resistance tends to be inferior.

  (A) The weight average molecular weight of the binder polymer is preferably 20,000 to 300,000, more preferably 40,000 to 150,000, and still more preferably, from the viewpoint of the balance between mechanical strength and alkali developability. Is 50,000 to 120,000. When the weight average molecular weight is less than 20,000, the developer resistance tends to decrease, and when it exceeds 300,000, the development time tends to be long. In the present embodiment, the weight average molecular weight is a value measured by a gel permeation chromatography method and converted by a calibration curve created using standard polystyrene.

  (B) As a photopolymerizable compound having at least one ethylenically unsaturated bond (hereinafter referred to as “component (b)” for convenience), for example, polyhydric alcohol is reacted with α, β-unsaturated carboxylic acid. Urethane monomers such as (meth) acrylate compounds having a urethane bond, compounds obtained by reacting α, β-unsaturated carboxylic acids with bisphenol A-based (meth) acrylate compounds, glycidyl group-containing compounds, Nonylphenoxypolyethyleneoxy (meth) acrylates such as nonylphenoxyoctaethyleneoxy (meth) acrylate, γ-chloro-β-hydroxypropyl-β ′-(meth) acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β ′ -(Meth) acryloyloxyethyl-o-phthalate, β-hydro Shipuropiru -Beta'- (meth) acryloyloxyethyl -o- phthalate, and (meth) acrylic acid alkyl ester. These may be used alone or in combination of two or more.

  Examples of the photopolymerization initiator of the component (c) include benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone (Michler ketone), N, N′-tetraethyl-4,4′-diaminobenzophenone. 4-methoxy-4'-dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, and 2-methyl-1- [4- (methylthio) phenyl]- Aromatic ketones such as 2-morpholino-propanone-1, 2-ethylanthraquinone, phenanthrenequinone, 2-tert-butylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone 2,3-diphenylanthraquinone, 1-chloro Quinones such as loanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenantharaquinone, 2-methyl-1,4-naphthoquinone, and 2,3-dimethylanthraquinone, benzoin methyl ether, benzoin ethyl ether And benzoin ether compounds such as benzoin phenyl ether, benzoin compounds such as benzoin, methylbenzoin, and ethylbenzoin, benzyl derivatives such as benzyldimethyl ketal, 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10 -Substituted anthracenes such as dipropoxyanthracene, 9,10-dibutoxyanthracene, and 9,10-dipentoxyanthracene, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) 2,4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer such as 2- (p-methoxyphenyl) -4,5-diphenylimidazole dimer, coumarin compound, oxazole Compounds, pyrazoline compounds, and the like. Here, the substituents of the aryl groups of two 2,4,5-triarylimidazoles may give the same and symmetric compounds, or differently give asymmetric compounds. Moreover, you may combine a thioxanthone type compound and a tertiary amine compound like the combination of diethyl thioxanthone and dimethylaminobenzoic acid. In addition, 2,4,5-triarylimidazole dimer is more preferable from the viewpoint of balance between adhesion and sensitivity. These are used alone or in combination of two or more.

  The content of the (a) binder polymer is preferably 30 to 80 parts by mass, more preferably 40 to 75 parts by mass with respect to 100 parts by mass of the total amount of the components (a) and (b). More preferably, it is 50-70 mass parts. When the content of the component (a) is within this range, the coating properties of the photosensitive resin composition and the strength of the photocured product become better. The content of the photopolymerizable compound (b) having at least one ethylenically unsaturated bond is preferably 20 to 70 parts by mass with respect to 100 parts by mass as a total of the components (a) and (b). More preferably, it is 25-60 mass parts, More preferably, it is 30-50 mass parts. When the content of the component (b) is within this range, the photosensitivity and coating property of the photosensitive resin composition become better.

  The content of the (c) photopolymerization initiator is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the components (a) and (b). 20 parts by mass, more preferably 0.2 to 10 parts by mass. When the content of the component (c) is within this range, the photosensitivity and the internal photocurability of the photosensitive resin composition become better.

