WO2005080074A1

WO2005080074A1 - Thin film composite material, method for producing same, and multilayer wiring board and electronic component using such thin film composite material

Info

Publication number: WO2005080074A1
Application number: PCT/JP2005/001673
Authority: WO
Inventors: Yuusuke Kondou; Yoshitaka Hirata; Yasushi Shimada; Yasushi Kumashiro
Original assignee: Hitachi Chemical Co., Ltd.
Priority date: 2004-02-19
Filing date: 2005-02-04
Publication date: 2005-09-01
Also published as: JPWO2005080074A1; TW200528580A; JP4375395B2

Abstract

Disclosed is a metal oxide thin film composite material which is excellent in adhesion to a metal layer formed thereon by plating and is hardly corroded by the plating solution. The thin film composite material comprises a copper foil with a metal thin film whose surface is provided with a dielectric thin film having such a structure wherein at least an amorphous metal oxide thin film layer containing Ti as an constituent element is included as the outermost layer.

Description

Specification

Thin film composite material, method for producing the same, and multilayer wiring board and electronic component using the thin film composite material

Technical field

The present invention relates to a metal oxide thin film composite material suitably used for an electronic device such as a capacitor, a method for producing the same, and a multilayer wiring board and an electronic component using the thin film composite material.

Background art

[0002] As electronic devices have become smaller and more sophisticated, materials such as capacitors and memories have been required to have higher dielectric constants. Metal oxides such as barium titanate, barium strontium titanate, lead zirconate titanate and other metal oxides have high dielectric constants and are therefore suitably used for these applications. Recently, demands for higher miniaturization and higher functionality have led to a demand for smaller and higher-density devices, and studies on incorporating thin-film devices into substrates have been actively conducted.

[0003] In order to form a device using a thin film, it is necessary to form a metal layer to be an electrode. For example, when a capacitor is formed of a thin film, it is common to adopt a so-called sandwich structure in which the thin film is sandwiched between metal layers. Conventionally, a dry process represented by sputtering has been generally used for forming a metal layer. However, dry processes are expensive and difficult to process large substrates. As a means to address this problem, for example, there is a method of forming a metal layer by plating, which is a very common technique in the field of printed wiring boards.

[0004] The technique of metallizing the metal oxide surface by plating is also widely used, but the conventional technique is to roughen the surface of the metal oxide to form a roughened shape, and to use the anchor effect. Generally, the adhesion between the metal layer and the metal oxide was maintained (for example, Japanese Patent Application Laid-Open No. 7-62547). However, since the thickness of a thin film is as thin as submicron, it is impossible to form a roughened shape large enough to have an anchor effect. In addition, the loss of uniformity of the film thickness causes the dielectric characteristics to vary when a capacitor is formed. Therefore, it is not preferable. Therefore, it was difficult to form a metal layer having sufficient adhesion on the surface of the metal oxide thin film by plating. On the other hand, on smooth surfaces such as resin and glass, plating methods that do not perform roughening are also being actively researched, and those using chemical bonding by a coupling agent instead of physical bonding by an anchor effect, etc. It is known. For example, Japanese Patent Application Laid-Open No. 2002-226972 discloses that a coating agent is uniformly attached to a functional group on a resin or a glass surface to improve the uniformity of a plating catalyst, and to improve a high adhesion to a plating metal layer. It has gained.

Disclosure of the invention

[0005] However, the surface of a metal oxide thin film such as barium titanate or strontium titanate has few functional groups contributing to the attachment of the coupling agent, so that the coupling agent does not adhere evenly. It was difficult to obtain sufficient adhesion between the metal oxide thin film and the plated metal layer. In addition, when the metal oxide thin film is slightly eroded by the plating solution and the uniformity of the film thickness is impaired, the dielectric characteristics of the obtained capacitor may be varied.

[0006] In view of the above problems, an object of the present invention is to provide a metal oxide thin film composite material that has excellent adhesion to a metal layer formed by a plating method and is hardly eroded by a plating solution. .

[0007] The thin film composite material of the present invention is a copper foil, formed on one surface of the copper foil, and at least one metal selected from the group consisting of Cr, Ni, Au, Ag, and an alloy thereof. And a dielectric thin film formed on the surface of the metal thin film layer, having a relative dielectric constant of 10-2000 and a film thickness of 0.052 xm, wherein the outermost layer of the dielectric thin film is It is characterized by being an amorphous metal oxide thin film layer containing Ti as a constituent element.

[0008] According to the present invention, it is possible to provide a high dielectric constant metal oxide thin film composite material that has excellent adhesion to a metal layer and is hardly eroded by a plating solution. Further, the thin film composite material of the present invention can be suitably used for electronic devices such as capacitors.

