JPH11260148A - Thin film dielectric, multilayer wiring board using the same, and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To cope with a complex shape by dispersing an inorganic filler into an organic resin, and specifying the dielectric constant and film thickness within specific ranges. SOLUTION: A thin film dielectric has the dielectric constant above 25, and the film thickness below 1.5 μm. It comprises (a) organic compounds having at least one epoxy group or an unsaturated double bond in a structure and a mixture thereof, (b) at least one of metallic alkoxide, metallic acetylacetonate, metallic organic acid salt, inorganic chloride and inorganic oxyacid salt, or their partially hydrolyzed condensates, and (c) a photoacid generating agent or a photobase generating agent as the essential components. A solution comprising (a), (b) and (c) is applied onto a lower electrode by coating, spraying or the like, drying the same to remove a solvent to form a thin film layer, then hardening the same by using the active light source such as a high pressure mercury lamp or the like through a mask of an arbitrary shape, and removing an unexposed part by the development, whereby the complex shape can be formed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thin-film dielectric which facilitates formation of a capacitor as a passive element in a multilayer wiring board to enable high-density mounting, a multilayer wiring board and a module using the same. The present invention relates to a substrate and a method for manufacturing the substrate.

[0002]

2. Description of the Related Art In order to realize high-density surface mounting, on a substrate, studies have been made on miniaturization of via holes, narrowing of a wiring pitch, adoption of a build-up method, and the like.
Furthermore, miniaturization of IC packages, increase in the number of pins, and miniaturization of passive components such as capacitors and resistors, and surface mounting are also being performed. On the other hand, with the progress of miniaturization of passive elements, handling during manufacture and mounting has become more difficult, and the limitations of the conventional method have become apparent. As a solution to this, it has been proposed to form passive elements directly on the surface or inside of a printed wiring board. As a result, it is not necessary to mount the chip component of the passive element on the printed wiring board, and it is possible to increase the density and improve the reliability. The method of coating and sintering using a paste of a metal or an insulator, which is performed on a ceramic substrate, cannot be directly applied to an organic substrate having poor heat resistance.

As a method of forming such a passive element on an organic substrate, a method of applying a mixture of an organic polymer and a high dielectric constant filler (P. Chanel et al., The 46th El.
ectric Componets and Technology Conference, 12th
5-132, 1996) and a method using electron cyclotron resonance chemical vapor deposition (ECR-CVD) that can form a film at a low temperature (T. Hitoshi Matsui et al., Circuit Technology, No. 9).
Vol., Pp. 497-502, 1994).

[0004]

In the above-mentioned method using a mixture of an organic polymer and a high dielectric constant filler, the thickness of the thin film capacitor depends on the diameter of the filler. There is a limit. In order to further increase the dielectric constant, the filler must be highly filled. Addition of a filler having a large specific surface area increases the viscosity of the resin, hinders the formation of a thin film, and causes defects in the dielectric. On the other hand, the method using ECR-CVD has problems in that a special apparatus is required, a dielectric thin film cannot be formed at low cost by batch processing, and it is difficult to form a dielectric thin film having a complicated shape. there were. An object of the present invention is to provide a thin-film dielectric having a complicated shape, to provide a multilayer wiring board formed by forming the thin-film dielectric in or on an organic wiring substrate, and to provide a method of manufacturing the same.

[0005]

The gist of the present invention will be described below.

First, a first invention is a thin film dielectric characterized in that an inorganic filler is dispersed in an organic resin and has a dielectric constant of 25 or more and a film thickness of 1.5 μm or less.

In a second aspect of the present invention, the inorganic filler contains metal alkoxide, alkylated metal alkoxide, metal acetylacetonate, metal organic acid salt, inorganic chloride,
2. The thin film dielectric according to claim 1, wherein the inorganic filler is an inorganic filler having a particle size of 0.8 [mu] m or less, obtained by condensing at least one mixture of a compound of an inorganic oxyacid salt and a partial condensate thereof. body.

According to a third aspect of the present invention, there is provided a multilayer wiring board in which a capacitor having a thin film dielectric layer interposed between electrodes is formed in a circuit, wherein the thin film dielectric layer has a dielectric constant of 25 or more and a film thickness of
A multilayer wiring board having a thickness of 1.5 μm or less.

According to a fourth aspect of the present invention, in the module substrate having at least a capacitor and a semiconductor chip mounted thereon, the capacitor has a thin film dielectric having a dielectric constant of 25 or more and a thickness of 1.5 μm or less interposed between the electrodes. A module substrate characterized by the above-mentioned.

According to a fifth aspect of the present invention, there is provided a module substrate having at least a capacitor and a semiconductor chip mounted thereon, wherein the capacitor comprises a metal alkoxide, an alkylated metal alkoxide, a metal acetylacetonate in an organic resin.
A module substrate comprising a thin film dielectric containing an inorganic filler obtained by condensing at least one mixture of a compound of a metal organic acid salt, an inorganic chloride, an inorganic oxyacid salt and a partial condensate thereof.

