KR101397839B1 - Method for forming an insulation layer and an embedded capacitor comprising the insulation layer fabricated by the same - Google Patents

Abstract

The present invention relates to a method for preparing a composite material comprising a metal precursor which is immiscible to a resin solution containing a curable resin, conductive particles, a curing agent and a solvent and is coated on a substrate and cured to form an outer surface of the composite comprising a curable resin and conductive particles To a method for producing an insulating layer containing a metal crystal by inducing crystallization of a metal precursor, and to an embedded capacitor including the insulating layer produced thereby. The built-in capacitor according to the present invention includes a metal crystal insulating layer surrounding the outer surface of the composite layer including the curable resin and the conductive particles between the first electrode and the second electrode to exhibit a low dielectric loss while maintaining a high dielectric constant.

Curable resin, insulating layer, metal precursor, metal crystal, built-in capacitor

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a method of manufacturing an insulating layer and a built-in capacitor including the insulating layer,

The present invention relates to a method of manufacturing an insulating layer and a built-in capacitor including the insulating layer produced thereby, and more particularly to a built-in capacitor comprising a metal precursor which is immiscible in a resin solution containing a curable resin, conductive particles, a curing agent and a solvent A method for producing an insulating layer comprising a metal crystal by applying the composition on a substrate and then curing the mixture to induce crystallization of the metal precursor to the outer surface of the composite including the curable resin and the conductive particles, To a built-in capacitor.

In general, passive elements such as resistors, capacitors, and the like are mounted on the printed circuit board in the form of discrete parts. When the passive elements are mounted on the printed circuit board in the form of discrete parts, the passive elements occupy a large area on the printed circuit board, and the connection distance between the elements is deep, so that the inductance is increased and the electrical characteristics may be deteriorated.

In order to solve the above problems, recently, printed circuit boards incorporating passive elements such as resistors and capacitors have been developed. The built-in capacitor can dramatically reduce the size of the product, and can be placed close to the input terminal of the active device, minimizing the length of the lead wire, greatly reducing the induced inductance, and also eliminating high frequency noise.

The built-in capacitors require a capacitance of 1 pF to 1 μF or more, depending on the electronic component material applied. In the manufacture of embedded capacitors, a thin film process such as sputtering or chemical vapor deposition can achieve a high capacity, but such a process requires a low temperature and the resulting thin film can easily break when applied to an organic substrate. On the other hand, when the polymer thick film process is used, the process is easy and the reliability of the organic substrate is secured, but the dielectric capacity is low.

Accordingly, there is a need to develop a method of manufacturing an embedded capacitor that has a high dielectric capacity and a low dielectric loss, but is easy to implement.

One aspect of the present invention is to provide a method of manufacturing an insulating layer having a high dielectric loss dielectric property.

It is another object of the present invention to provide an embedded capacitor including an insulating layer according to the present invention having a high dielectric constant, an improved dielectric property of a low dielectric loss, and an electronic component material including such an embedded capacitor.

According to one aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: preparing a coating solution by adding an immiscible metal precursor to a resin solution containing a curable resin, conductive particles, a curing agent and a solvent; Applying the coating liquid onto a substrate to form a material layer; And forming an insulating layer comprising a metal crystal by UV curing or thermally curing the material layer to induce crystallization of the immiscible metal precursor to the outer surface of the composite comprising the curable resin and conductive particles, And a method for producing the same.

Another aspect of the present invention for solving the above problems is a built-in capacitor having a composite layer including a curable resin and conductive particles between a first electrode and a second electrode, And an insulating layer formed on the insulating layer.

Another aspect of the present invention for solving the above-mentioned problems relates to an electronic component material including the built-in capacitor of the present invention.

Hereinafter, the present invention will be described in more detail with reference to the accompanying drawings.