[0009] The present application is based on Japanese Patent Application No. 2004-042749 (filed on February 19, 2004) and Japanese Patent Application No. 2004-272041 (filed on September 1, 2004) filed by the same applicant. 7)), which are hereby incorporated by reference. Shall be incorporated.

Brief Description of Drawings

[FIG. 1] FIG. 1 is a cross-sectional view showing a thin film composite material 1 produced in an example, and includes a copper foil 6, a Ni thin film layer 5, a first composite metal oxide thin film layer 2, A dielectric thin film 13 composed of a second composite metal oxide thin film layer 3 and a Ti-containing amorphous metal oxide thin film layer 4.

FIG. 2 is a cross-sectional view showing a state after forming an electroless Ni—P plating layer 7 and an electric Cu plating layer 8 on the thin film composite material 1 of FIG. 1 in Example 1. is there.

FIG. 3 is a cross-sectional view showing a state after forming the upper electrode 9 by etching the plating layer of FIG. 2 in Example 1.

FIG. 4 is a cross-sectional view showing a multilayer wiring board including a thin film composite material of the present invention included in a structure manufactured in Example 3, which is laminated and integrated on six surfaces of copper foil of thin film composite material 1. It includes a pre-predator 11 and a copper foil 12, an upper electrode 9 formed in the same manner as in Example 1, and a lower electrode 10 formed by etching the thin film composite material 1.

BEST MODE FOR CARRYING OUT THE INVENTION

The thin film composite material of the present invention includes a copper foil, a metal thin film layer formed on the copper foil, and an amorphous metal oxide thin film layer formed on the metal thin film and containing Ti as a constituent element. A thin film composite material including a dielectric thin film having at least an outer layer. By using an amorphous metal oxide thin film layer containing Ti as a constituent element as the outermost layer (surface) of the dielectric thin film, it is possible to simultaneously improve the adhesion of the silane coupling agent and the effect of preventing chemical erosion. In other words.

[0012] The copper foil is not particularly limited as long as it is a commonly used copper foil. For example, a copper foil whose surface is treated with Zn or chromate for the purpose of heat resistance and protection, for improving adhesion. Any of those having a rough surface and those having other elements, for example, a small amount of Sn added for the purpose of improving characteristics, can be suitably used. The roughened surface of the copper foil having a roughened surface is preferably a surface on which the metal thin film layer is not formed, from the viewpoint of maintaining good insulation of the capacitor. The thickness of the copper foil is not particularly limited, but is preferably 10 μm to 100 μm in terms of handling.

[0013] The metal thin film layer is selected from the group consisting of Cr, Ni, Au, Ag, and alloys thereof. Ni is more preferable from the viewpoint of environmental pollution, in which one or more metals are contained, and Cr and / or Ni are more preferable in terms of cost. Cr and Ni suppress the oxidation of the copper foil during the formation of the metal oxide thin film layer, because themselves form a stable oxide film, and Au and Ag do not easily oxidize themselves. This contributes to securing the insulation of the capacitor. Other metals, such as Pt and Ti, which are often used to suppress oxidation on Si〇 substrates

2

When Pd is formed on a copper foil as in the present invention, cracks occur in the metal oxide thin film layer and it is difficult to obtain a highly reliable capacitor immediately. Preferably, the alloy contains at least one or more components selected from the group consisting of Cr, Ni, Au and Ag in an amount of 80% by weight or more in the alloy. Such alloys include, for example, Ni-P alloy, Ni-B alloy, Ni-P_B alloy, Ni-Co alloy, Ni-Cr alloy, Ni-Cr-A1 alloy, Ni-Cr-Si alloy, Ag_Nd alloy. is there . If the content of at least one or a plurality of components selected from Cr, Ni, Au and Ag is less than 80% by weight, the effect of securing the insulation of the capacitor may be reduced. Ni-P alloys are more preferable in terms of cost and ease of formation.

The thickness of the metal thin film layer is preferably in the range of 50 nm to 1 μm, more preferably in the range of 100 nm to 800 nm. If the thickness is less than 50 nm, the insulating property is undesirably reduced. It is generally disadvantageous in terms of cost to increase the thickness beyond 1 μΐη. The thickness of the thin film layer can be measured by excavating the thin film layer with a focused ion beam processing device (FIB), observing the obtained cross section with a scanning ion microscope (SIM), and measuring the length.

[0015] The method of forming the metal thin film layer on the copper foil is not particularly limited, but, for example, a plating method, a vapor deposition method, a sputtering method, or the like can be suitably used.

