JPH08259265A - Glass-ceramic dielectric material - Google Patents

Abstract

PURPOSE: To obtain a glass-ceramic dielectric material having a high relative permittivity and a small dielectric loss at frequency in a microwave region, capable of using silver or copper as an electrode or conductor material because the dielectric material can be fired at a low temp., having high mechanical strength and satisfactory heat resistance and suitable for use as a microwave circuit part material. CONSTITUTION: This glass-ceramic dielectric material consists of 40-90wt.% glass powder and 60-10wt.% ceramic powder. The glass powder consists of, by weight, 10-35% SiO2 , 5-35% Ln2 O3 (lanthanoid oxide), 15-50% TiO2 , 3-45% RO (alkaline earth metal oxide) 0.1-25% ZnO, 0-30% PbO, 0-30% Bi2 O3 and 0-25% ZrO2 . A ceramic material having a relative permittivity of >=9 and a dielectric loss of <=20×10<-4> at 1GHz frequency is preferably used as the ceramic powder.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention has a high relative dielectric constant and a low dielectric loss, particularly at frequencies in the microwave region, specifically at frequencies of 0.1 GHz and above, and is suitable as a microwave circuit component material. Glass ceramic dielectric material.

[0002]

2. Description of the Related Art In the advanced information age, information transmission tends to be faster and higher in frequency. In mobile communication devices typified by car phones and personal radios, and new media devices typified by satellite broadcasting, satellite communication, CATV, etc., compactification of the devices is strongly promoted, and along with this, dielectric resonators, etc. There is also a strong demand for miniaturization of the microwave circuit element.

The size of the microwave circuit element is based on the wavelength of the electromagnetic wave used. The wavelength λ of the electromagnetic wave propagating through the dielectric having the relative permittivity ε is λ = λ ₀ / √ε, where λ ₀ is the wavelength in vacuum. The circuit element can be miniaturized in inverse proportion to the square root of ε, but when the element has a large relative permittivity, electromagnetic wave energy is concentrated in the element, which also has an advantage of reducing electromagnetic wave leakage.

In view of the above circumstances, in recent years, various ceramics having a high relative dielectric constant at frequencies in the microwave region have been developed as circuit component materials.

Further, a material in which a resin is reinforced with glass fiber having a high relative dielectric constant at the above-mentioned frequency has been developed, which is disclosed in JP-A-4-322007 and JP-A-4-367.
This is specifically disclosed in Japanese Patent No. 537.

[0006]

As the above-mentioned ceramic materials, for example, BaO--TiO ₂ system ceramics, B
aO-Ln ₂ O ₃ -TiO ₂ based ceramic, composite perovskite ceramic, ZrO ₂ -TiO ₂ -SnO ₂
Ceramics and the like are known. These ceramic materials have high permittivity, low dielectric loss, and high strength. However, when these materials are formed into a sheet, and a plurality of sheets are laminated and then fired to produce a high-frequency device or circuit board of a laminated type, it is necessary to fire at a temperature of 1200 ° C. or higher, and therefore electrodes and conductors are required. As a material, silver or copper cannot be used, and it is necessary to use an expensive material having higher heat resistance, which has a drawback that the material cost becomes high.

Further, the above-mentioned material in which the resin is reinforced by the glass fiber is superior to ceramics in the point of cutting and punching, but at a frequency of 0.1 GHz or more,
In order to obtain a relative permittivity of 10 or more, instead of the epoxy resin which has been widely used for circuit boards from the past, polyvinylidene fluoride (ε = 13) or cyano resin (ε = 16 to
It is necessary to use a resin having a high relative dielectric constant such as 20). However, such resins are not suitable for high frequencies (especially 10
The dielectric loss (tan δ) at 0 MHz or higher) is high, and the performance is not good as a microwave circuit board material. Moreover, the circuit board using such a resin has a drawback that it is basically low in heat resistance.