  Although it is preferable that the photosensitive resin composition is (d) filler-less without filling with an inorganic filler, it may be filled with a small amount. (D) By filling a small amount of the inorganic filler, the shrinkage amount becomes small, the rigidity becomes high, and the thickness dimensional accuracy can be improved. However, when the amount exceeds 5 parts by mass with respect to 100 parts by mass of the total amount of the photosensitive resin composition, the resolution is remarkably lowered. Therefore, when (d) an inorganic filler is filled, the filling amount is photosensitive. It is preferable to set it as 5 mass parts or less with respect to 100 mass parts of total amounts of a resin composition.

(D) Examples of inorganic fillers include barium sulfate, barium titanate, powdered silicon oxide, amorphous silica, talc, clay, calcined kaolin, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, and mica powder. Inorganic fillers can be used. In particular, it is desirable to use a silane coupling agent in order to disperse the silica particle in the resin without agglomeration with the primary particle size.
When the photosensitive resin composition contains (d) an inorganic filler, the maximum particle size is 5 μm or less, preferably 2 μm or less, more preferably 1 μm or less. In addition, (d) the average particle size of the inorganic filler is preferably 300 nm or less, more preferably 100 nm or less, from the viewpoint of resolution.

  In addition, the photosensitive resin composition includes, if necessary, dyes such as malachite green, Victoria pure blue, brilliant green, and methyl violet, tribromophenyl sulfone, leuco crystal violet, diphenylamine, benzylamine, triphenylamine, Photochromic agents such as diethylaniline, o-chloroaniline and tertiary butyl catechol, thermochromic inhibitors, plasticizers such as p-toluenesulfonamide, pigments, fillers, antifoaming agents, flame retardants, adhesion-imparting agents, 0.01 to 20 parts by mass of a leveling agent, a peeling accelerator, an antioxidant, a fragrance, an imaging agent, a thermal crosslinking agent, a polymerization inhibitor and the like with respect to 100 parts by mass of the total amount of the component (a) and the component (b). Can be contained. These are used alone or in combination of two or more.

  If necessary, the photosensitive resin composition is dissolved in a solvent such as methanol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N, N-dimethylformamide, propylene glycol monomethyl ether, or a mixed solvent thereof. And can be applied as a solution having a solid content of 30 to 60% by mass. These are used alone or in combination of two or more.

  Although there is no restriction | limiting in particular in the photosensitive resin composition, Metal surfaces, for example, iron-type alloys, such as copper, a copper-type alloy, nickel, chromium, iron, stainless steel, Preferably copper, a copper-type alloy, and an iron-type alloy It is preferable that the surface is applied as a liquid resist and dried, and then coated with a protective film, if necessary, or used in the form of a photosensitive element.

  The form of the photosensitive element includes a support and a photosensitive resin composition layer (resin layer) formed by uniformly applying and drying the solution of the photosensitive resin composition on the support. In addition, a protective film for coating the photosensitive resin composition layer may be further provided. The support can be obtained, for example, by applying and drying a photosensitive resin composition on a polymer film having heat resistance and solvent resistance such as polyethylene terephthalate, polypropylene, polyethylene, and polyester. From the viewpoint of transparency, it is preferable to use a polyethylene terephthalate film.

  Although the thermosetting resin composition used for manufacture of the semiconductor device 10 is not specifically limited, the following are suitable. That is, a thermosetting resin composition suitable for forming a sealing material is a resin composition containing at least one selected from the group consisting of an epoxy resin, a phenol resin, a polyamideimide resin, and a thermosetting polyimide resin, and a maximum And an inorganic filler having a particle size of 5 μm or less and an average particle size of 1 μm or less.

  The epoxy resin is preferably an epoxy resin having one or more glycidyl groups in the molecule. The filling amount of the inorganic filler is preferably in the range of 0 to 90% by mass, more preferably in the range of 20 to 70% by mass, and still more preferably 30 to 60% by mass.

  The epoxy resin can be used without limitation as long as it is an epoxy resin having two or more glycidyl groups, but is preferably a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a novolak phenol type epoxy resin, or a biphenyl type. Water such as epoxy resin, bisphenol S type epoxy resin such as bisphenol S diglycidyl ether, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, bixylenol type epoxy resin such as bixylenol diglycidyl ether, and hydrogenated bisphenol A glycidyl ether These are added bisphenol A type epoxy resins, dibasic acid-modified diglycidyl ether type epoxy resins, and the like, which can be used alone or in combination of two or more.