[0016] The dielectric thin film has at least an amorphous metal oxide thin film layer containing Ti as a constituent element (hereinafter, Ti-containing amorphous metal oxide thin film layer) as the outermost layer of the structure. Note that the “outermost layer” refers to a layer formed at the farthest position in the thickness direction of the metal thin film layer from among a plurality of thin film layers constituting the dielectric thin film, and Layer. Of course, the Ti-containing amorphous metal oxide thin film layer alone may be used as the dielectric thin film.

[0017] Examples of the Ti-containing amorphous metal oxide thin film layer include a thin film of TiO or TiO.

2

It is preferably a layer. These have silane coupling agents, possibly due to having polar groups. Can be more uniformly attached. That is, the uniformity of the plating catalyst is improved, and it becomes possible to form a plating metal layer having high adhesion. In addition, since it has excellent corrosion resistance, it is possible to suppress variations in device characteristics where erosion by a chemical solution is small. Further, the Ti-containing amorphous metal oxide thin film layer may include a crystal region. By making the crystalline region superior, the erosion by the chemical solution can be further reduced, and by making the amorphous region superior, the adhesion to the metal layer can be further improved.

Further, the thickness of the Ti-containing amorphous metal oxide thin film layer is preferably in the range of 10 nm to 200 nm, more preferably in the range of 20 to 150 nm. When the thickness is less than lOnm, it is difficult to uniformly apply a plating catalyst that easily generates pinholes in the layer, and the layer tends to be easily eroded by a chemical solution. On the other hand, when the thickness exceeds 200 nm, device characteristics are liable to deteriorate, which is not preferable.

When the dielectric thin film is composed of a plurality of layers, layers other than the Ti-containing amorphous metal oxide thin film layer, which is the outermost layer, include, for example, a composite containing Ba and / or Sr and Ti as constituent elements. It is preferable to use a metal oxide thin film layer. More preferably, a composite metal oxide thin film layer composed of an amorphous composite metal oxide containing Ba and / or Sr as a constituent element and Ti, and a crystalline layer containing Ba and / or Sr and Ti as a constituent element A composite metal oxide thin film layer composed of a composite metal oxide, a composite metal oxide thin film layer containing both the amorphous composite metal oxide and the crystalline composite metal oxide, and the like. The body thin film can also be a high-dielectric-constant dielectric thin film that is not eroded by a chemical solution that adheres to the metal layer. In order to increase the insulation of the device, it is particularly preferable to include a composite metal oxide thin film layer composed of an amorphous composite metal oxide containing Ba and / or Sr and Ti as constituent elements as a constituent of the dielectric thin film. Therefore, the dielectric thin film of the present invention is preferably a composite metal oxide thin film layer composed of an amorphous composite metal oxide containing Ba and / or Sr as constituent elements and Ti, and Ti as a constituent element. , And more preferably, a first composite metal oxide thin film layer composed of an amorphous composite metal oxide containing Ba, Z or Sr, and Ti as constituent elements. A second composite metal oxide thin film layer containing Ba and / or Sr as elements and Ti, and an element containing Ti as a constituent element; It is composed of a morphus metal oxide thin film layer. Composite metal oxides containing Ba and / or Sr and Ti as constituent elements have a particularly high dielectric constant (for example, BaTiO

3 for about 1500, SrTiO for about 200)

Three

Can do. Of course, composite metal oxides added with other elements and metal oxides, such as

Complex metal oxides with higher dielectric constant by adding La to BaTiO, and BaTiO

3 3

Composite metal oxides whose properties have been adjusted by adding CaTiO can also be suitably used.

Three

[0020] The thickness of the composite metal oxide thin film layer, particularly the composite metal oxide thin film layer composed of the amorphous composite metal oxide, is preferably in the range of 10 nm to 200 nm from the viewpoint of ensuring insulation properties. More preferably in the range of 150 nm. To increase the insulation, an amorphous region of the composite metal oxide is required. The amorphous region has a lower relative permittivity than the crystalline region. The dielectric characteristics of the device depend on the thickness of the composite metal oxide thin film layer. It is not preferable that the film becomes thicker than necessary, because it is inversely proportional to the thickness of the film. Therefore, it is desirable that the upper limit of the thickness does not exceed 200 nm. On the other hand, when the thickness is less than 10 nm, pinholes tend to be generated, and it tends to be difficult to secure necessary insulating properties.

[0021] The relative dielectric constant of the dielectric thin film composed of the metal oxide thin film layer as described above is preferably 10 to 2000, more preferably 20 to 2000. If the dielectric constant of the dielectric thin film is less than 10, the capacitance density tends to be low, and sufficient device characteristics (capacitor capacitance) tend not to be obtained. In addition, in order for the dielectric constant to exceed 2000, the film must be fired at a high temperature, which is difficult to use in a normal wiring board manufacturing process.