The object of the present invention is to have high relative permittivity and low dielectric loss at frequencies in the microwave region and to be able to fire at low temperatures, so that silver or copper can be used as an electrode or conductor material. Moreover, it is an object of the present invention to provide a glass ceramic dielectric material having high mechanical strength and good heat resistance, which is suitable as a microwave circuit component material.

[0009]

Means for Solving the Problems As a result of various experiments conducted by the present inventors, SiO ₂ , Ln ₂ O ₃ , TiO ₂ , R
It was found that a glass-ceramic material capable of achieving the above object can be obtained by combining a crystalline glass powder containing O and ZnO as main components with a ceramic powder having a high dielectric constant and a low dielectric loss, and proposed as the present invention. To do.

That is, the glass-ceramic dielectric material of the present invention is composed of 40 to 90% by weight of glass powder and 60 to 10% of ceramic powder, and the glass powder is Si.
O ₂ 10-35%, Ln ₂ O ₃ 5-35%, TiO ₂ 1
5-50%, RO 3-45%, ZnO 0.1-25
%, PbO 0-30%, Bi ₂ O ₃ 0-30%, Zr
It is characterized in that it consists of O ₂ 0 to 25%.

In the present invention, the reason why the ratio of the glass powder and the ceramic powder is limited as described above is that the glass powder is less than 40% (that is, the ceramic powder is 60%).
%), It is difficult to densify at the time of firing, so that the strength of the fired body is remarkably reduced, or a large number of pores are formed inside the fired body, and the dielectric constant is reduced. On the other hand, when the glass powder content is more than 90% (that is, the ceramic powder content is less than 10%), the glass component is raised from the surface of the fired body, and the adhesive strength with the conductor printed on the surface is lowered.

The reasons for limiting the composition of the glass powder are as follows.

SiO ₂ is a glass network former, and its content is 10 to 35%, preferably 15%.
~ 30%. If the SiO ₂ content is less than 10%, it will be out of the vitrification range and stable glass will not be obtained.
If it exceeds 5%, the relative dielectric constant of the glass tends to be low.

Ln ₂ O ₃ (La ₂ O ₃ , CeO ₂ , Pr
(Lanthanoid oxides such as ₆ O ₁₁ and Nd ₂ O ₃ ) are components for increasing the relative dielectric constant and are also components for the precipitated crystals. The total content is 5 to 35%, preferably 10%.
~ 30%. When the total amount of Ln ₂ O ₃ is less than 5%, the amount of precipitated crystals decreases, the relative dielectric constant decreases, and the strength of the fired product decreases, and when it exceeds 35%, devitrification tends to occur during glass forming.

TiO _{2 is} also a component for increasing the relative dielectric constant and a component for the precipitated crystals. Further, it becomes a glass network former like SiO _2, and its content is 15 to 50%, preferably 20 to 45%. Ti
When O ₂ is less than 15%, the amount of precipitated crystals decreases, the relative permittivity decreases, and the strength of the fired body decreases.
%, The glass tends to devitrify during glass forming.

RO (alkaline earth metal oxide such as BaO, CaO, SrO) is also a component for increasing the relative dielectric constant and a component for the precipitated crystals, and its content is 3 in total.
~ 45%, preferably 5-35%. When the RO content is less than 3%, the number of precipitated crystals decreases, the relative dielectric constant decreases, the strength of the fired body decreases, and the solubility deteriorates. If RO is more than 45%, devitrification tends to occur during glass forming.

Each component of RO is BaO 3 to 35.
%, CaO 0 to 15%, SrO 0 to 15%, preferably BaO 5 to 30%, CaO.
It is desirable that they are 0 to 10% and SrO 0 to 10%.

ZnO is a component that increases the amount of precipitated crystals and improves the solubility, and the content thereof is 0.1-0.1%.
It is 25%, preferably 1 to 20%. ZnO is 0.1
If it is less than 25%, the amount of precipitated crystals becomes insufficient and the solubility decreases, and if it exceeds 25%, devitrification tends to occur during glass forming.