  Commercially available epoxy resins include naphthalene type epoxy resins such as EXA4700 (tetrafunctional naphthalene type epoxy resin) manufactured by DIC Corporation, NC-7000 (polyfunctional solid epoxy resin containing naphthalene skeleton) manufactured by Nippon Kayaku Co., Ltd .; Nippon Kayaku Epoxidized product (trisphenol type epoxy resin) of a condensate of phenols such as EPPN-502H (trisphenol epoxy resin) and aromatic aldehyde having a phenolic hydroxyl group; Epicron HP-7200H (di) Dicyclopentadiene aralkyl epoxy resin such as cyclopentadiene skeleton-containing polyfunctional solid epoxy resin); biphenyl aralkyl epoxy resin such as NC-3000H (biphenyl skeleton-containing polyfunctional solid epoxy resin) manufactured by Nippon Kayaku Co., Ltd .; DIC Corporation Epicron N660, Epicron N690, Nippon Kayaku Co., Ltd. EOCN-104S and other novolak type epoxy resins; Nissan Chemical Industries, Ltd. TEPIC etc. Tris (2,3-epoxypropyl) isocyanurate, DIC Corporation Epicron 860, Epicron 900-IM, Epicron EXA-4816, Epicron EXA-4822, Araldite AER280 manufactured by Asahi Ciba Co., Ltd., Epototo YD-134 manufactured by Tohto Kasei Co., Ltd., JER834 manufactured by Japan Epoxy Resin Co., Ltd., JER872, ELA manufactured by Sumitomo Chemical Industries Bisphenol A type epoxy resin such as -134; naphthalene type epoxy resin such as DIC Corporation Epicron HP-4032; phenol novolac type epoxy resin such as Epicron N-740 manufactured by DIC Corporation , The epoxy resin of a condensate of phenol with salicylaldehyde; Nippon Kayaku Co., Ltd. EPPN-500 series, and the like. These epoxy resins may be used alone or in combination of two or more.

  Among the above epoxy resins, biphenyl aralkyl type epoxy resins such as NC-3000H (biphenyl skeleton-containing polyfunctional solid epoxy resin) manufactured by Nippon Kayaku Co., Ltd. are excellent in terms of excellent adhesion to copper, insulation and wall smoothness. Moreover, it is more preferable to use Nippon Kayaku Co., Ltd. EPPN-500 series (a novolak-type epoxy resin having a triphenylmethane skeleton) in terms of high crosslinking density and high Tg.

  The content of the epoxy resin is preferably 30 to 90 parts by mass and more preferably 40 to 80 parts by mass with respect to 100 parts by mass of the resin component excluding the inorganic filler component.

  As the curing agent combined with the epoxy resin, various conventionally known epoxy resin curing agents or epoxy resin curing accelerators can be blended. For example, phenol resins, imidazole compounds, acid anhydrides, aliphatic amines, alicyclic polyamines, aromatic polyamines, tertiary amines, dicyandiamide, guanidines, or epoxy adducts or microencapsulated products thereof, triphenyl Regardless of the curing agent or curing accelerator, organic phosphine compounds such as phosphine, tetraphenylphosphonium, tetraphenylborate, DBU (diazabicycloundecene) or its derivatives, etc. Or it can use in combination of 2 or more types. Although it will not specifically limit if hardening of an epoxy resin is advanced, Specifically, 4, 4'- diamino diphenyl sulfone, 4, 4'-bis (4-aminophenoxy) biphenyl, 2, 2-bis [4- (4-Aminophenoxy) phenyl] propane, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, trimethylenebis (4-aminobenzoate), 3,3 ′ -Dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, bis [4- (4-amino Phenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] sulfone, 9,9′-bis (4-aminophenyl) fluoro Len, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane and the like can be exemplified, and can be used alone or in combination of two or more.