The thickness of the dielectric thin film is preferably in the range of 0.05 to 2 μm. If the thickness of the dielectric thin film is less than 0.05 / m, it tends to be difficult to achieve both insulating properties and device characteristics.On the other hand, if the film thickness exceeds 2 zm, the device characteristics deteriorate. There is a tendency that it is difficult to obtain a desired capacitor capacity easily, and furthermore, when a multilayer board is manufactured, the board thickness is increased, which is disadvantageous for thinning the board.

The method for forming a dielectric thin film composed of the above-described metal oxide thin film layer on the metal thin film is not particularly limited, and may be a known method. Examples thereof include a sol-gel method, a sputtering method, and a chemical method. Chemical vapor deposition (CVD). The sol-gel method is preferred because the composite metal oxide can be easily adjusted to a desired composition. In addition, the composite metal oxide thin film layer The heat treatment temperature at the time of formation is preferably 400 ° C. or less, and more preferably 350 ° C. or less, in order to suppress oxidation of the copper foil. In particular, when forming the composite metal oxide thin film layer in contact with the metal thin film layer, it is preferable to perform a heat treatment at 400 ° C. or lower.

[0024] The surface of the Ti-containing amorphous metal oxide thin film layer, that is, on the surface of the dielectric thin film, contains at least one metal such as Ni alloy such as Ni, Ni-P and Ni-B, and Cu. The metal layer may be formed as a single layer or multiple layers. This metal layer is a layer that can later become an electrode or a circuit. The method for forming such a metal layer is not particularly limited, according to a known method such as plating and sputtering. However, when an electroless plating method is applied, the cost is superior to a dry process such as sputtering. In addition, a metal layer having high adhesion can be formed, and a large substrate can be easily processed. More preferably, the metal thin film is subjected to a step of treating the surface of the dielectric thin film with a silane coupling agent, a step of applying a plating catalyst to the surface treated with the silane coupling agent, and a step of performing electroless plating using the catalyst as a nucleus. Form a layer. By applying a silane coupling agent to the surface of the dielectric thin film before the electroless plating treatment, it is possible to obtain a more uniform and highly adhesive metal layer. In addition, Ni plating film has better adhesion than Cu plating film, but has poor electrical properties. Therefore, Ni alloy such as Ni-P or Ni-B is coated on the substrate, and Cu is thickened on it by electric plating. Therefore, it is preferable that the metal layer has a multilayer structure.

[0025] The thickness of the metal layer is preferably 50 nm-30 / im. Is less than 50nm a uniform metal layer is obtained exceeds a flame member 30 _beta m during electrode processing uneconomical because the load is increased.

The thin film composite material of the present invention is suitable for producing a multilayer wiring board and an electronic component. For example, a capacitor / filter circuit is formed by etching the metal layer or the composite metal oxide thin film. It is possible to do.

The method for producing a multilayer wiring board and an electronic component including the thin film composite material of the present invention in its configuration includes, for example, 1) a step of laminating the thin film composite material of the present invention on a pre-preda or an inner substrate, 2) A process of treating the surface of the dielectric thin film with a silane coupling agent, 3) a process of applying a plating catalyst to the surface treated with a silane coupling agent, and 4) a process of performing electroless plating using the catalyst as a core. And the like. Also, after the above steps, In the case of forming an electrode for a semiconductor, for example, it can be formed by forming an electrolytic plating layer on the electroless plating layer formed in the above step 4) and then etching these plating layers sequentially. . When a thin film composite material in which the above-described metal layer is formed in advance on a dielectric thin film is used, the above steps 2) -4) for forming a similar metal layer are unnecessary. Therefore, the manufacturing process of the multilayer wiring board and the like in this case is further simplified.

Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these.

Example

[0029] (Thin film composite material 1)

Ba (〇C H) and Ti (0—i-C H) are mixed so that the molar ratio of Ba and Ti is 1: 1.

2 5 2 3 7

It was dissolved in 2-methoxyethanol which had been dehydrated with a molecular sieve to obtain a 0.6M solution. Next, this solution was refluxed at 120 ° C. for 18 hours while stirring to obtain a mixed metal alkoxide: BaTi (〇C H OCH 2).