The insulating layer according to an embodiment of the present invention may be formed by adding a metal precursor that is immiscible to a resin solution containing a curable resin, conductive particles, a curing agent, and a solvent, and coating the resultant on a substrate, And inducing crystallization of the metal precursor to the outer surface of the composite.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic process diagram for explaining a method of manufacturing an insulating layer according to an embodiment of the present invention. FIG. Referring to FIG. 1, in order to manufacture an insulating layer according to an embodiment of the present invention, a resin solution is prepared by dispersing a curable resin, conductive particles and a curing agent in a solvent. Subsequently, the metal precursor is added to the prepared resin solution, and the metal precursor does not mix with the resin solution because the metal precursor has a higher polarity than the curable resin and has a low solubility with respect to the curable resin.

A resin solution containing the metal precursor thus prepared is applied on a substrate to form a material layer. Such a material layer is formed in the form of a composite of a conductive particle and a curable resin.

The application may be accomplished by a convenient method such as spin coating, electrophoretic deposition, casting, inkjet printing, spraying, offset printing, and the like.

The layer of material is then cured to induce crystallization of the immiscible metal precursor. In this process, the tail portion of the metal precursor composed of the head portion and the tail portion is separated and crystallized as the aggregation of the metal occurs on the outer surface of the composite including the curable resin and the conductive particles. The metal crystals can be crystallized into nanosize, and such a crystallization process occurs on the outer surface of the composite comprising the curable resin and the conductive particles, so that the metal crystal can be oxidized.

Since the upper part of the substrate and the lower part of the composite including the curable resin and the conductive particles are in contact with each other and the activation energy of the lower part of the complex is larger than the upper or side of the complex, the crystallization process may be started first or on the upper side of the complex.

Thus, the metal precursor crystallizes without participating in the curing reaction to form the insulating layer containing the metal crystal surrounding the surface of the composite including the resin and the conductive particles, thereby assisting the insulation of the entire system.

The curing may be carried out by various methods known in the art, such as UV curing and thermal curing, depending on the type of curable resin used. In this case, the thermal curing can be carried out by heating at a temperature of 150 to 180 DEG C for 1 to 2 hours.

The metal precursor usable in the present invention has a low conductivity and is composed of a head portion and a tail portion. The head portion may be at least one selected from the group consisting of Si, Ti, Mg, Ge, Zr, Hf, Cu, Ni and Cr , And the tail portion is selected from the group consisting of phosphoric acid inorganic salt, carbonic acid inorganic salt, nitric acid inorganic salt, alkoxide, (NHR) ₄ , Acetate, and acetylacetonate. However, the present invention is not limited thereto.

In the production method according to the present invention, the resin that can be contained in the composite containing the curable resin and the conductive particles is a thermosetting or photo-curable resin, and is preferably an epoxy resin, a polyurethane resin, a melamine resin, a urea resin, , A urethane acrylate resin, and a polyester acrylate resin, but is not limited thereto.

In the manufacturing method according to the present invention, the conductive particles that can be included in the composite including the curable resin and the conductive particles are selected from the group consisting of carbon black, carbon nanotube, carbon nanowire, carbon fiber, graphite, metal, But the present invention is not limited thereto.

In the production process according to the present invention, the curing agent used in the curing reaction may be a novolac phenolic resin of high purity, an acid anhydride, an amine, or the like, but is not limited thereto.

Examples of the solvent usable in the resin solution of the present invention include aliphatic hydrocarbon solvents such as hexane; Aromatic hydrocarbon solvents such as anisol, mesitylene and xylene; Ketone-based solvents such as methyl isobutyl ketone, 1-methyl-2-pyrrolidinone, and acetone; Ether-based solvents such as cyclohexanone, tetrahydrofuran, isopropyl ether and the like; Acetate-based solvents such as ethyl acetate, butyl acetate and propylene glycol methyl ether acetate; Alcohol-based solvents such as isopropyl alcohol and butyl alcohol; Amide solvents such as dimethylacetamide and dimethylformamide; Silicon-based solvent; Or a mixture thereof.

In a preferred example, the amount of the metal precursor of the present invention may be 0.1 to 10% by weight based on the total resin solution.