The thermosetting resin composition used in the present invention preferably contains a maleimide compound having at least two unsaturated N-substituted maleimide groups in the molecular structure. Specifically, for example, N, N′-ethylene bismaleimide, N, N′-hexamethylene bismaleimide, N, N ′-(1,3-phenylene) bismaleimide, N, N ′-[1,3 -(2-methylphenylene)] bismaleimide, N, N '-[1,3- (4-methylphenylene)] bismaleimide, N, N'-(1,4-phenylene) bismaleimide, bis (4- Maleimidophenyl) methane, bis (3-methyl-4-maleimidophenyl) methane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethane bismaleimide, bis (4-maleimidophenyl) ether, bis (4 -Maleimidophenyl) sulfone, bis (4-maleimidophenyl) sulfide, bis (4-maleimidophenyl) ketone, bis (4-maleimidocyclohexyl) me Tan, 1,4-bis (4-maleimidophenyl) cyclohexane, 1,4-bis (maleimidomethyl) cyclohexane, 1,4-bis (maleimidomethyl) benzene, 1,3-bis (4-maleimidophenoxy) benzene, 1,3-bis (3-maleimidophenoxy) benzene, bis [4- (3-maleimidophenoxy) phenyl] methane, bis [4- (4-maleimidophenoxy) phenyl] methane, 1,1-bis [4- ( 3-maleimidophenoxy) phenyl] ethane, 1,1-bis [4- (4-maleimidophenoxy) phenyl] ethane, 1,2-bis [4- (3-maleimidophenoxy) phenyl] ethane, 1,2-bis [4- (4-Maleimidophenoxy) phenyl] ethane, 2,2-bis [4- (3-maleimidophenoxy) phene Ru] propane, 2,2-bis [4- (4-maleimidophenoxy) phenyl] propane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] butane, 2,2-bis [4- (4 -Maleimidophenoxy) phenyl] butane, 2,2-bis [4- (3-maleimidophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- ( 4-maleimidophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 4,4-bis (3-maleimidophenoxy) biphenyl, 4,4-bis (4-maleimidophenoxy) biphenyl, Bis [4- (3-maleimidophenoxy) phenyl] ketone, bis [4- (4-maleimidophenoxy) phenyl] ketone, 2,2′-bis (4-maleimidophenyl) Nyl) disulfide, bis (4-maleimidophenyl) disulfide, bis [4- (3-maleimidophenoxy) phenyl] sulfide, bis [4- (4-maleimidophenoxy) phenyl] sulfide, bis [4- (3-maleimidophenoxy) ) Phenyl] sulfoxide, bis [4- (4-maleimidophenoxy) phenyl] sulfoxide, bis [4- (3-maleimidophenoxy) phenyl] sulfone, bis [4- (4-maleimidophenoxy) phenyl] sulfone, bis [4 -(3-maleimidophenoxy) phenyl] ether, bis [4- (4-maleimidophenoxy) phenyl] ether, 1,4-bis [4- (4-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1 , 3-Bis [4- (4-maleimidophenoxy ) -Α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimidophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (3-maleimidophenoxy)- α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4- Maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, 1 , 3-bis [4- (3-maleimidophenoxy) -3,5-dimethyl-α, α-dimethylbenzyl] benzene, polyphenylmethanemaleimide, and the like. A compound may be used independently or may be used in mixture of 2 or more types.

  Moreover, you may use a polyimide resin, a polyamidoimide resin, and various carboxylic acid containing resin as another resin with which an epoxy resin is made to react. Examples of the polyamide-imide resin include “Bilomax HR11NN”, “Bilomax HR12N2”, and “Bilomax HR16NN” manufactured by Toyobo Co., Ltd. Examples of the carboxylic acid-containing resin include acrylic resins, acid-modified epoxy acrylates, and acid-containing urethane resins.

  It is preferable that content of the said hardening | curing agent is 5-50 mass parts with respect to 100 mass parts of resin components except an inorganic filler component, and it is more preferable that it is 10-40 mass parts.

  As the inorganic filler, all conventionally known inorganic fillers and organic fillers can be used, and are not limited to specific ones. For example, extender pigments such as barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, silicon nitride, aluminum nitride, , Copper, tin, zinc, nickel, silver, palladium, aluminum, iron, cobalt, gold, platinum, and other metal powders.