2 4 3 6

Next, a solution B was obtained by diluting a part of the solution A with 2-methoxyethanol so that the solution concentration became 0.2 M. On the other hand, to a part of the solution A, water having a molar ratio to Ti of 1: 1 and ammonia having a molar ratio of 1: 0.15 were added to 100. After stirring with C for 3 hours, a solution C containing crystalline metal oxide particles diluted to 2-M with 2-methoxyethanol was obtained. The two solutions B and C prepared at 0.2 M were mixed in a volume ratio of 1: 1 to obtain a solution D (total of composite metal alkoxide compounds / crystalline metal oxide particles = 50 mol% Z50 mol%).

Further, a solution E was obtained by diluting tetraisopropoxide orthotitanate with a solution obtained by mixing 2_methoxyethanol and acetic acid at a volume ratio of 3: 1 to 0.4 M.

On the other hand, a copper foil 6 (manufactured by Mitsui Mining & Smelting Co., Ltd., trade name 3EC-VLP-70) having a size of 10 cm × 10 cm and a thickness of 500 nm By forming the Ni thin film layer 5, a copper foil with a Ni thin film layer was obtained.

Next, solution B was spin-coated on the Ni thin film layer 5 side of the copper foil with the Ni thin film layer. 350

After drying on a hot plate at 4 ° C for 4 minutes, spin-coat solution B again and dry in the same manner. Thus, the first composite metal oxide thin film layer 2 having a thickness of 80 nm was formed. Further, the operation of spin-coating the solution D on the first composite metal oxide thin film layer 2 and drying it in the same manner is repeated eight times to form the second composite metal oxide thin film layer 3 having a thickness of 400 nm. did. Further, the solution E was spin-coated once on the second composite metal oxide thin film layer 3, and then 350. By baking for 2 hours on a C hot plate, a Ti-containing amorphous metal oxide thin film layer 4 having a thickness of 50 nm was formed. As a result, the first composite metal oxide thin film layer 2, the second composite metal oxide thin film layer 3, and the Ti-containing amorphous metal oxide thin film layer 4 are formed on the Ni thin film layer 5 of the copper foil with the Ni thin film layer. Thus, a thin film composite material 1 having a dielectric constant of 37 and a dielectric thin film 13 with a thickness of 530 nm was obtained (FIG. 1). The thickness of each layer and the relative dielectric constant of the dielectric thin film were measured as follows.

[0034] <Thickness>

A 5 mm wide polyimide tape (for example, Kapton tape manufactured by Nitto Denko Corporation) is attached to the dielectric thin film surface of the thin film composite material at an arbitrary length, and high-pressure water washing using an aqueous treatment solution containing alumina with an average particle size of 30 μm is applied. , The dielectric thin film was removed by etching. After performing the ultrasonic cleaning, the polyimide tape was peeled off, and the thickness of the dielectric thin film (each metal oxide layer) was measured using a stylus type step 'surface shape measuring device XP-2 manufactured by Ambis.

A metal mask was fixed on the surface of the dielectric thin film of the thin film composite material, and a 50 nm thick Cr layer and a 200 nm thick Cu layer were formed by sputtering to form an upper electrode having a size of 1 mm X lmm. Next, the metal oxide thin film layer near the upper electrode is shaved with a diamond pen to expose the copper foil under the Ni thin film, and the capacitance between the upper electrode and the exposed copper foil is determined by the capacitance of the capacitor. It was regarded as the capacity and its value was measured. The relative dielectric constant of the dielectric thin film was determined from the measured value of the capacitance and the film thickness using the following equation. The capacitance was measured at three measurement points using an Agilent 4285A Precision LCR meter at 25 ° C at a frequency of 1 MHz, and the average value was measured. Using.

C = ε ε (S / d)

0

(Where C is the capacitance, ε is the dielectric constant of vacuum, ε is the relative dielectric constant of the dielectric thin film, and S is

0 r

Area, d indicates the thickness of the dielectric thin film) (Thin Film Composite Material 2)

The specific dielectric constant was increased by the same process as for the thin film composite material 1 except that the number of times of spin coating of the solution E was changed from once to three times, and a 150 nm thick Ti-containing amorphous metal oxide thin film layer was formed. 32. A thin film composite material 2 having a dielectric thin film having a thickness of 630 nm was obtained.

[0037] (Composite thin film material 3)

A thin film having a dielectric thin film having a relative dielectric constant of 40 and a film thickness of 480 nm by the same process as that of the composite thin film material 1 except that the spin coating of the solution E was omitted and the Ti-containing amorphous metal oxide thin film layer was not formed. Composite material 3 was obtained.