The resin solution according to the present invention may further comprise a curing accelerator. Examples of the curing accelerator include tertiary amines such as benzyldimethylamine, triethanolamine, triethylenediamine, dimethylaminoethanol and tri (dimethylaminomethyl) phenol; Imidazoles such as 2-methylimidazole and 2-phenylimidazole; Organic phosphines such as triphenylphosphine, diphenylphosphine and phenylphosphine; And tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate and triphenylphosphine tetraphenylborate. However, the present invention is not limited thereto. The amount to be used is preferably 0.1 to 0.5% by weight based on the composition of the whole resin solution.

The resin solution according to the present invention may further contain an inorganic filler. As the inorganic filler usable in the present invention, it is preferable to use fused or synthetic silica having an average particle size of 0.1 to 35 탆, It is preferably 1 to 10% by weight based on the composition constituting the solution.

In the resin solution of the present invention, a coloring agent such as a higher fatty acid, a higher fatty acid metal salt, an organic / inorganic dye, a coupling agent such as an epoxy silane, an aminosilane, an alkylsilane, or a modified silicone oil may be used Can be used according to. At this time, the amount to be used is preferably 0.05 to 5% by weight with respect to the composition of the whole resin solution.

2 is a cross-sectional schematic diagram of a metal crystal insulating layer 200 surrounding an outer surface of a curable resin and conductive particle composite layer 300 according to an embodiment of the present invention.

The metal crystal insulating layer 200 formed by the above-described method has a low dielectric loss characteristic by blocking leakage current which is the greatest cause of dielectric loss.

The thickness of the insulating layer according to the present invention may vary depending on the curing temperature or the concentration of the metal precursor to be added, and may be 5 to 100 nm, but is not limited thereto.

Another aspect of the present invention is

A built-in capacitor having a composite layer including a curable resin and conductive particles between a first electrode and a second electrode,

And a metal crystal insulating layer surrounding the outer surface of the composite layer.

3 is a cross-sectional schematic view of an embedded capacitor according to an embodiment of the present invention. Referring to FIG. 3, the embedded capacitor of the present invention includes a first electrode 100, a second electrode 400, a composite layer of a curable resin and conductive particles And a metal crystal insulating layer 200 surrounding the semiconductor layer 300.

As shown in FIG. 3, the built-in capacitor of the present invention is formed by stacking a metal crystal insulating layer 200 surrounding a composite layer 300 of a curable resin and a conductive particle on a first electrode 100, (400) may be stacked.

As the metal used for the first electrode 100 and the second electrode 400 in the built-in capacitor of the present invention, metals such as Pt, Au, Ag, Pd, Cu, Ni, Cr and Mo may be used. It is not.

The metal that can be used for the metal crystal insulating layer 200 may be at least one selected from the group consisting of Si, Ti, Mg, Ge, Zr, Hf, Cu, Ni and Cr.

The resin that can be used for the composite layer 300 is selected from the group consisting of an epoxy resin, a polyurethane resin, a melamine resin, a urea resin, a phenol resin, an alkyd resin, a urethane acrylate resin, and a polyester acrylate resin as curable resins But the present invention is not limited thereto.

The conductive particles usable in the composite layer 300 may be at least one selected from the group consisting of carbon black, carbon nanotubes, carbon nanowires, carbon fibers, graphite, metals, and metal oxides, but is not limited thereto .

In the built-in capacitor of the present invention, the thickness of the composite layer may be 5 to 30 占 퐉, and the thickness of the metal crystal insulating layer surrounding the outer surface of the composite layer may be 5 to 100 nm, but is not limited thereto.

The present invention also provides an electronic component material including the built-in capacitor.

The electronic component materials include, but are not necessarily limited to, printed circuit boards, portable radios, hand held products, or computer accessory boards.

Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are only the preferred embodiments of the present invention, and the present invention is not limited by the following examples.

Manufacturing example  1: Preparation of an epoxy resin solution containing a metal precursor

6.308 g of cycloaliphatic epoxy resin, 1.525 g of carbon black (ketjen black 300, mitzubishi) and 4.205 g of hexahydro-4-methylphthalic anhydride were dispersed in ethyl acetate to prepare a resin solution . 0.608 g of tetraethyl orthosilicate (TEOS) was added to the prepared resin solution to prepare an epoxy resin solution containing a metal precursor.