  In the case of using a silica filler, it is desirable to use a silane coupling agent in order to disperse the filler in the resin without agglomeration while maintaining the primary particle size. The inorganic filler preferably has a maximum particle size of 5 μm or less, and more preferably 1 μm or less. Moreover, it is preferable that an average particle diameter is 1 micrometer or less. As the silane coupling agent, generally available ones can be used, for example, alkyl silane, alkoxy silane, vinyl silane, epoxy silane, amino silane, acrylic silane, methacryl silane, mercapto silane, sulfide silane, isocyanate silane, Sulfur silane, styryl silane, alkylchlorosilane, and the like can be used.

  Specific compound names include methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, methyltriethoxysilane, methyltriphenoxysilane, ethyltrimethoxysilane, n-propyltrimethoxysilane, diisopropyldimethoxysilane, isobutyltrimethoxy. Silane, diisobutyldimethoxysilane, isobutyltriethoxysilane, n-hexyltrimethoxysilane, n-hexyltriethoxysilane, cyclohexylmethyldimethoxysilane, n-octyltriethoxysilane, n-dodecylmethoxysilane, phenyltrimethoxysilane, diphenyldimethoxy Silane, triphenylsilanol, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, n-octyldi Tylchlorosilane, tetraethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane 3-phenylaminopropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldipropoxysilane Bis (3- (triethoxysilyl) propyl) disulfide, bis (3- (triethoxysilyl) propyl) tetrasulfide, vinyltriacetoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, Nyltriisopropoxysilane, allyltrimethoxysilane, diallyldimethylsilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, Examples include 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltriethoxysilane, N- (1,3-dimethylbutylidene) -3-aminopropyltriethoxysilane, and aminosilane.

  As described above, the average particle size of the inorganic filler is preferably 1 μm or less, more preferably 300 nm or less, and more preferably 100 nm or less. As the average particle size of the inorganic filler is smaller, the surface after alkali treatment (desmear treatment) tends to be smoother. The filling amount of the inorganic filler is preferably 0 to 90% by mass, more preferably 20 to 70% by mass, and further preferably 30 to 60% by mass.

  As mentioned above, although the preferable embodiment of the manufacturing method of the semiconductor device which concerns on this invention, and the thermosetting resin composition suitable for this invention was described, this invention is not necessarily limited to embodiment mentioned above, The You may change suitably in the range which does not deviate from the meaning.

<Preparation of printed wiring board>
First, a printed wiring board for flip chip mounting was prepared. A core base material (MCL-E-679FG manufactured by Hitachi Chemical Co., Ltd.) and a film solder resist (FZ-2700G manufactured by Hitachi Chemical Co., Ltd.) were used as constituent members of the printed wiring board. The thickness of the core base material was 100 μm, and the thickness of the solder resist was 25 μm (see FIG. 1).

<Formation of layer made of photosensitive resin composition>
Next, as shown in FIG. 2, as a photosensitive resin composition, a dry film resist (Hitachi Chemical Industry Co., Ltd., Photoc H-7025) is attached to the surface with a roll laminator, and a photo tool having a pattern is brought into close contact with the stock. The exposure was performed with an energy amount of 50 mJ / cm ² using an EXM-1201 type exposure machine manufactured by Oak Manufacturing Co., Ltd. Next, spray development was performed for 90 seconds with a 1% by mass aqueous sodium carbonate solution at 30 ° C. to form a pattern 3a of the photosensitive resin composition (see FIG. 2).

<Mounting of semiconductor elements and filling of underfill>
Next, as shown in FIG. 3, a semiconductor element (size: 7.3 × 7.3 mm, thickness: 100 μm, bump type: copper post + Sn-3.0Ag-0.5Cu, bump pitch: 80 μm, bump height: 25 μm, bump arrangement (peripheral type) was mounted on a predetermined portion of the printed wiring board. The non-cleaning type flux was used. After drying at 165 ° C. for 2 hours, the gap between the semiconductor element and the printed wiring board is filled with an underfill material (CEL-C-3730S, manufactured by Hitachi Chemical Co., Ltd.) and cured at 165 ° C. for 2 hours. went.