According to a sixth aspect of the present invention, there is provided a multilayer wiring board having a blind via hole connecting upper and lower conductor layers and having a capacitor comprising a thin film dielectric and an electrode on at least one conductor layer. 3. A multilayer wiring board comprising the thin film dielectric according to claim 1 or 2.

A seventh aspect of the present invention relates to (a) an organic compound having at least one or more epoxy group or unsaturated double bond in a structure, (b) a metal alkoxide, an alkylated metal alkoxide, a metal acetylacetonate, A thin film comprising at least one compound selected from an organic acid salt, an inorganic chloride, and an inorganic oxyacid salt and a partial condensate thereof; and (c) a photoacid generator or a photobase generator. Dielectric.

An eighth invention relates to a method of manufacturing a multilayer wiring board having a capacitor in a circuit, wherein (i) a step of forming an electrode and a circuit, and (ii) an inorganic filler is dispersed in an organic resin between the electrodes. Forming a thin film dielectric layer,
ii) A method for manufacturing a multilayer wiring board, the method including at least a step of forming the thin film dielectric layer into an arbitrary shape by using exposure light for activation and development.

According to a ninth aspect, in a method of manufacturing a module substrate having a capacitor in a circuit, (i) a step of forming an electrode and a circuit, and (ii) an inorganic filler is dispersed in an organic resin between the electrodes. A method of manufacturing a module substrate, comprising at least a step of forming a thin-film dielectric layer, and (iii) a step of forming the thin-film dielectric layer into an arbitrary shape using exposure to activating light and development.

Further, the present invention provides (a) an organic compound having at least one or more epoxy group or unsaturated double bond in a structure, and a mixture thereof, (b) a metal alkoxide, an alkylated metal alkoxide, a metal At least one compound among acetylacetonate, metal organic acid salt, inorganic chloride and inorganic oxyacid salt or a partially hydrolyzed condensate thereof, and (c) a photoacid generator or a photobase generator. A photosensitive resin, characterized in that:

The present invention also relates to a multilayer wiring board using a thin film dielectric made of the photosensitive resin composition of the invention.

The present invention will be described in detail with reference to the schematic sectional views of FIGS. 1, 2, and 3.

In FIG. 1, reference numeral 1 denotes (a) an organic compound having at least one or more epoxy group or unsaturated double bond in the structure, and a mixture thereof, (b) a metal alkoxide, an alkylated metal alkoxide, a metal At least one compound among acetylacetonate, metal organic acid salt, inorganic chloride and inorganic oxyacid salt or a partial hydrolysis condensate thereof, and (c) a photoacid generator or a photobase generator are essential components. (A)
(B) The solution composed of (c) is applied to the lower electrode 2 and sprayed to remove the solvent to form a thin film layer. Then, an active light source such as a high-pressure mercury lamp is applied through a mask having an arbitrary shape. By using, a complicated shape can be formed by curing and developing to remove the unexposed portions. Also,
Here, laser drilling may be used in combination to obtain an arbitrary shape.

FIG. 2 is a top view of one thin film dielectric portion. Here, the activation light source is used because (c) generates an acid or a base and (a) causes crosslinking,
This is because (b) causes dehydration condensation to form inorganic fine particles to form a high dielectric constant thin film layer as shown. Further, an electrode 2 is formed on the dielectric thin film, and can be connected to the semiconductor chip 6 and other elements by the wiring 3. Either one or both of the upper and lower electrodes may be formed by vapor deposition of metal or plating.

As a starting material of the multilayer wiring board, an organic wiring board indicated by 7, which is obtained by etching a copper-clad laminate or by forming wiring on the laminate by an additive method can be used. When the conductor wiring is made of copper, the adhesion between the conductor wiring and the photosensitive layer can be increased by subjecting the surface of the copper to known copper surface formation, oxide film formation, oxide film reduction, or nickel plating. As the insulating layer 4, an organic insulator used for a build-up type printed wiring board can be applied. For example, materials such as polyimide, photosensitive epoxy resin, and benzocyclobutene are used. As a method of forming the insulating layer 4, after sequentially forming the insulating layer, a via hole for connecting the wiring of the upper and lower layers may be formed by a laser or the like, or a via hole may be formed using a photosensitive resin. . Alternatively, a method in which a via hole is formed after bonding a film on which a wiring is formed or a film having no wiring may be employed. The wiring on the front and back and the wiring on the inner layer can be conducted through the through hole 5. The inside of the via hole is roughened with an alkaline solution, a mixed solution of chromic acid, an aqueous solution of permanganic acid, and then neutralized.
Removal of the roughened residue, application and activation of a plating catalyst, and then chemical plating or a combination of chemical plating and electroplating can be performed.