Example  One: The insulating layer  Manufacture of embedded capacitors

Cu was deposited on the silicon substrate to a thickness of about 100 nm to form a first electrode. Then, the resin solution according to Preparation Example 1 was printed at a thickness of 15 μm on the first electrode and cured at 160 ° C. for 60 minutes to form carbon A metal crystal insulating layer surrounding the black / epoxy composite was prepared.

Cu was deposited on the resultant metal crystal insulating layer to a thickness of about 100 nm to form a second electrode to prepare a capacitor.

Manufacturing example  2: Preparation of epoxy resin solution

6.308 g of cycloaliphatic epoxy resin, 1.525 g of carbon black (ketjen black 300, mitzubishi) and 4.205 g of hexahydro-4-methylphthalic anhydride were dispersed in ethyl acetate to prepare a resin solution .

Comparative Example  1: Manufacture of built-in capacitors

Cu was deposited on the silicon substrate to a thickness of about 100 nm to form a first electrode. Then, the resin solution according to Production Example 2 was printed on the first electrode to a thickness of 15 μm and cured at 160 ° C. for 60 minutes to form carbon A metal crystal insulating layer surrounding the black / epoxy composite was prepared.

Cu was deposited on the resultant metal crystal insulating layer to a thickness of about 100 nm to form a second electrode to prepare a capacitor.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the invention as set forth in the appended claims. Modifications and variations are intended to be included within the scope of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic process diagram for explaining a method of manufacturing an insulating layer according to an embodiment of the present invention;

2 is a schematic sectional view of a metal crystal insulating layer 200 surrounding an outer surface of a curable resin and a conductive particle composite layer 300 according to an embodiment of the present invention.

3 is a schematic cross-sectional view of an embedded capacitor according to an embodiment of the present invention.

Description of the Related Art [0002]

100: first electrode 200: metal crystal insulating layer

300: Composite layer of curable resin and conductive particles

 400: second electrode

Claims (11)

Preparing a coating liquid by adding an immiscible metal precursor to a resin solution containing a curable resin, conductive particles, a curing agent and a solvent; Applying the coating liquid onto a substrate to form a material layer; And Forming an insulating layer including a metal crystal by inducing crystallization of the immiscible metal precursor to the outer surface of the composite comprising the curable resin and the conductive particles by UV curing or thermosetting the material layer, Gt; The method of claim 1, wherein the metal precursor includes a head portion and a tail portion, and the head portion is at least one selected from the group consisting of Si, Ti, Mg, Ge, Zr, Hf, Cu, (NHR) ₄ , a phosphoric acid-based inorganic salt, a nitric acid-based inorganic salt, an alkoxide, Wherein the insulating layer is at least one selected from the group consisting of acetate and acetylacetonate. The curable resin composition according to claim 1, wherein the curable resin is at least one selected from the group consisting of an epoxy resin, a polyurethane resin, a melamine resin, a urea resin, a phenol resin, an alkyd resin, a urethane acrylate resin, and a poly Wherein the insulating layer is formed on the insulating layer. The method of manufacturing an insulating layer according to claim 1, wherein the conductive particles are at least one selected from the group consisting of carbon black, carbon nanotubes, carbon nanowires, carbon fibers, graphite, metals, and metal oxides. The method according to claim 1, wherein the composition ratio of the metal precursor is 0.1 to 10 wt% with respect to the total resin solution. The method according to claim 1, wherein the thermosetting is performed by heating at a temperature of 150 to 180 ° C for 1 to 2 hours.  The method of claim 1, wherein the insulating layer has a thickness of 5 to 100 nm. A built-in capacitor having a composite layer including a curable resin and conductive particles between a first electrode and a second electrode, And a metal crystal insulating layer surrounding the outer surface of the composite layer. 9. The built-in capacitor of claim 8, wherein the composite layer has a thickness of 5 to 30 占 퐉. The built-in capacitor according to claim 8, wherein the metal-crystal insulating layer has a thickness of 5 to 100 nm. An electronic component material comprising the embedded capacitor of claim 8.

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