(Example 1)

An aqueous solution adjusted to pH 9 with sodium hydroxide is mixed with lwt% of silane coupling agent A-1100 (trade name, manufactured by Nippon Tunicer Co., Ltd.), and the thin film composite material 1 is immersed in the aqueous solution at 60 ° C for 5 minutes. did. After that, the thin film composite material 1 was washed with warm water of 40 ° C for 3 minutes, washed with Neogant B (manufactured by Atotech Co., Ltd.), Neogant 834 (manufactured by Atotech Co., Ltd.), washed with water, and Neogant WA (Atotech (Manufactured by Co., Ltd., trade name) and water washing in this order to provide a plating catalyst. Subsequently, an electroless Ni—P plating layer 7 was formed to a thickness of 0.4 μm on the surface of the dielectric thin film 13 of the thin film composite material 1 using ICP Nicoron U (trade name, manufactured by Okuno Pharmaceutical Co., Ltd.). Furthermore, a Cu plating layer 8 was formed at 15 / im by electric Cu plating (Fig. 2). Next, an etching resist was formed by a photolithographic method. As a resist material, H-9330 (trade name, manufactured by Hitachi Chemical Co., Ltd.), a dry film resist of an alkali development type, was used. Thereafter, the Cu plating layer 8 was removed by etching with a 15% aqueous solution of ammonium persulfate. The etching resist was removed with a 5% aqueous sodium hydroxide solution, and the electroless Ni—P plating layer 7 was removed by etching using Top Lip AZ (trade name, manufactured by Okuno Pharmaceutical Co., Ltd.). Thus, an upper electrode 9 having a size of lmm × 1 mm was formed on the surface of the dielectric thin film 13 of the thin film composite material 1 (FIG. 3).

(Example 2)

An upper electrode having a size of lmm X lmm was formed on the surface of the dielectric thin film in the same process as in Example 1 except that the thin film composite material 1 was changed to the thin film composite material 2.

(Example 3) 12 / m thick copper foil 12 (Furukawa Circuit Co., Ltd.) on 6 surfaces of copper foil of thin film composite material 1 via glass epoxy pre-predder 11 (Hitachi Kasei Kogyo Co., Ltd., trade name GEA-679F) Foil Co., Ltd., trade name: GTS-12), laminated and integrated under the conditions of 180 ° C, 1.5MPa pressure and 60 minutes of heating and pressurizing time, to produce a multilayer board. Next, an upper electrode 9 was formed on the surface of the dielectric thin film 13 of the thin film composite material 1 in the same process as in Example 1. Next, an etching resist is formed again at a predetermined position on the surface of the dielectric thin film 13 of the thin film composite material 1 by photolithography, and the dielectric thin film is washed by high-pressure water using an aqueous treatment solution containing alumina having an average particle diameter of 30 am. 13 was removed by etching. After ultrasonic cleaning, the etching resist was peeled off with a 5% aqueous sodium hydroxide solution, and an etching resist was formed by a photolithography method. Subsequently, the Ni thin film layer 5 was removed by etching with Top Lip BT (trade name, manufactured by Okuno Pharmaceutical Co., Ltd.). /. The copper foil 6 was removed by etching with an aqueous solution of ammonium persulfate. The etching resist was stripped with a 5% aqueous sodium hydroxide solution to form a lower electrode 10 (FIG. 4).

(Comparative Example 1)

An upper electrode having a size of lmm X lmm was formed on the surface of the dielectric thin film in the same process as in Example 1 except that the thin film composite material 1 was changed to the thin film composite material 3.

(Comparative Example 2)

The thin film composite material 3 is treated with an aqueous solution adjusted to pH 9 with sodium hydroxide and then washed with water. Neogant B (manufactured by Atotech, trade name), Neogant 834 (manufactured by Atotech, trade name), washed with water, neogant WA ( Treated in the order of Atotech Co., Ltd.) and water washing. Subsequently, an electroless Ni_P plating layer was formed on the surface of the dielectric thin film of the thin film composite material 3 using ICP Nicoron U (trade name, manufactured by Okuno Pharmaceutical Co., Ltd.). Further, a Cu plating layer of 15 zm was formed by electric Cu plating. Next, an etching resist was formed by photolithography. H-9330 (trade name, manufactured by Hitachi Chemical Co., Ltd.), which is a dry film resist of an alkali developing type, was used as a resist material. Thereafter, the Cu plating layer was removed by etching with a 15% aqueous solution of ammonium persulfate. Five. /. The etching resist was removed with an aqueous solution of sodium hydroxide, and the electroless Ni—P plating layer was removed by etching with Top Lip AZ (trade name, manufactured by Okuno Pharmaceutical Co., Ltd.). In this way An upper electrode having a size of lmm × 1 mm was formed on the surface of the dielectric thin film of the film composite material 3.