These may be used as a multilayer wiring board having a blind via hole for connecting the upper and lower conductor layers shown in FIG. 3 and having a capacitor comprising a thin film dielectric and an electrode on at least one conductor layer. The thin film dielectric used here is square. Further, the structures shown in FIGS. 1 and 3 described above may be mixed on the same substrate.

A typical example of the component (a) is a polyfunctional epoxy resin. As a preferable example from the viewpoint of developability and the like, a bifunctional epoxy resin having an epoxy equivalent of 130 to 500 g / eq, more preferably an epoxy equivalent of 130 to 3
00g / eq bifunctional epoxy resin and epoxy equivalent 160
５００500 g / eq of trifunctional or higher epoxy resin, and mixtures thereof. Also, a brominated epoxy resin may be used in combination as a flame retardant.

Specific examples thereof include various bisphenol A type epoxy resins, bisphenol F type epoxy resins, aliphatic type epoxy resins and alicyclic epoxy resins as bifunctional epoxy resins having an epoxy equivalent of 130 to 300 g / eq. Yuka Shell Epoxy Co. Epicoat 80
1,802,807,815,819,825,82
7, 828, 834, Nadecor EX-201, 212, 821 manufactured by Nagase Kasei Kogyo Co., Ltd., and KRM 2110, 2410 manufactured by Asahi Denka Kogyo KK. Further, Epicoat 1001, 1004, 10 manufactured by Yuka Shell Epoxy Co., Ltd.
For example, the bifunctional epoxy resin having a low epoxy equivalent may be added to the bifunctional epoxy resin having an epoxy equivalent of 300 g / eq or more such as 09 and adjusted to 130 to 300 g / eq. It is not preferable to use a bifunctional epoxy resin having an epoxy equivalent of 300 g / eq or more alone since the glass transition point is lowered. As the epoxy resin having three or more functions, a multifunctional epoxy resin such as a phenol novolak type epoxy resin and an orthocresol novolak type epoxy resin is used. Examples include Yuko Shell Epoxy Co., Ltd. Epicoat 180S65, 1031S, and Sumitomo Chemical Co., Ltd. E
SCN195,220, BREN-10 manufactured by Nippon Kayaku Co., Ltd.
4,105, E0CN-104S, EPPN-201,
501 and KRM-2650 manufactured by Asahi Denka Kogyo KK.

A resin having at least one phenolic hydroxyl group in the molecule may be added to the compound having an epoxy group to promote crosslinking. Examples thereof include novolak resin, meta-paraphenol novolak resin, polyhydroxystyrene, polyhydroxyphenylmaleimide, and the like. Particularly preferred examples include various resol resins having a phenolic hydroxyl group and a methylol group in the same molecule. Since the resole resin causes a self-condensation reaction by an acid catalyst, the crosslink density of the photosensitive layer increases compared to other phenol resins, giving a cured film having a higher glass transition point and reducing the amount of phenolic hydroxyl groups remaining in the cured film. It reduces plating solution resistance.

Representative examples of the resin having an unsaturated double bond group include monomers or oligomers such as acrylic acid and methacrylic acid, and vinyl ester resins having a vinyl group. The vinyl ester resin mentioned here is a resin disclosed by Shibata (Journal of the Adhesion Society of Japan, vol. 31, No. 8, p. 334 (1995)). More generally, there is a main chain compound obtained by adding acrylic acid or methacrylic acid to a polyfunctional epoxy. Examples of the polyfunctional epoxy of the main chain compound include various bisphenol A epoxy resins, bisphenol F epoxy resins,
There are aliphatic epoxy resins, alicyclic epoxy resins, phenol novolak type epoxy resins, orthocresol novolak type epoxy resins, and the like, and bromides thereof may be used. Further, two or more of these resins having a radical polymerizable group may be mixed and used. When these are used in combination with a compound having an epoxy group, a cured film having a high glass transition point can be obtained, but they can be used alone. When (a) is only a resin having an unsaturated double bond group, it is necessary to add a photo radical generator,
Examples include the combination of benzophenone, Michler's ketone, isobutylxanthone, and the like, which are hydrogen-abstractable, with alcohols, thiols, amines, and the like, which act as hydrogen donors, when they absorb ultraviolet light and are cleaved to generate radicals. These may be used in combination of two or more.

Examples of (b) are tetraethoxysilane, tetramethoxysilane, isopropoxysilane, methyltrimethoxysilane, methyltriethoxysilane,
Vinylethoxysilane, allylethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, tetraethoxytitanium, tetraethoxyzirconium, tetramethoxyzirconium, zirconiumpropoxide, aluminum Butoxide, aluminum isopropoxide, zirconium propoxide, tetraethoxylead, barium ethoxide, indium acetylacetonate, zinc acetylacetonate,
Examples include lead acetate, yttrium stearate, aluminum oxychloride, zirconium oxychloride, titanium tetrachloride, and the like, and the starting materials widely used in the sol-gel method can be used. These may be used in combination of two or more. Further, a compound obtained by partially condensing these and a mixture thereof in advance can also be used.