PbO is a component that increases the relative permittivity and the solubility, and its content is 0 to 30%, preferably 0 to 25%. When PbO is more than 30%, the amount of precipitated crystals decreases and the strength of the sintered body decreases.

Like PbO, Bi ₂ O ₃ is also a component that enhances the relative permittivity and solubility, and the content thereof is 0 to 30%, preferably 0 to 25%. Bi ₂
If O ₃ is more than 30%, the amount of precipitated crystals decreases and the strength of the sintered body decreases.

ZrO ₂ is a component that enhances the chemical durability of glass, and its content is 0 to 25%, preferably 0 to 25%.
20%. If ZrO ₂ is more than 25%, the solubility becomes poor.

As the ceramic powder used in the present invention, various materials can be used as long as they have a high relative dielectric constant and a low dielectric loss. Particularly, it is preferable to use a ceramic material having a relative permittivity of 9 or more at 1 GHz and a dielectric loss of 20 × 10 ⁻⁴ or less.

Suitable examples of such ceramic materials include Al ₂ O ₃ , ZrO ₂ , ZrSiO ₄ , and ZrTi.
RO-TiO ₂ based ceramics such as O ₄ , TiO ₂ , BaTi ₄ O ₉ , Ba ₂ Ti ₉ O ₂₀ , CaTiO ₃ and SrTiO ₃ , Ln such as Nd ₄ Ti ₉ O ₂₄ and La ₄ Ti ₉ O _24.
2 O ₃ —TiO ₂ system ceramic, and BaNd ₂ Ti ₅
O ₁₄ and SrPr ₂ Ti ₃ O _10, etc. RO-Ln ₂ O ₃ -T
_They can be used alone or in combination of two or more selected from the group of iO ₂ -based ceramics.

[0024]

The glass-ceramic dielectric material of the present invention can be baked to remove Ba ₂ Ti ₉ O ₂₀ and Ca from the glass.
TiO _3, RO-TiO ₂ system such SrTiO ₃ crystal and,
La ₄ Ti ₉ O ₂₄ , Nd ₄ Ti ₉ O _24, etc. Ln ₂ O ₃ −
TiO ₂ type crystals, SrPr ₂ Ti ₃ O ₁₀ , BaNd ₂
Ti ₅ O _14, etc. RO-Ln ₂ O ₃ -TiO ₂ based crystal is precipitated. Furthermore, in the crystals of these systems, PbO and Bi ₂ O
_May include ₃ . Since each crystal has a high relative dielectric constant, a low dielectric loss, and a high mechanical strength, it is possible to obtain a fired body excellent in these characteristics.

[0025]

EXAMPLES The glass ceramic dielectric material of the present invention will be described below based on examples.

Table 1 shows glass powders (Samples A to F) used in this example.

[0027]

[Table 1]

The glass samples in Table 1 were prepared as follows.

First, as raw materials, pure silica powder, lanthanum oxide,
Cerium oxide, praseodymium oxide, neodymium oxide,
Titanium oxide, barium carbonate, calcium carbonate, strontium carbonate, zinc oxide, lead oxide, bismuth oxide, zirconium oxide are prepared, and the raw materials are mixed so as to have the respective compositions in the table, and then placed in a platinum crucible and 1400 to 1500. After being melted at 3 ° C. for 3 to 6 hours, it was formed into a thin plate by a water-cooled roller. Next, after crushing this molded body roughly, water is added and wet crushed by a ball mill to obtain an average particle size of 1.5 to
The powder was 3.0 μm.

The glass powder thus obtained has a frequency of 1 GHz.
At a frequency of 15.9 to 18.6 and a dielectric constant of 13 to 20
It had a dielectric loss of × 10 ^-4 .

Table 2 shows the ceramic powder (samples a to g) used in this example.

[0032]

[Table 2]

In Table 2, Al ₂ O ₃ of sample a and Z of sample b
A commercially available product was used as rO ₂ . For other ceramic powders, zirconium oxide, pure silica powder, titanium oxide, barium carbonate, and neodymium oxide were prepared as raw materials, and Table 2
After each raw material was blended so as to obtain the above-mentioned ceramics, water was added and wet-mixed in a ball mill for 24 hours, followed by drying and then firing under the firing conditions shown in the table. It was prepared by pulverizing to 1.5 to 3.0 μm.

The ceramic powder thus obtained has 1
A relative permittivity of 9.0 to 100.0 at a frequency of GHz,
It had a dielectric loss of 0.5 to 8.0 × 10 ⁻⁴ .

Tables 3 and 4 show glass-ceramic dielectric materials (Sample Nos. 1 to 16) produced by mixing the glass powder of Table 1 and the ceramic powder of Table 2.

[0036]

[Table 3]

[0037]

[Table 4]

A method for producing a green sheet made of these glass ceramic dielectric materials, laminating a plurality of the green sheets and sintering them will be described below.

First, glass powder and ceramic powder are mixed in the ratios shown in the table, and then a predetermined amount of binder, plasticizer and solvent are added to prepare a slurry. As the binder, for example, polyvinyl butyral resin, methacrylic acid resin, etc., as the plasticizer, for example, dibutyl phthalate, etc., and as the solvent, for example, toluene, methyl ethyl ketone, etc. can be used.

Then, the above slurry is applied onto a polyester film by a doctor blade method to prepare a green sheet having a thickness of about 0.2 mm. After that, dry this green sheet, cut it to a predetermined size,
A through hole is formed by mechanical processing, and a low resistance metal material serving as a conductor or an electrode is printed on the surface of the through hole and the green sheet. Then, a plurality of such green sheets are laminated and integrated by thermocompression bonding.

The laminated green sheet thus obtained is heated to about 500 ° C. at a rate of about 3 ° C./minute and kept at this temperature for about 30 minutes to remove the organic substances in the green sheet. After that, the temperature is raised to the firing temperature in the table at a rate of about 10 ° C./min, and the temperature is maintained for the firing time for sintering.

As is clear from Tables 3 and 4, each sample of the examples can be fired at a low temperature of 900 ° C., and the obtained fired body has a relative dielectric constant of 20.4 to 58.7 at a frequency of 1 GHz. And a dielectric loss of 12 to 20 × 10 ^-4 . Moreover, the bending strength was as high as 1800 kg / cm ² or more, and the thermal expansion coefficient was 81 to 90 × 10 ^-7 / ° C.

The values of relative permittivity and dielectric loss in the table were obtained at a temperature of 25 ° C. using an impedance analyzer. The thermal expansion coefficient was measured using a quartz push rod type dilatometer. The softening point was measured by the well-known fiber method. Furthermore, bending strength is 10 × 45
The fired body produced so as to have a size of × 1 mm was measured by a three-point load measuring method.

In the embodiment, the example of the green sheet is given as the method for producing the glass ceramic of the present invention.
The present invention is not limited to this, and various methods generally used for manufacturing ceramics can be applied.

[0045]

As described above, the glass-ceramic dielectric material of the present invention can be fired at a low temperature of 1000 ° C. or lower, and silver or copper can be used as an electrode or a conductor material. Further, it has a high relative permittivity and a low dielectric loss at frequencies in the microwave region, and has high heat resistance and high mechanical strength, so that it is suitable as a microwave circuit component material.

Claims (2)

[Claims] 1. Glass powder 40-90% by weight percentage,
The ceramic powder is composed of 60 to 10%, and the glass powder is SiO ₂ 10 to 35%, Ln ₂ O ₃ (lanthanoid oxide) 5 to 35%, TiO ₂ 15 to 50%, and RO.
(Alkaline earth metal oxide) 3 to 45%, ZnO
0.1-25%, PbO 0-30%, Bi ₂ O ₃ 0-
A glass-ceramic dielectric material comprising 30% and ZrO ₂ 0 to 25%. 2. The glass-ceramic dielectric material according to claim 1, wherein the ceramic powder is made of a ceramic material having a relative dielectric constant of 9 or more at 1 GHz and a dielectric loss of 20 × 10 ⁻⁴ or less.