(Adhesion evaluation)

Next, the adhesiveness between the upper electrode and the outermost layer of the dielectric thin film of the evaluation substrates produced in Examples 13 and 13 and Comparative Examples 1 and 2 was examined by a tape test. Evaluation was carried out by crimping cellophane tape CFIS Z 1522 at six locations on the upper electrode, and immediately peeling it off 10 seconds later and observing the peeling of the electrode. The results are shown in Table 1. The number of NGs in the table is the number of peelings at six electrodes.

[Table 1]

[0045] In Examples 1 to 3, no electrode was peeled off. This is an effect that the hydroxyl group on the outermost layer surface of the dielectric thin film is chemically and uniformly bonded to the silane coupling agent, and high adhesion is obtained. On the other hand, in Comparative Examples 1 and 2, the polar groups on the surface of the outermost layer of the dielectric thin film were poor, so that sufficient adhesion was not obtained and electrode peeling occurred. As described above, according to the present invention, the adhesion between the metal layer formed by plating and the dielectric thin film can be improved.

(Evaluation of capacitance variation)

Subsequently, variations in the capacitance of the capacitors on the substrates prepared in each of the examples and the comparative examples were evaluated. For the substrates fabricated in Example 1-2 and Comparative Example 1-2, the metal oxide thin film layer near each upper electrode was scraped with a diamond pen to expose the copper foil under the Ni thin film. Then, the capacitance between the upper electrode and the exposed copper foil was evaluated as the capacitance of the capacitor. For the substrate of Example 3, the capacitance between the upper electrode and the lower electrode formed by etching was evaluated as the capacitance of the capacitor. The capacitance was measured at 30 measurement points using an Agilent 4285A Precision LCR meter manufactured by Agilent Technologies at 25 ° C and a frequency of 1 MHz. Table 2 shows the results.

[Table 2] Item Average (pF) Maximum (DF) Minimum (DF) Variation

Example 1 640 770 51 0 ± 20%

Example 2 450 520 390 ± 15%

Example 3 61 0 730 490 ± 20%

Comparative Example 1 800 1040 560 ± 30%

Comparative Example 2 81 0 1050 560 ± 30%

[0048] In Examples 1 to 3, the variation in the capacitance is relatively small and remains in the range of ± 20%. However, in Comparative Examples 1 and 2, the capacity variation was as large as about ± 30%. This is due to the non-uniform adhesion of the plating catalyst and the reduced uniformity of the thickness of the composite metal oxide thin film layer. Since the thin film composite material according to the present invention shows uniform adhesion of the plating catalyst and high corrosion resistance, it is possible to suppress the occurrence of such variations.

[0049] It will be appreciated by those skilled in the art that the foregoing is a preferred embodiment of the invention, and that many changes and modifications may be made without departing from the spirit and scope of the invention.

Claims

The scope of the claims

[1] copper foil,

A metal thin film layer formed on one surface of the copper foil and containing at least one metal selected from the group consisting of Cr, Ni, Au, Ag, and alloys thereof; and

A dielectric thin film formed on the surface of the metal thin film layer, having a relative dielectric constant of 10 to 2000 and a thickness of 0.052 zm,

A thin-film composite material comprising: a dielectric thin film, wherein the outermost layer of the dielectric thin film is an amorphous metal oxide thin film layer containing Ti as a constituent element.

[2] The dielectric thin film is composed of a composite metal oxide thin film layer containing Ba and / or Sr as constituent elements and Ti, and an amorphous metal oxide thin film layer containing Ti as a constituent element. 2. The thin film composite material according to claim 1, wherein:

[3] The dielectric thin film is composed of a composite metal oxide thin film layer made of an amorphous composite metal oxide containing Ba and / or Sr as the constituent elements and Ti, and an amorphous metal oxide containing Ti as a constituent element. 2. The thin film composite material according to claim 1, comprising a thin film layer.

[4] The dielectric thin film is a first composite metal oxide thin film layer composed of an amorphous composite metal oxide containing Ba, Z or Sr as constituent elements, and Ti, and Ba and / or 2. The thin film composite according to claim 1, comprising a second composite metal oxide thin film layer containing Sr and Ti, and an amorphous metal oxide thin film layer containing Ti as a constituent element. material.

[5] The amorphous metal oxide thin film layer containing Ti as the constituent element is made of Ti〇 or Ti〇

5. The thin film composite material according to claim 4, wherein the thin film composite material is a thin film layer of No. 2.

[6] The thickness force S of the composite metal oxide thin film layer composed of an amorphous composite metal oxide containing Ba and Z or Sr as the constituent elements and Ti is in a range of 10 nm to 200 nm. Item 5. The thin film composite material according to item 3 or 4.