<Manufacture of a film-like thermosetting resin composition>
The following were prepared as thermosetting resin compositions used for sealing semiconductor devices.

<Thermosetting resin composition A>
As the epoxy resin, 70 parts by mass of a biphenyl aralkyl type epoxy resin, product name NC-3000H (manufactured by Nippon Kayaku Co., Ltd.) was used.
Synthesis of Curing Agent Example 1: Heat and coolable reaction vessel equipped with a thermometer, a stirrer, a moisture meter with a reflux condenser, and a volume of 2 liters, bis (4-aminophenyl) sulfone: 26.40 g , 2,2′-bis [4- (4-maleimidophenoxy) phenyl] propane: 484.50 g, p-aminobenzoic acid: 29.10 g, and dimethylacetamide: 360.00 g were added at 140 ° C. for 5 hours. It was made to react and the solution of the hardening | curing agent (A-1) which has a sulfone group in a molecular principal chain, and has an acidic substituent and an unsaturated N-substituted maleimide group was obtained. 30 parts by mass of this curing agent was blended.

  As the inorganic filler component, silica filler having an average particle size of 50 nm and silane coupling treatment with vinylsilane was used. In addition, the inorganic filler component was blended so as to be 30% by mass with respect to the resin content. The dispersion state was measured using a dynamic light scattering nanotrack particle size distribution analyzer “UPA-EX150” (manufactured by Nikkiso Co., Ltd.) and a laser diffraction scattering type microtrack particle size distribution analyzer “MT-3100” (manufactured by Nikkiso Co., Ltd.). Measurement was performed and it was confirmed that the maximum particle size was 1 μm or less.

<Thermosetting resin composition B>
As the epoxy resin, 70 parts by mass of a biphenyl aralkyl type epoxy resin, product name NC-3000H (manufactured by Nippon Kayaku Co., Ltd.) was used.
Curing Agent Synthesis Example 2: Wandamine HM (WHM) [(4,4′-diamino) dicyclohexylmethane, trade name, manufactured by Shin Nippon Rika Co., Ltd.] 52.7 g as a diamine compound, as a diamine having a reactive functional group 6 g of 3,3′-dihydroxy-4,4′-diaminobiphenyl, 108 g of trimellitic anhydride (TMA) as a tricarboxylic anhydride and 1281 g of N-methyl-2-pyrrolidone (NMP) as an aprotic polar solvent, The temperature in the flask was set to 80 ° C. and stirred for 30 minutes. After completion of the stirring, 192 g of toluene was further added as an aromatic hydrocarbon azeotropic with water, and the temperature in the flask was raised to 160 ° C. and refluxed for 2.5 hours. After confirming that the theoretical amount of water was stored in the moisture determination receiver and that no water distilling was observed, the temperature in the flask was adjusted to 180 ° C. while removing water and toluene in the moisture determination receiver. And toluene in the reaction solution was removed. After cooling the solution in the flask to 60 ° C., hydrogenated α, ω-polybutadiene dicarboxylic acid (CI-1000, manufactured by Nippon Soda Co., Ltd.) as a dicarboxylic acid having a long-chain hydrocarbon chain skeleton (about 50 carbon atoms), Product name) 309.5 g was added and stirred for 10 minutes. After the completion of stirring, 119.7 g of 4,4′-diphenylmethane diisocyanate (MDI) was added as a diisocyanate, and the temperature in the flask was raised to 160 ° C. for reaction for 2 hours to obtain a resin solution. It was 47000 when the weight average molecular weight (Mw) of this polyamide-imide resin solution was measured by the gel permeation chromatography. The average reactive functional group number N per polyamideimide molecule was 4.4. 30 parts by mass of this curing agent was blended. As an inorganic filler component, the same thing as the thermosetting resin composition A was used.

<Thermosetting resin composition C>
As the epoxy resin, a cresol novolac type epoxy resin, 70 parts by mass of the product name Epicron N660 (manufactured by DIC Corporation) was used.
As a curing agent, 25 parts by mass of phenoxy resin YP-55 (manufactured by Nippon Steel Chemical Co., Ltd.) and 30 parts by mass of melamine-modified phenol novolac resin LA7054 (manufactured by DIC Corporation) were used. As an inorganic filler component, barium sulfate having an average particle diameter of 300 nm is blended so as to be 46% by mass with respect to the resin content, and Starmill LMZ (manufactured by Ashizawa Finetech Co., Ltd.) is used to prepare zirconia beads having a diameter of 1.0 mm. And adjusted by dispersing for 3 hours at a peripheral speed of 12 m / s. The dispersion state was measured by the same method as that for the resin composition A, and it was confirmed that the maximum particle size was 2 μm.

  Thermosetting is achieved by uniformly applying the solution of each thermosetting resin composition obtained as described above onto a polyethylene terephthalate film (G2-16, manufactured by Teijin Ltd.) having a thickness of 16 μm as a support layer. A resin composition layer was formed. Then, the thermosetting resin composition layer was obtained on the support layer by drying the thermosetting resin composition layer at 100 ° C. for about 10 minutes using a hot air convection dryer. The film thickness of the thermosetting resin composition layer prepared the thing of 100 micrometers-200 micrometers.

  Next, a polyethylene film (NF-15, manufactured by Tamapoly Co., Ltd., trade name) is placed on the surface opposite to the side in contact with the support layer so that dust or the like does not adhere to the film-like thermosetting resin composition. The film was bonded as a protective film to obtain a film type thermosetting resin composition.

  The layer 5 of the thermosetting resin composition was formed on the printed wiring board using the obtained film type thermosetting resin composition (see FIG. 4). Specifically, first, only the protective film of the film type thermosetting resin composition comprising the thermosetting resin composition A, B or C is peeled off, and the film-like heat is applied to the surface of the printed wiring board (semiconductor element mounting surface). A curable resin composition was placed. A film-type thermosetting resin composition was laminated on the surface of the printed wiring board using a press-type vacuum laminator (MVLP-500, manufactured by Meiki Seisakusho Co., Ltd., trade name). The press conditions were as follows: hot plate temperature of 80 ° C., evacuation time of 20 seconds, laminating press time of 30 seconds, atmospheric pressure of 4 kPa or less, and pressing pressure of 0.4 MPa. Subsequently, thermosetting was performed in a clean oven at a predetermined temperature for a predetermined time to form a thermosetting resin layer.

Then, the photosensitive resin composition is obtained by grinding the layer 5 of the thermosetting resin composition by performing grinding treatment and chemical treatment (desmear treatment) for removing the pattern of the photosensitive resin composition along the steps shown in Table 1. While exposing the pattern 3a of the thing, the pattern 3a of the photosensitive resin composition was peeled and removed, and a part of the thermosetting resin composition layer 5 was opened (refer FIG. 5, FIG. 6). It is swollen with a swelling dip securigant P containing diethylene glycol and an ethylene glycol solvent, and is ground by etching and the photosensitive resin composition pattern is removed with a concentrated compact CP of KMnO ₄ and NaOH aqueous solution.

  Thereafter, a solder paste was filled in the opened via using a metal mask, and a reflow process was performed using a reflow apparatus in a nitrogen atmosphere to obtain the semiconductor device 10 (see FIG. 7).

  The semiconductor device 10 has a substrate size of 14 mm × 14 mm and is provided with vias having diameters of 100 μm, 150 μm, 200 μm, and 250 μm on each side of the outer periphery.

The embedding property of the thermosetting resin composition was evaluated based on the following criteria.
○: No gap and good embedding.
X: Insufficient embedding in opening.

The chemical resistance of the thermosetting resin composition was visually confirmed and evaluated based on the following criteria.
◯: Interlayer insulating material (thermosetting resin composition) does not peel off after desmear treatment.
X: Interlayer insulating material peeled off after desmear treatment.

About resolution (opening property), it observed with the metal microscope and evaluated based on the following references | standards.
A: Opening with a diameter of 100 μm or less.
○: Opening with a diameter of 150 μm or less.
Δ: Opened with a diameter of 200 μm or less.
X: Opening with a diameter of 250 μm or less.
Xx: The thing whose diameter is 250 micrometers or less and cannot open.

About the wall surface smoothness of the opening part, it confirmed with the electron microscope and evaluated based on the following references | standards.
○: The wall surface is smooth.
X: The wall has a missing filler or a step.

The residue removability of the opening was evaluated based on the following criteria.
○: There is no dry film resist residue on the copper surface, and it can be peeled off and removed.
X: The thing with the residue of a dry film resist.

The results are shown in Tables 4 and 5.
Depending on the thermosetting resin compositions A, B and C used, the embedding property of the flat top cone (trapezoid cone) of the photosensitive resin composition having a diameter of 100 to 250 μm and a height of 100 to 250 μm is good and photosensitive. In order to expose the pattern of the resin composition, the surface of the thermosetting resin composition is ground with an alkaline chemical solution, and the chemical resistance after removing the pattern of the photosensitive resin composition exposed in the same process is the printed wiring board. And the thermosetting resin composition serving as an interlayer insulating material was maintained, and no peeling occurred and the adhesion was good. The resolution showed the same resolution as the thickness of the used photosensitive resin composition, and the thinner, the higher the resolution. The wall smoothness was affected by the average particle size and the maximum particle size of the inorganic filler. The smaller the wall smoothness, the smoother the residue, and the better the residue removability of the openings in any of the examples.
In the present invention, it is unnecessary to introduce equipment necessary for via formation with a conventional laser or the like, and there is no connection failure due to oxidation of thermosetting resin due to laser heat, and processing time is not increased, and manufacturing can be performed collectively. The method also improves reliability.

  This process is not limited to the vias of the semiconductor device, but can be applied to all of those having openings such as a solder resist opening process, a wafer level package rewiring process, and a via formation of a build-up substrate.

DESCRIPTION OF SYMBOLS 1 ... Semiconductor element, 2 ... Printed wiring board, 3 ... Layer which consists of photosensitive resin compositions, 3a ... Pattern which consists of photosensitive resin compositions, 4 ... Electrode, 5 ... Layer which consists of thermosetting resin compositions (Heat Curable resin composition layer), 5h, opening, 10, 10A, semiconductor device.

Claims (7)

(I) a step of forming a pattern of a photosensitive resin composition on a printed wiring board having a conductor circuit, and then subjecting the layer to exposure and development to form a pattern;
(II) mounting a semiconductor element on a printed wiring board;
(III) a step of thermosetting after forming a layer made of a thermosetting resin composition so as to cover at least part of the semiconductor element and the photosensitive resin composition;
(IV) a step of grinding a surface of a layer made of the thermosetting resin composition to expose a pattern of the photosensitive resin composition;
(V) removing the pattern of the photosensitive resin composition by alkali treatment, and forming an interlayer insulating layer made of a cured product of the thermosetting resin composition and having an opening reaching the surface of the printed wiring board;
(VI) A method of manufacturing a semiconductor device comprising: a printing method, an electrolytic plating method, or a step of forming a conductive metal or resin in an opening by ball mounting.   The method for manufacturing a semiconductor device according to claim 1, wherein the curing temperature in the step (III) is 150 to 250 ° C. and the heating time is 30 to 300 minutes.   The method for manufacturing a semiconductor device according to claim 1, wherein the thermal curing in the step (III) is performed in an inert gas atmosphere. The thickness T ₁ of the layer of the photosensitive resin composition is 50 to 300 [mu] m, a manufacturing method of a semiconductor device according to any one of claims 1 to 3. The thickness T ₂ of the layers of the heat-curable resin composition is a 50 to 300 [mu] m, manufacturing method of semiconductor device according to claim 1. The ratio (T ₂ / T ₁ ) of the layer thickness T ₂ of the thermosetting resin composition to the layer thickness T ₁ of the photosensitive resin composition is 1.0 to 2.0. Item 6. A method for manufacturing a semiconductor device according to any one of Items 1 to 5. The ratio (D / _Rmin ) of the depth D of the opening with respect to the diameter _Rmin of the opening in the opening having the minimum diameter of the thermosetting resin composition is 0.1 to 1.0. The manufacturing method of the semiconductor device as described in any one of -6.

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