Next, examples of the photoacid generator (c) will be described. It is used for the polymerization of (a) and (b). For example, various onium salts include BF ₄ ⁻ , PF ₆ ⁻ ,
There are sulfonium salts and iodonium salts having AsF ₆ ⁻ and SbF ₆ ⁻ as counter anions. For example, examples of sulfonium salts include triphenylsulfonium salt, dimethylphenylsulfonium salt, diphenylbenzylsulfonium salt, tolyl sulfonium salt, 4-butoxyphenyldiphenylsulfonium salt, tris (4-phenoxyphenyl) sulfonium salt, and 4-acetoxy. -Phenyldiphenylsulfonium salt, tris (4-thiomethoxyphenyl) sulfonium salt, di (methoxynaphthyl) methylsulfonium salt, dimethylnaphthylsulfonium salt, and phenylmethylbenzyloxysulfonium salt. Examples of iodonium salts include diphenyliodonium salt, phenyl-2-thienyliodonium salt, di (2,4-methoxyphenyl) iodonium salt,
Di (3-methoxycarbonylphenyl) iodonium salt, di (4-acetamidophenyl) iodonium salt,
(4-octyloxyphenyl) phenyliodonium salt, and the like. Further, an iron-allene compound that generates a Lewis acid can also be used. These may be used in combination of two or more. On the other hand, examples of the photobase generator include ammonium salts of phenylglyoxylic acid, o-nitrobenzoylcarbamate, α, α-dimethyl-3,
5-dimethoxybenzyloxycarbamate, cobalt
(III) alkylamine complexes, zinc hydroxide + guanidine picolinate, and the like.

In order to improve the resin properties of the photosensitive resin for forming a thin film dielectric layer of the present invention, component (a) (b)
Various organic materials can be added as additives independently of how the component (c) is selected. Examples of additives that can be used include a rubber component, a thermosetting catalyst, a photoradical generator, a flame retardant, a curable resin, a sensitizer of a photoacid or base generator, and a thermoplastic resin.

The rubber component imparts flexibility to the photosensitive layer, suppresses the occurrence of cracks, and increases the adhesive force with the electrode. Examples thereof include polybutadiene and its epoxidized products, copolymers of acrylonitrile-butadiene having a vinyl, amine, and carboxyl group at its terminals, and their copolymers with epoxy resins.
Of these, two or more can be used in combination.

The thermosetting catalyst is a catalyst for polymerizing a radically polymerizable resin and an epoxy resin by heating, and is a catalyst for curing the resin remaining in the photocuring reaction by heating. As a result, the crosslinking density of the photosensitive layer is increased and the glass transition point is increased as compared with a case where the photosensitive layer is cured only with the photocuring agent. Examples of the former include various peroxides and azide compounds, and examples of the latter include various epoxy resin thermosetting catalysts such as triphenylphosphine and imidazole. There is a heat-sensitive onium salt that generates. One example of the latter is 2-butenyltetramethylenesulfonium hexafluoroantimonate (CP-66) manufactured by Asahi Denka Co., Ltd.

When an organic compound having an unsaturated double bond is added, the photoradical generator is used for crosslinking. Examples thereof include 1-hydroxycyclohexylphenyl ketone, α, α-dimethoxy-α-phenylacetophenone, 1,3-diphenyl-2-propanone, benzoin butyl ether, 2-methyl-1- [4- (methylthio) phenyl]. -2-Monforinopropane-1,2-
Hydroxy-2-methyl-1-phenylpropane-1-
On, 2-benzyl-2-dimethylamino-1- (4-
Morpholimophenyl) -butanone-1, benzyldimethyl ketal, diethoxyacetophenone, acyloxime ester, hydroxyacetophenone, trichloroacetophenone, pt-butyltrichloroacetophenone, dimethoxyacetophenone, diethoxyacetophenone, 1-phenyl-2-hydroxy- 2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholino-propan-1-one, 1-
Hydroxycyclohexyl phenyl ketone, thioxanthone, substituted thioxanthone, methyl-o-benzoylbenzoate, benzoin, benzoin methyl ether,
There are benzoin ethyl ether, benzoin propyl ether, benzophenone, hydroxybenzophenone, and the like, and regardless of these, compounds that generate radicals by absorbing activating light can be widely used. A plurality of these may be used in combination, and these initiator auxiliaries may be further added.

The flame retardant can be widely used as long as it is known as a commonly used flame retardant or flame retardant auxiliary. For example, epoxy, aromatic, aliphatic and alicyclic halides. Phosphorus compounds such as red phosphorus, yellow phosphorus, non-halogen phosphate, halogen-containing phosphate, polyphosphate, polyphosphonate, phosphorus-containing polyol and polyphosphoric acid. Antimony-based flame retardants such as antimony trioxide are exemplified. In addition, two or more arbitrarily selected flame-retardant materials can be used in combination and their synergistic effect can be utilized. It is sufficient that these additives be added in an amount of 2 parts by weight or more based on 100 parts by weight of the total amount of the organic components. If the amount is small, the flame retardancy is not sufficiently exhibited, and if the amount is large, the resolution, the adhesive strength, the contamination of the plating solution and the like are adversely affected.
Further, when it is contained in an amount of 3 to 10 parts by weight, the material is balanced with other characteristics, and is most preferable.

The rubber component is a component that increases the adhesive force with the conductor wiring formed by plating. If the amount is too small, no increase in the adhesive force is observed, and if it is too large, the developability decreases. This also has the function of increasing the adhesive strength between the dielectric layer and the underlying electrode and the electrode formed by plating.If the amount is too small, no increase in the adhesive force is observed, and if the amount is too large, the developability and the glass transition point of the photosensitive layer are reduced. descend. Triphenylphosphine based thermosetting agent,
When an imidazole compound is used, it is desirable to use it in an amount of 1 part by weight or less, and if it is more than that, the photocuring reaction may be inhibited. When a radical polymerization initiator or an onium salt is used, the photocuring reaction is not hindered, but if the amount exceeds 10 parts by weight, the photosensitive layer after curing tends to become brittle. The type and amount of the thermosetting agent can be adjusted depending on properties such as a glass transition point and an elastic modulus required for the photosensitive layer after curing.

The photosensitive resin composition is used as a varnish of a general-purpose organic solvent such as methyl ethyl ketone, toluene, xylene, methyl cellosolve, butyl cellosolve, carbitol, butyl carbitol, ethyl acetate, butyl acetate, cellosolve acetate, tetrahydrofuran and the like. Can be saved and used. A preferred solid content concentration is 30 to 80% by weight,
It is adjusted by a thin film forming method such as spraying or printing.

As the aqueous developer of the photosensitive resin composition, an aqueous solution of a water-soluble high-boiling organic solvent or an aqueous solution of a high-boiling organic solvent to which an alkali component is added is used. 2-butoxyethanol as the aqueous organic solvent,
2,2'-butoxyethoxyethanol and the like are preferably used, and as the alkaline component, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, borax and the like are used. The concentration of the aqueous organic solvent is about 10 to 80% by weight which does not cause flammability, and the concentration of the alkali component is 1 to 2%.
It is desirable to use it in the range of about 0% by weight.

An example of forming a multilayer wiring board using the photosensitive resin composition of the present invention will be described with reference to the schematic diagrams of FIGS.

Here, 1 is (a) an organic compound having at least one or more epoxy group or unsaturated double bond in the structure, and a mixture thereof, (b) metal alkoxide, metal acetylacetonate, metal organic At least one compound selected from acid salts, inorganic chlorides, and inorganic oxyacid salts or a partially hydrolyzed condensate thereof, and (c) a photoacid generator or a photobase generator. A thin-film dielectric is applied to the lower electrode 2 by applying, spraying, spin-coating, etc., drying it to remove the solvent, forming a thin-film layer, and then applying a high-pressure mercury lamp through a mask of any shape. By using an active light source such as this, it is possible to form a complicated shape by curing and developing to remove unexposed portions. Here, laser drilling may be used together to obtain an arbitrary shape. FIG. 2 is a view of the thin film dielectric portion viewed from above.

Here, the activation light source is used in that (c) generates an acid or a base, (a) causes crosslinking, and (b) acts as a catalyst, and (b) causes dehydration condensation to form inorganic fine particles. This is for the purpose of forming the high dielectric constant thin film layer shown in the figure. Further, the electrode 2 is sputtered at a low temperature on this dielectric thin film,
Alternatively, it can be formed by a method such as plating and can be connected to the semiconductor chip 6 and other elements by the wiring 3. As a starting material of the multilayer wiring board, an organic wiring board indicated by 7, which is obtained by etching a copper-clad laminate or by forming wiring on the laminate by an additive method can be used. When the conductor wiring is made of copper, the adhesion between the conductor wiring and the photosensitive layer can be increased by subjecting the surface of the copper to known copper surface formation, oxide film formation, oxide film reduction, or nickel plating. Insulating layer 4
Organic insulators used for build-up type printed wiring boards can be widely applied. For example, materials such as polyimide, photosensitive epoxy resin, and benzocyclobutene are used. As a method of forming the insulating layer 4, after sequentially forming the insulating layer, a via hole for connecting the wiring of the upper and lower layers may be formed by a laser or the like, or a via hole may be formed using a photosensitive resin. . Alternatively, a method in which a via hole is formed after bonding a film on which a wiring is formed or a film having no wiring may be employed. The wiring on the front and back and the wiring on the inner layer can be conducted through the through hole 5. The inside of the via hole is roughened with an alkaline solution, a mixed solution of chromic acid, an aqueous solution of permanganic acid, etc., and then neutralized, the roughened residue is removed, and a plating catalyst is applied and activated to perform chemical plating or chemical plating and electric plating. It can be performed by using plating in combination.

FIG. 5 is a schematic view of a multichip module prepared by mounting a semiconductor package on such an organic wiring board.

[0040]

DESCRIPTION OF THE PREFERRED EMBODIMENTS [Examples 1 to 6] Table 1 shows the compositions of the photosensitive resin compositions of Examples 1 to 5 and Comparative Examples 1 and 2 of the invention. Each component was dissolved and dispersed in 1-acetoxy-2-ethoxyethane to prepare a varnish having a solid content of 30% by weight.

[0041]

[Table 1]

Ep-828: Yuka Shell Epoxy Co., Ltd.
Bisphenol A epoxy resin (189 g / eq) Ep-807: Yuka Shell Epoxy Co., Ltd., Bisphenol F epoxy resin (168 g / eq) ESCN-195: Sumitomo Chemical Co., Ltd., Cresol novolak epoxy Resin (198 g / eq) KRM-2650: manufactured by Asahi Denka Co., Ltd., cresol novolak type epoxy resin (220 g / eq) HP-180R: manufactured by Hitachi Chemical Co., Ltd., resole resin PSF2803: manufactured by Nippon Kayaku Co., Ltd. Meta-paraphenol novolak resin DPCA-60: Nippon Kayaku Co., Ltd., acrylate oligomer SP-70: Nippon Kayaku Co., Ltd., triallylsulfonium hexafluoroantimonate GTMS: Wako Pure Chemical Co., Ltd., 3- Glycidyloxypropyltrimethoxysilane TEOS: Wako Pure Chemical Industries, Ltd., Tetra Tokishishiran Ti (i-Pr) _4: manufactured by Wako Pure Chemical Industries, Ltd., titanium tetraisopropoxide DT-8208: Daito Sangyo Co., Ltd., epoxy-modified rubber CP-66: Asahi Denka Co., Ltd., 2-butenyl Tetramethylene sulfonium hexafluoroantimonate perenol S43: polysiloxane copolymer manufactured by San Nopco Co., Ltd. (1) Evaluation of developability Metal foil having a two-layer structure of aluminum and copper (Mitsui Metals Co., Ltd.)
(A 50 μm thick UTC foil) was coated with a photosensitive resin varnish using a bar coater and dried at 120 ° C. for 15 minutes to prepare a sample having a photosensitive layer with a film thickness of about 20 μm.

The sample was irradiated with 3 J / cm ² of white light from an ultra-high pressure mercury lamp through a via hole mask having a diameter of 1 to 30 μm (every 5 μm), and then heated at 120 ° C. for 15 minutes to promote curing. The following evaluation was performed by spray development with a developer, and the resolution was evaluated by the ratio (aspect ratio) between the diameter and the thickness of the via hole that can be developed.

[Composition of developer] 2,2'-butoxyethoxyethanol: 10 g 15% aqueous solution of tetramethylammonium hydroxide: 10 g Pure water: 20 g (2) Measurement of glass transition temperature 500 μm), and (1)
Drying at 120 ° C. for 15 minutes, (2) exposure 3 J / cm ² , (3)
Curing proceeded on a schedule of heating at 120 ° C. for 15 minutes, (4) heating at 140 ° C. for 30 minutes, and (5) heating at 180 ° C. for 120 minutes. A sample was prepared by cutting the cured film into a size of 30 mm × 5 mm. The glass transition temperature was determined from tan δ by measuring dynamic viscoelasticity using DVA-200 manufactured by IT Measurement Control Co., Ltd. Measurement condition is distance between fulcrum 2
0 mm, measurement frequency 10 Hz, heating rate 5 ° C./min, measurement range, room temperature to 300 ° C.

(3) Measurement of Dielectric Properties FIG. 4 shows an example of a dielectric constant measurement test piece. A photosensitive resin BL9700 (manufactured by Hitachi Kasei Kogyo Co., Ltd.) 20 for forming a build-up substrate is applied onto a glass epoxy substrate 21 from which the copper foil of a glass epoxy substrate with a copper foil is entirely etched out, exposed and cured. Then, after the electrode 18 shown in the figure was formed in advance, a photosensitive resin having the composition shown in Table 1 was formed by spin coating, and (1) dried at 90 ° C. for 15 minutes.
(2) exposure 3 J / cm ² , (3) development, (4) heating at 120 ° C. for 15 minutes, (5) heating at 140 ° C. for 30 minutes, (6)
Curing proceeded on a schedule of heating at 180 ° C. for 120 minutes. Further, an electrode 18 was formed thereon by sputtering.

The capacitance of this capacitor at a frequency of 1 MHz was evaluated using an LCR meter, and the dielectric constant of the dielectric was determined from the film thickness separately measured. The thickness of the thin film is approximately 0.55
In μm, the effective area of the electrode is 3 × 2 mm.

Table 2 shows the characteristics of the photosensitive resin obtained together with the values of the comparative examples.

Comparative Examples 1 to 3 In Comparative Examples 1 to 3, high dielectric constant ceramic powders shown below were added to the same photosensitive resin as in the examples. Details of the composition are shown in Table 1.

T1: BaTiO ₃ average particle size 0.1 μm (dielectric constant 率 4400) T2: BaTiO ₃ average particle size 1.43 μm (dielectric constant〜35)
00) T3: TiO ₂ average particle size: 0.05 μm (dielectric constant: 98) (1) Evaluation of developability The evaluation was performed in the same manner as the evaluation of the examples.

(2) Measurement of glass transition temperature The measurement was performed in the same manner as in the evaluation of the examples.

(3) Measurement of Dielectric Properties The measurement was performed in the same manner as in the evaluation of the examples. However, since the thickness could not be reduced as in the example, the thickness was adjusted to approximately 10 μm.

[Comparative Examples 4 and 5] Comparative Example 4 is an example not containing the acid generator and the base generator as the component (c), and Comparative Example 5 is an example of a photosensitive resin not containing the component (b). It is.

Table 2 shows the characteristics of the photosensitive resin obtained together with the values of the comparative examples.

[0054]

[Table 2]

Example 7 An organic wiring board (BT resin substrate) 7 having an inner wiring 3 subjected to a blackening reduction treatment was placed on
The insulating layer 4 is formed using a photosensitive resin BL9700 (manufactured by Hitachi Chemical Co., Ltd.). The photosensitive resin layer was exposed to 2.5 J / cm ² through a via hole mask (not shown). Here, a high-pressure mercury lamp was used as a light source for exposure. After heating at 120 ° C. for 15 minutes, the unexposed portions are dissolved and removed with a developer to form via holes 15. afterwards,
It was heated at 140 ° C. for 30 minutes for post-curing.

Next, the surface of the insulating layer 4 and the inside of the via hole are roughened with an oxidizing agent, and a plating catalyst is applied, a plating resist is formed and a pattern is formed, the catalyst is activated, and a normal full additive method such as electroless plating is used. Form wiring. Finally, the coating was heated at 180 ° C. for 120 minutes to remove the plating resist, thereby forming a first layer. The above operation was repeated to form a multilayer. On this, the photosensitive resin of Example 1 was sprayed and dried. On a predetermined electrode 2 on the pattern,
A mask is arranged so that the dielectric layer 1 is located, and exposure, development, and curing are performed as described above. Here, the thickness of the dielectric layer 10 was adjusted to 1 μm. A plating resist was formed thereon, and an electrode 2 'was formed in the same manner as above. The above operation is repeated to form a multilayer, and finally, a through-hole 5 is formed, and a semiconductor chip 6 is mounted thereon to obtain a final product.

[Embodiment 8] Organic wiring board (FR4 glass epoxy board) having inner layer wiring subjected to blackening reduction treatment
17, an organic insulator 13 is formed using a photosensitive resin BL9700 (manufactured by Hitachi Chemical Co., Ltd.). The photosensitive resin layer was exposed to 2.5 J / cm ² through a via hole mask (not shown). Here, the light source used for exposure is
A high pressure mercury lamp was used. After heating at 120 ° C for 15 minutes,
The unexposed portion is dissolved and removed with a developer to form a via hole 15. Then, it heated at 140 degreeC for 30 minutes as post-hardening.

Next, the surface of the organic insulator 13 and the inside of the via hole are roughened with an oxidizing agent, and a normal full additive method such as application of a plating catalyst, formation and pattern formation of a plating resist, activation of the catalyst, and electroless plating is performed. To form a wiring. Finally, the coating was heated at 180 ° C. for 120 minutes to remove the plating resist, thereby forming a first layer. On this, the photosensitive resin of Example 2 was sprayed and dried. A mask is arranged so that the dielectric layer 10 is located on a predetermined electrode 11 on the pattern, and exposure, development, and curing are performed as described above. Here, the thickness of the dielectric layer 10 was adjusted to 1 μm. A plating resist was formed thereon, and an electrode 11 'was formed in the same manner as above. The above operation is repeated to form a multi-layer, and finally a through-hole 14 is formed, and a semiconductor chip 16 is mounted thereon to obtain a final product.

[Embodiment 9] FIG. 5 shows a multi-chip module in which a semiconductor package 23 is mounted on the organic wiring board prepared in Embodiment 8.

[0060]

According to the present invention, a thinner film can be easily formed as compared with the method of adding a high dielectric constant ceramic powder, and as shown in Table 2, a capacitor having a higher capacity than the conventional method can be formed. Further, since a thin film layer having a high dielectric constant can be formed at a low temperature, a capacitor, which is a passive element, can be formed in an organic substrate, and a miniaturized and high-density multilayer wiring board can be provided. Through holes can also be formed, and the aspect ratio of the holes is higher than that of the photosensitive resin according to the conventional method, so that a complicated shape can be handled. By using such a multilayer wiring board, a higher-density multichip module can be provided.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing a multilayer wiring board of the present invention.

FIG. 2 is a schematic view of the capacitor according to the invention shown in FIG. 1 as viewed from above a thin film dielectric.

FIG. 3 is a schematic sectional view showing a multilayer wiring board of the present invention.

FIG. 4 is a schematic view of a sample for dielectric constant measurement.

FIG. 5 is a schematic diagram showing a multi-chip module using the multilayer wiring board of the invention.

[Explanation of symbols]

1, 8 ... thin film dielectric, 2, 2 ', 11, 11', 18 ...
Electrodes, 3, 12, 24 ... wiring, 4 ... insulating layers, 5, 14 ...
Through holes, 6, 16, ... semiconductor chips, 7, 17, 2
6 organic wiring board, 9 via, 10, 19 dielectric layer,
13: Organic insulator, 15, 25: Blind via hole, 20: Photosensitive epoxy resin, 21: Glass epoxy substrate, 22: Capacitor, 23: Semiconductor package.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI H05K 1/16 H05K 1/16 D 3/46 3/46 Q N

Claims (9)

[Claims] 1. A thin-film dielectric comprising an organic resin having an inorganic filler dispersed therein and having a dielectric constant of 25 or more and a film thickness of 1.5 μm or less. 2. The method according to claim 1, wherein the inorganic filler is a compound of a metal alkoxide, an alkylated metal alkoxide, a metal acetylacetonate, a metal organic acid salt, an inorganic chloride, an inorganic oxyacid salt and a partial condensate thereof in an organic resin. 2. The thin film dielectric according to claim 1, wherein the inorganic filler has a particle diameter of 0.8 [mu] m or less obtained by condensing at least one mixture. 3. A multilayer wiring board in which a capacitor having a thin film dielectric layer interposed between electrodes is formed in a circuit, wherein the thin film dielectric layer has a dielectric constant of 25 or more and a film thickness of 1.5 μm or less. A multilayer wiring board, characterized in that: 4. A module substrate having at least a capacitor and a semiconductor chip mounted thereon, wherein the capacitor has a thin film dielectric having a dielectric constant of 25 or more and a film thickness of 1.5 μm or less interposed between the electrodes. Module board. 5. A module substrate having at least a capacitor and a semiconductor chip mounted thereon, wherein the capacitor is a metal alkoxide, an alkylated metal alkoxide, a metal acetylacetonate, a metal organic acid salt, an inorganic chloride, an inorganic chloride in an organic resin. A module substrate comprising a thin film dielectric containing an inorganic filler obtained by condensing at least one mixture of a compound of an oxyacid salt and a partial condensate thereof. 6. A multilayer wiring board having a blind via hole for connecting upper and lower conductor layers and having a capacitor comprising a thin film dielectric and an electrode on at least one conductor layer, wherein the thin film dielectric is one of claims 1 and 2. Item 8. A multilayer wiring board comprising the thin film dielectric of Item 2. (A) an organic compound having at least one or more epoxy groups or unsaturated double bonds in the structure,
(B) at least one compound of a metal alkoxide, an alkylated metal alkoxide, a metal acetylacetonate, a metal organic acid salt, an inorganic chloride, an inorganic oxyacid salt and a partial condensate thereof, (c) a photoacid generator or A thin film dielectric comprising: a photobase generator. 8. A method for manufacturing a multilayer wiring board having a capacitor in a circuit, comprising: (i) a step of forming an electrode and a circuit; and (ii) a thin film dielectric obtained by dispersing an inorganic filler in an organic resin between the electrodes. A method for manufacturing a multilayer wiring board, comprising at least a step of forming a layer, and (iii) a step of forming the thin-film dielectric layer into an arbitrary shape by using exposure to light and development. 9. A method for manufacturing a module substrate having a capacitor in a circuit, comprising: (i) a step of forming an electrode and a circuit; and (ii) a thin film dielectric layer in which an inorganic filler is dispersed in an organic resin between the electrodes. And (iii) a step of forming the thin film dielectric layer into an arbitrary shape by using exposure light and development by activating light, and a method of manufacturing a module substrate.