7. The thin film composite according to claim 1, wherein the thickness of the amorphous metal oxide thin film layer containing Ti as a constituent element is in a range of 10 nm to 200 nm. material.

[8] The thin film composite material according to any one of [17] to [17], wherein the thickness of the metal thin film layer is in the range of 50 nm to 1 μm.

9. The thin film according to claim 28, wherein a heat treatment is performed at 400 ° C. or less when forming the composite metal oxide thin film layer in contact with the metal thin film layer. Composite materials.

[10] copper foil,

A metal thin film layer formed on one surface of the copper foil and containing at least one metal selected from the group consisting of Cr, Ni, Au, Ag, and alloys thereof;

A dielectric thin film formed on the surface of the metal thin film layer and having a relative dielectric constant of 10 to 2000 and a thickness of 0.052 μm, and

A metal layer formed on the surface of the dielectric thin film and containing at least one metal selected from the group consisting of Ni, Ni_P, Ni_B, and Cu;

[11] The dielectric thin film is composed of a composite metal oxide thin film layer containing Ba and / or Sr as constituent elements and Ti, and an amorphous metal oxide thin film layer containing Ti as a constituent element. 11. The thin film composite material according to claim 10, wherein:

[12] The dielectric thin film is a composite metal oxide thin film layer composed of an amorphous composite metal oxide containing Ba and / or Sr as constituent elements and Ti, and an amorphous metal oxide containing Ti as a constituent element. 11. The thin film composite material according to claim 10, comprising a thin film layer.

[13] The dielectric thin film is a first composite metal oxide thin film layer composed of an amorphous composite metal oxide containing Ba and Z or Sr as constituent elements and Ti, and Ba and / or The thin film composite according to claim 10, comprising a second composite metal oxide thin film layer containing Sr and Ti, and an amorphous metal oxide thin film layer containing Ti as a constituent element. material.

[14] The amorphous metal oxide thin film layer containing Ti as the constituent element is made of Ti〇 or Ti〇 14. The thin-film composite material according to claim 1, wherein the thin-film composite material is a thin-film layer.

[15] The composite metal oxide thin film layer comprising an amorphous composite metal oxide containing Ba and / or Sr as a constituent element and Ti as a component has a thickness of 10 nm to 200 nm. 14. The thin film composite material according to 13.

[16] The thickness of the amorphous metal oxide thin film layer containing Ti as the constituent element is 10 nm-2

The thin film composite material according to claim 4, wherein the composite thickness is in the range of OOnm.

17. The thin film composite material according to claim 10, wherein the thickness of the metal thin film layer is in a range of 50 nm and 1 μm.

18. The method according to claim 11, wherein a heat treatment is performed at 400 ° C. or less when forming the composite metal oxide thin film layer in contact with the metal thin film layer. Thin film composite material.

[19] The method according to claim 10, wherein the thickness of the metal layer is in a range of 50 nm-30 μΐη.

19. The thin film composite material according to any one of 18.

[20] forming a metal thin film layer on one surface of the copper foil, the metal thin film layer containing one or more metals selected from the group consisting of Cr, Ni, Au, Ag, and alloys thereof;

On the surface of the metal thin film layer, the relative dielectric constant is 10-2000 and the film thickness is 0.05-2 μΐη, and the outermost layer is an amorphous metal oxide thin film layer containing Ti as a constituent element. Forming a thin film,

A step of treating the dielectric thin film surface with a silane coupling agent,

A step of applying a plating catalyst to the surface treated with the silane coupling agent; and, by electroless plating with the plating catalyst as a nucleus, a group force of Ni, Ni_P, Ni_B, Cu force selected from one or more types. Forming a metal layer containing a metal,

A method for producing a thin film composite material, comprising:

[21] A multilayer wiring board comprising, in its configuration, the thin-film composite material according to any one of claims 10 to 19 or the thin-film composite material produced by the production method according to claim 20.

[22] The thin film composite material according to any one of claims 10 to 19, or the lamella according to claim 20 An electronic component comprising in its configuration a thin film composite material produced by the production method according to (1). A step of laminating a pre-preda or an inner layer substrate on a copper foil surface of the thin film composite material according to claim 1,

A step of treating the surface of the dielectric thin film with a silane coupling agent,

A step of applying a plating catalyst to the surface treated with the silane coupling agent, and at least one selected from the group consisting of Ni, Ni_P, Ni_B, and Cu by electroless plating with the plating catalyst as a nucleus. Forming a metal layer containing a metal,

A method for manufacturing a multilayer wiring board, comprising: