JP3359427B2 - High frequency dielectric ceramic composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel dielectric ceramic composition having a high dielectric constant and a high Q value in a high frequency region such as a microwave and a millimeter wave. The present invention relates to a dielectric ceramic composition most suitable for a substrate, a dielectric waveguide, a dielectric antenna, a capacitor, and the like.

[0002]

2. Description of the Related Art In the high frequency region such as microwaves and millimeter waves, dielectric ceramics are widely used for dielectric resonators, MIC dielectric substrates, and the like.

[0003] Conventionally, as this kind of dielectric porcelain,
For example, MgTiO ₃ -CaTiO ₃ based materials are known. Such a material has a dielectric constant of about 20 and 1 GHz.
It has a characteristic that the Q value converted to is about 20,000.

Further, for example, as disclosed in JP-B-59-48483, a composition formula based on a molar ratio is expressed as xBa.
When expressed as O.yZnO.zNb ₂ O ₅ , 0.50 ≦
x ≦ 0.75, 0.10 ≦ y ≦ 0.30, 0.10 ≦ z
Some satisfy ≦ 0.30. Such a dielectric porcelain has the characteristic that the dielectric constant is 30 to 36, and the Q value converted to 1 GHz is 36000 to 39000.

[0005]

However, in recent years, the frequency of use has become higher due to the diversification of equipment used, and dielectric properties in such a high-frequency region, particularly a high Q value, have been required. However, at present, the conventional dielectric materials as described above have not yet obtained a practically high Q value.

Accordingly, an object of the present invention is to provide a novel dielectric ceramic composition having a high Q value and a high relative dielectric constant in a high frequency region.

[0007]

SUMMARY OF THE INVENTION The dielectric ceramic composition for high frequencies of the present invention comprises at least Ba, Z
A composite oxide containing n, Nb, and W, wherein the composition formula based on the molar ratio of these metal elements is aBaO.bZnO.
When expressed as cNb ₂ O ₅ .dWO ₃ , a, b, c,
d is 0.40 ≦ a ≦ 0.70, 0.10 ≦ b ≦ 0.3
5, 0 <c ≦ 0.30, 0 <d ≦ 0.35, 0.14 ≦
c + d ≦ 0.36 and a + b + c + d = 1.00 are satisfied.

Further, at least Ba, Z
A composite oxide containing n, Nb, W, and Ta, wherein the composition formula based on the molar ratio of these metal elements is aBaO.bZ
When expressed as nO.cNb ₂ O ₅ .dWO ₃ .eTa ₂ O ₅ , said a, b, c, d and e are 0.40 ≦ a ≦ 0.7
0, 0.10 ≦ b ≦ 0.35, 0 <c ≦ 0.30, 0 <
d ≦ 0.35, 0 <e ≦ 0.30, 0.16 ≦ c + e ≦
This is a high frequency dielectric ceramic composition satisfying 0.31, a + b + c + d + e = 1.00.

In the dielectric ceramic composition of the present invention, Ba
The molar ratio of O was set to 0.40 ≦ a ≦ 0.70 because
When a is smaller than 0.40, the Q value decreases,
This is because sintering tends to be difficult, and when it is larger than 0.70, sintering tends to be difficult. In particular,
It is preferable that 0.44 ≦ a ≦ 0.63.

Further, the molar ratio of ZnO is 0.10 ≦ b ≦
The reason for setting the value to 0.35 is that when b is less than 0.10, sintering becomes difficult or the Q value decreases. When b is more than 0.35, the Q value decreases, This is because sintering becomes difficult. In particular, 0.16 ≦ b ≦ 0.
It is preferably 35.

The reason for setting the molar ratio of Nb ₂ O ₅ to 0 <c ≦ 0.30 is that when c is larger than 0.30, the Q value decreases and sintering becomes difficult.

The reason why the molar ratio of WO ₃ is 0 <d ≦ 0.35 is that when d is larger than 0.35, the Q value decreases,
This is because sintering becomes poor. In particular, 0.003 <d ≦ 0.
It is preferably 25.

Further, when the molar ratio of Ta ₂ O ₅ is 0 <e ≦
The reason for setting it to 0.30 is that sintering becomes difficult when e is larger than 0.30.

Further, the value of c + d is set to be 0.14 ≦ c + d ≦
The reason for setting the value of 0.36 and c + e to be 0.16 ≦ c + e ≦ 0.31 is that if the value of c + d or c + e is out of this range, Q
This is because the value decreases or sintering becomes poor.

The high frequency dielectric ceramic composition of the present invention has a composition formula of aBaO.bZnO.cNb ₂ O ₅ .dWO _3.
When expressed as eTa ₂ O ₅ , a, b, c, d, and e are 0.4
4 ≦ a ≦ 0.63, 0.16 ≦ b ≦ 0.35, 0 <c ≦
0.30, 0.003 <d ≦ 0.25, 0 <e ≦ 0.3
0, 0.16 ≦ c + e ≦ 0.31, a + b + c + d + e
= 1.00 is desirable.

Further, the dielectric material of the present invention comprises Ba, Z
A composite oxide containing n, Nb, W or Ba, Zn, Nb, W, Ta, which is mainly composed of a perovskite-type crystal phase, and may contain other than a perovskite-type crystal phase. . The material having such a crystal may be in any form of a polycrystal such as a sintered body or a single crystal.

As a method for producing a porcelain based on the present invention, for example, an oxide of Ba, Zn, Nb, W or Ta or a metal salt such as a carbonate or a nitrate which forms an oxide by firing is used as a raw material. Is weighed so as to be in the above-mentioned range, then wet-pulverized by a ball mill, and dehydrated and dried. After this, the mixture is heated at 500-1500C for 0.1-
After calcining for 100 hours, the calcined product is put into a ball mill, mixed and pulverized with a solvent and an organic binder, and granulated or sized. Alternatively, oxides of Ba, Zn, and Nb or metal salts such as carbonates and nitrates that form oxides by firing, or oxides of Ta or metal salts such as carbonates and nitrates that generate oxides by firing. , And powders of Ba, Zn, and W or metal salts such as carbonates and nitrates that generate oxides by firing are separately prepared, pulverized, and calcined, and these calcined products are subjected to ball milling. , Mixed and pulverized with a solvent and an organic binder, and granulated or sized. Then, for example, it is possible to obtain a dielectric porcelain having a relative density of 90% or more by press-molding at a predetermined pressure to form into a predetermined shape and firing in the air at 1200 to 1750 ° C. for 0.1 to 200 hours. .

The high frequency dielectric ceramic composition of the present invention contains at least Ba, Zn, Nb, M
g, W, and Ta are composite oxides, and the composition formula based on the molar ratio of these metal elements is aBaO.bZnO.
When expressed as cNb ₂ O ₅ .dMgO.eWO ₃ .fTa ₂ O ₅ , a, b, c, d, e, and f are 0.43 ≦ a
≦ 0.68, 0.01 ≦ b ≦ 0.30, 0 ≦ c ≦ 0.3
0, 0 <d ≦ 0.35, 0 <e ≦ 0.35, 0 <f ≦
0.30, 0.50 ≦ (b + d) / (c + e + f) ≦
1.60, a + b + c + d + e + f = 1.00.

In the dielectric ceramic composition of the present invention, Ba
The reason for setting the molar ratio of O to 0.43 ≦ a ≦ 0.68 is that
This is because if a is smaller than 0.43 and larger than 0.68, sintering failure occurs. In particular, 0.52 ≦ a ≦
Preferably, it is 0.62.

Further, the molar ratio of ZnO is 0.01 ≦ b ≦
The reason for setting the value to 0.30 is that when b is smaller than 0.01, the Q value decreases, and when b is larger than 0.30, sintering failure occurs. This ZnO is 0.08 ≦ b
It is desirable that ≦ 0.21.

The reason for setting the molar ratio of Nb ₂ O ₅ to 0 ≦ c ≦ 0.30 is that if it is larger than 0.30, sintering will be defective. In particular, the molar ratio c of Nb ₂ O ₅ is 0.001.
It is preferable that ≦ c ≦ 0.11.

The reason why the molar ratio of MgO is set to 0 <d ≦ 0.35 is that when d is larger than 0.35, sintering becomes defective. Is reduced. This MgO is, in particular, 0.001 ≦ d ≦ 0.
It is preferably 150.

The reason why the molar ratio of WO ₃ is set to 0 <e ≦ 0.35 is that if e is larger than 0.35, sintering failure occurs. Is reduced. In particular, it is preferable that 0.001 ≦ e ≦ 0.150.

The reason for setting the molar ratio of Ta ₂ O ₅ to 0 <f ≦ 0.30 is that when f is larger than 0.30, sintering is poor, and when f = 0, the Q value and the ratio This is because the dielectric constant decreases. In particular, it is preferable that 0.08 ≦ f ≦ 0.20.

Also, 0.50 ≦ (b + d) / (c + e +
f) ≦ 1.60 because the Q value is reduced or the sintering is poor outside this range.

The high frequency dielectric ceramic composition of the present invention has a composition formula of aBaO.bZnO.cNb ₂ O ₅ .dMgO.
When expressed as eWO ₃ · fTa ₂ O ₅ , a, b, c, d,
e and f are 0.52 ≦ a ≦ 0.62, 0.08 ≦ b ≦
0.21, 0.001 ≦ c ≦ 0.11, 0.001 ≦ d
≦ 0.150, 0.001 ≦ e ≦ 0.150, 0.08
≦ f ≦ 0.20, 0.50 ≦ (b + d) / (c + e +
f) It is desirable to satisfy 1.60 and a + b + c + d + e + f = 1.00.

The dielectric material of the present invention comprises Ba, Zn, N
This is a composite oxide containing b, Mg, W, and Ta, which is mainly composed of a perovskite-type crystal phase, and may further contain a substance other than the perovskite-type crystal phase. The material having such a crystal may be in any form of a polycrystal such as a sintered body or a single crystal. When the dielectric ceramic of the present invention contains other than the perovskite-type crystal phase, the intensity ratio of the main peak of the crystal phase other than the perovskite-type crystal phase to the main peak of the perovskite-type crystal phase is identified by X-ray diffraction. It is desirable that it is 10% or less.

Further, for example, Al, Fe, Pb, Mn,
Elements such as Si, V, La, Sb, Ca, Zr, or at least one of these compounds are added in an amount of 1 to the total amount.
You may contain 0 mol% or less.

As a method for producing a porcelain based on the present invention, for example, an oxide of Ba, Zn, Nb, Mg, W, or Ta or a metal salt such as a carbonate or a nitrate which forms an oxide by firing is used as a raw material. These are weighed so as to be in the above-mentioned range, then wet-pulverized by a ball mill, and dehydrated and dried. In addition to Ba, Zn, Nb, Mg, W and Ta,
For example, Ni, Co, Y, Al, Fe, Pb, Mn, S
Elements such as i, V, La, Sb, Ca, Zr or at least one of these compounds are added to the total amount by 10%.
You may add below mol%.

Thereafter, the mixture is calcined at 500 to 1500 ° C. for 0.1 to 100 hours, and the calcined product is put in a ball mill and mixed and pulverized with a solvent and an organic binder.
Granulate or size. Then, for example, press molding is performed at a predetermined pressure to form a predetermined shape, and the pressure is adjusted to 0.1 to 1750 ° C. in an atmosphere containing 1% by volume or more of oxygen.
By firing for 1 to 200 hours, the dielectric ceramic of the present invention can be obtained.

The high frequency dielectric ceramic composition of the present invention comprises at least Ba, Y, Nb, Mg, W, T
a is a composite oxide containing a, and the composition formula based on the molar ratio of these metal elements is aBaO.bY ₂ O ₃ .cNb ₂
When expressed as _{O 5 · dMgO · eWO 3 ·} fTa 2 O 5,
A, b, c, d, e, and f are 0.40 ≦ a ≦ 0.7.
6, 0 <b ≦ 0.26, 0 <c ≦ 0.26, 0 ≦ d ≦
0.35, 0 ≦ e ≦ 0.35, 0 ≦ f ≦ 0.25, 0.
60 ≦ (b + d) / (c + e + f) ≦ 1.50, d + e
+ F> 0 and a + b + c + d + e + f = 1.00 are satisfied.

In the dielectric ceramic composition of the present invention, Ba
The molar ratio of O was set to 0.40 ≦ a ≦ 0.76 because
When a is smaller than 0.40, the Q value decreases,
This is because sintering tends to be difficult, and when it is larger than 0.76, sintering becomes difficult. In particular, 0.45 ≦
It is preferable that a ≦ 0.71.

The molar ratio of Y ₂ O ₃ is set to 0 <b ≦ 0.2
The reason for setting the value to 6 is that when b is larger than 0.26, the Q value decreases and sintering becomes difficult. In particular, 0.
It is preferable that 002 ≦ b ≦ 0.210.

The reason why the molar ratio of Nb ₂ O ₅ is 0 <c ≦ 0.26 is that when c is larger than 0.26, the Q value is reduced, and sintering becomes difficult. In particular, 0.001
It is preferable that ≦ c ≦ 0.210.

The reason that the molar ratio of MgO is 0 ≦ d ≦ 0.35 is that when d is larger than 0.35, the Q value decreases,
This is because sintering becomes poor. In particular, 0.030 ≦ d ≦ 0.
It is preferably 300.

The reason why the molar ratio of WO ₃ is 0 ≦ e ≦ 0.35 is that when e is larger than 0.35, the Q value decreases,
This is because sintering becomes poor. In particular, 0.030 ≦ e ≦ 0.
It is preferably 300.

The reason why the molar ratio of Ta ₂ O ₅ is 0 ≦ f ≦ 0.25 is that if f is larger than 0.25, sintering will be defective. In particular, it is preferable that 0.01 ≦ f ≦ 0.21.

Further, in the present invention, 0.60 ≦
It is necessary that (b + d) / (c + e + f) ≦ 1.50. If the ratio is out of this range, the Q value decreases or sintering becomes poor.

The high frequency dielectric porcelain composition of the present invention has a composition formula based on a molar ratio of aBaO.bY ₂ O ₃ .cNb ₂ O
_When expressed as ₅ · dMgO · eWO ₃ · fTa ₂ O ₅ ,
a, b, c, d, e, and f are 0.45 ≦ a ≦ 0.71,
0.002 ≦ b ≦ 0.210, 0.001 ≦ c ≦ 0.2
10, 0.030 ≦ d ≦ 0.300, 0.030 ≦ e ≦
0.30, 0.01 ≦ f ≦ 0.21, 0.60 ≦ (b +
d) / (c + e + f) ≦ 1.50, d + e + f> 0, a
It is desirable to satisfy + b + c + d + e + f = 1.00.

Further, the dielectric material of the present invention comprises Ba, Y,
A composite oxide containing Nb, Mg, W, and Ta, which is mainly composed of a perovskite-type crystal phase, and may further contain a material other than the perovskite-type crystal phase. The material having such a crystal may be in any form of a polycrystal such as a sintered body or a single crystal.

As a method for producing a porcelain based on the present invention, for example, an oxide of Ba, Y, Nb, Mg, W or Ta or a metal salt such as a carbonate or a nitrate which forms an oxide upon firing is used as a raw material. After they are weighed so as to be in the above-mentioned range, they are wet-pulverized by a ball mill and dehydrated and dried. After this, the mixture is heated at 500-1500C for 0.1-
After calcining for 100 hours, the calcined product is put into a ball mill, mixed and pulverized with a solvent and an organic binder, and granulated or sized. Alternatively, an oxide of Ba, Y, Nb, Ta, or a metal salt such as a carbonate or a nitrate that generates an oxide by firing, and an oxide of Ba, Mg, or W, or a carbonate or a nitrate that generates an oxide by firing Are separately prepared, pulverized, and calcined separately, put together in these calcined ball mills, mixed and pulverized with a solvent and an organic binder, and granulated or sized. Then, for example, press molding at a predetermined pressure to form a predetermined shape is performed at a temperature of 1200 to 1750 ° C. in an oxygen-containing atmosphere at 0.1 to 20 ° C.
By firing for 0 hour, the dielectric ceramic of the present invention can be obtained.

The dielectric ceramic composition for high frequencies of the present invention comprises at least Ba, Y, Zn, Nb, W, T
a is a complex oxide containing a, and the composition formula based on the molar ratio of these metal elements is aBaO.bY ₂ O ₃ .cZnO.
・ When expressed as dNb ₂ O ₅ .eWO ₃ .fTa ₂ O ₅ ,
a, b, c, d, e, and f are 0.40 ≦ a ≦ 0.70,
0 <b ≦ 0.30, 0 <c ≦ 0.35, 0 ≦ d ≦ 0.3
0, 0 <e ≦ 0.35, 0 ≦ f ≦ 0.30, 0.20 ≦
(B + c) / (d + e + f) ≦ 1.66, a + b + c +
It is a dielectric ceramic composition for high frequency that satisfies d + e + f = 1.00.

In the dielectric ceramic composition of the present invention, Ba
The molar ratio of O was set to 0.40 ≦ a ≦ 0.70 because
When a is smaller than 0.40, the Q value decreases,
This is because sintering tends to be difficult, and when it is larger than 0.70, sintering tends to be difficult. a is
It is preferable that 0.45 ≦ a ≦ 0.65, and it is particularly preferable that 0.48 ≦ a ≦ 0.62.

When the molar ratio of Y ₂ O ₃ is 0 <b ≦ 0.3
The reason for setting 0 is that if b is greater than 0.30, Q
This is because the value decreases. This Y ₂ O ₃ is 0.010
≦ b ≦ 0.25 is desirable, and more preferably 0.1 ≦ b ≦ 0.25.
It is preferable that 030 ≦ b ≦ 0.20.

The reason why the molar ratio of ZnO is set to 0 <c ≦ 0.35 is that when the molar ratio is larger than 0.35, the Q value decreases,
This is because sintering becomes difficult. c is 0.010 ≦ c ≦
0.30, preferably 0.030 ≦ c
It is desirable that ≦ 0.25.

The reason for setting the molar ratio of Nb ₂ O ₅ to 0 ≦ d ≦ 0.30 is that when d is larger than 0.30, the Q value decreases and sintering becomes difficult. d is 0.010 ≦
Optimally, d ≦ 0.25, and more preferably, 0.030 ≦ d ≦ 0.20.

The reason why the molar ratio of WO ₃ is 0 <e ≦ 0.35 is that when e is larger than 0.35, the Q value decreases,
This is because sintering becomes poor. e is 0.010 ≦ e ≦ 0.
It is most preferable to satisfy the condition of 30, especially 0.030 ≦ e ≦ 0.25.

The reason why the molar ratio of Ta ₂ O ₅ is 0 ≦ f ≦ 0.30 is that when f is larger than 0.30, the Q value is reduced. f preferably satisfies 0 ≦ f ≦ 0.25, and most preferably 0.05 ≦ f ≦ 0.23.

0.20 ≦ (b + c) / (d + e + f) ≦
The reason why the ratio is set to 1.66 is that if the ratio is out of this range, the Q value is reduced or sintering is poor.

The dielectric ceramic composition of the present invention has a composition formula a
_{BaO · bY 2 O 3 · cZnO} · dNb 2 O 5 · eWO
_When expressed as ₃ · fTa ₂ O ₅ , a, b, c, d, e, f
Is 0.48 ≦ a ≦ 0.62, 0.03 ≦ b ≦ 0.20,
0.030 ≦ c ≦ 0.25, 0.03 ≦ d ≦ 0.20,
0.03 ≦ e ≦ 0.25, 0.05 ≦ f ≦ 0.23,
It is desirable that 0.20 ≦ (b + c) / (d + e + f) ≦ 1.66.

Further, the dielectric material of the present invention comprises Ba, Y,
A composite oxide containing Zn, Nb, W, and Ta, which is mainly composed of a perovskite-type crystal phase, and may further contain a material other than the perovskite-type crystal phase. The material having such a crystal may be in any form of a polycrystal such as a sintered body or a single crystal.

As a method for producing a porcelain based on the present invention, for example, an oxide of Ba, Y, Zn, Nb, W or Ta or a metal salt such as a carbonate or a nitrate which forms an oxide by firing is used as a raw material. After they are weighed so as to be in the above-mentioned range, they are wet-pulverized by a ball mill and dehydrated and dried. In addition to Ba, Y, Zn, Nb, W and Ta, Mg,
Ni, Co, Al, Fe, Pb, Mn, Si, V, Z
oxides such as r, La, Sb, Ca, etc.
You may add below mol%. After this, the mixture is
After calcining at 1500 ° C. for 0.1 to 100 hours, the calcined product is put into a ball mill, mixed and pulverized with a solvent and an organic binder, and granulated or sized. Or Ba,
A raw material powder to which a metal salt such as an oxide of Y, Nb, or Ta or a carbonate or a nitrate that forms an oxide upon firing is added;
Oxides of Ba, Zn, W or metal salts such as carbonates and nitrates that form oxides upon firing are separately prepared, pulverized, and calcined separately, and the calcined products are put together in a ball mill, and the solvent and the organic solvent are mixed. Mix and crush with the binder,
Granulate or size. Then, for example, press molding is performed at a predetermined pressure to form a predetermined shape.
By firing at 00 to 1750 ° C. for 0.1 to 200 hours, the dielectric ceramic of the present invention can be obtained.

[0053]

According to the dielectric ceramic composition for high frequencies of the present invention, a high Q value can be obtained while maintaining a relatively high dielectric constant in a high frequency range. Further, the temperature coefficient τf of the resonance frequency can be suppressed within a certain range near zero.

[0054]

【Example】

Example 1 BaCO ₃ , ZnO, Nb having a purity of 99% or more as raw materials
Using powders of ₂ O ₅ and WO ₃ , these were weighed in the proportions shown in Table 1 and put into a ball mill lined with rubber together with water, and wet-mixed using ZrO ₂ balls having a diameter of 10 mm.

Next, after dehydrating and drying this mixture,
After calcining at 1200 ° C. for 2 hours, the calcined product was wet-pulverized by putting water and an organic binder in a ball mill.

Thereafter, the pulverized product was dried, and then granulated through a No. 50 mesh net.
/ Cm ^{2 at} a pressure of 20 cmφ × 10 mm. Further, this disc is placed between 1350 and 1550.
A porcelain sample was obtained by firing under the conditions of ° C. × 6 hours. The porcelain sample was processed to obtain a cylinder having a size of 13 mmφ × 6 mm.

With respect to the porcelain sample thus obtained, the relative dielectric constant (εr) and the Q value at a frequency of 4 to 7 GHz were measured by the dielectric resonator method, and the resonance frequency in the temperature range from 25 ° C. to 85 ° C. The temperature change was measured, and the temperature coefficient (τf) of the resonance frequency was calculated. The Q value was converted to a Q value at 1 GHz based on a fixed relation between the Q value generally established in the microwave dielectric and the measurement frequency f = constant. The results are shown in Table 1.

[0058]

[Table 1]

According to Table 1, Sample No. whose composition is out of the range of the present invention. Nos. 13 to 18 caused sintering failure. In contrast, the sample of the present invention achieved a relative dielectric constant of 22 to 40 and a Q value of 45000 or more.

Example 2 BaCO ₃ , ZnO, Nb having a purity of 99% or more as raw materials
Using powders of ₂ O ₅ , WO _3, and Ta ₂ O ₅ , they were weighed to the proportions shown in Table 2, and thereafter, a porcelain sample was obtained in the same manner as in Example 1. The relative permittivity, temperature coefficient of resonance frequency (τf), and Q value of this porcelain sample were determined in the same manner as in Example 1 above, and these are shown in Table 2.

[0061]

[Table 2]

According to Table 2, the sample No. whose composition was out of the range of the present invention. Nos. 25 to 30 caused poor sintering. On the other hand, the sample of the present invention has a relative dielectric constant of 25-3.
9. A Q value of 41,000 or more was achieved.

Further, the present inventors have found that Ba, Zn, Nb,
A raw material powder to which an oxide of Ta or a metal salt such as a carbonate or a nitrate which forms an oxide upon firing is added;
Oxides of n and W or metal salts such as carbonates and nitrates that form oxides by firing are separately prepared, pulverized, and calcined separately, put into a calcined ball mill together, and mixed with a solvent and an organic binder. It was confirmed that, even when crushed, formed into a predetermined shape, and fired in the air, it had excellent dielectric properties within the scope of the present invention.

Example 3 BaCO ₃ , ZnO, Nb having a purity of 99% or more as raw materials
Using powders of ₂ O ₅ , MgCO ₃ , WO ₃ and Ta ₂ O ₅ , they were weighed in the proportions shown in Tables 3, 4 and 5 and put together with water into a ball mill lined with rubber to obtain a 10 mm diameter. Wet mixing was performed using a ZrO ₂ ball. Next, after dehydrating and drying this mixture, it was calcined at 1200 ° C. for 2 hours, and the calcined product was wet-pulverized by putting water and an organic binder into a ball mill.

Thereafter, the pulverized product was dried, and then granulated through a No. 50 mesh net.
/ Cm ^{2 at} a pressure of 12 cmφ × 8 mm. In addition, this disk was 148
The porcelain sample was obtained by firing at 0 to 1600 ° C. This porcelain sample was processed to obtain a column having a size of 8 mmφ × 5 mm.

With respect to the porcelain sample thus obtained, the relative dielectric constant (εr) and Q value at a frequency of 6 to 10 GHz were measured by the dielectric resonator method, and the resonance frequency in the temperature range from 25 ° C. to 85 ° C. The temperature change was measured, and the temperature coefficient (τf) of the resonance frequency was calculated. The Q value was converted to a Q value at 1 GHz based on a fixed relation between the Q value generally established in the microwave dielectric and the measurement frequency f = constant. The results are shown in Tables 3, 4 and 5.

[0067]

[Table 3]

[0068]

[Table 4]

[0069]

[Table 5]

According to Tables 3, 4 and 5, Sample No. 3 having a composition deviating from the scope of the present invention was obtained. In Nos. 66 to 76, sintering failure occurred and the relative dielectric constant and Q value were low. In contrast, the sample of the present invention has a relative dielectric constant of 19 to 38 and a Q value of 50.
000 to 230,000, and the temperature coefficient τf of the resonance frequency is −
42- + 31 ppm / ° C was achieved.

Example 4 BaCO ₃ , Y ₂ O ₃ , N
Using powders of b ₂ O ₅ , MgCO ₃ , WO ₃ and Ta ₂ O ₅ , these were weighed in the proportions shown in Table 6 and put together with water in a ball mill lined with rubber, and ZrO ₂ balls having a diameter of 10 mm And wet-mixed. Next, the mixture was dehydrated and dried, and then calcined at 1200 ° C. for 2 hours.
The calcined product was wet-pulverized by putting water and an organic binder in a ball mill.

Thereafter, the pulverized material was dried, and then granulated through a No. 50 mesh net.
/ Cm ^{2 at} a pressure of 20 mmφ × 11 mm. Further, this disc is placed between 1550 and 1700
It was fired at ℃ to obtain a porcelain sample. This porcelain sample was processed to obtain a cylinder having a size of 13 mmφ × 7 mm.

With respect to the porcelain sample thus obtained, the relative dielectric constant (εr) and Q value at a frequency of 4 to 7 GHz were measured by the dielectric resonator method, and the resonance frequency in the temperature range from 25 ° C. to 85 ° C. The temperature change was measured, and the temperature coefficient (τf) of the resonance frequency was calculated. The Q value was converted to a Q value at 1 GHz based on a fixed relation between the Q value generally established in the microwave dielectric and the measurement frequency f = constant. Table 6 shows the results.

[0074]

[Table 6]

According to Table 6, the sample No. whose composition was out of the range of the present invention. Nos. 27 to 32 caused sintering failure. In contrast, the sample of the present invention achieved a relative dielectric constant of 16 to 36 and a Q value of 40000 or more. In the table, poor sintering means cracks, deformation, unsintered evaporation, and other sintering defects.

The present inventors have proposed that Ba, Y, Nb, T
raw material powder to which an oxide of a or a metal salt such as a carbonate or a nitrate which forms an oxide upon firing is added;
g, W oxides, or metal salts such as carbonates and nitrates that form oxides upon firing are separately prepared, pulverized, calcined, put together in these calcined ball mills, and mixed with a solvent and an organic binder. Even when crushed, molded into a predetermined shape, and fired in an atmosphere containing oxygen,
Within the range of the present invention, it was confirmed that the composition had excellent dielectric properties.

Example 5 BaCO ₃ , Y ₂ O ₃ , Z
Using powders of nO, Nb ₂ O ₅ , WO ₃ and Ta ₂ O ₅ , these were weighed in the proportions shown in Table 7 and put together with water into a rubber-lined ball mill, and ZrO ₂ balls having a diameter of 10 mm were added. And wet mixed. Next, the mixture was dehydrated and dried, and then calcined at 1200 ° C. for 2 hours.
The calcined product was wet-pulverized by putting water and an organic binder in a ball mill.

Thereafter, the pulverized product was dried, and then granulated through a No. 50 mesh net.
/ Cm ^{2 at} a pressure of 20 mmφ × 11 mm. In addition, this disc was placed in air for 1450-
It was fired under the condition of 1550 ° C. × 2 hours to obtain a porcelain sample.
This porcelain sample was processed to obtain a cylinder having a size of 13 mmφ × 7 mm.

With respect to the porcelain sample thus obtained, the relative dielectric constant (εr) and Q value at a frequency of 4 to 7 GHz were measured by the dielectric resonator method, and the resonance frequency in the temperature range from 25 ° C. to 85 ° C. The temperature change was measured, and the temperature coefficient (τf) of the resonance frequency was calculated. The Q value was converted to a Q value at 1 GHz based on a fixed relation between the Q value generally established in the microwave dielectric and the measurement frequency f = constant. Table 7 shows the results.

[0080]

[Table 7]

According to Table 7, Sample No. whose composition was out of the range of the present invention. 21 to 31 were poor in sintering, and the relative dielectric constant and Q value could not be measured, or the Q value was low. In contrast, the sample of the present invention achieved a relative dielectric constant of 21 to 37 and a Q value of 42000 to 81000.

The present inventors have proposed that Ba, Y, Nb, T
raw material powder to which an oxide of a or a metal salt such as a carbonate or a nitrate that forms an oxide upon firing is added;
Oxides of n and W or metal salts such as carbonates and nitrates that form oxides by firing are separately prepared, pulverized, and calcined separately, put into a calcined ball mill together, and mixed with a solvent and an organic binder. It was confirmed that, even when crushed, formed into a predetermined shape, and fired in the air, it had excellent dielectric properties within the scope of the present invention.

[0083]

As described in detail above, according to the present invention, a high dielectric constant and a high Q value can be obtained in a high frequency range. As a result, resonator materials and MIC dielectric substrate materials used in microwave and millimeter wave regions,
The present invention can be sufficiently applied to other electronic components such as a dielectric waveguide, a dielectric antenna and the like.

──────────────────────────────────────────────────続 き Continued on the front page (31) Priority claim number Japanese Patent Application No. 6-22258 (32) Priority date February 21, 1994 (Feb. 21, 1994) (33) Priority claim country Japan (JP) (58) Field surveyed (Int.Cl. ⁷ , DB name) H01B 3/00-3/14 C04B 35/495 H01P 7/10

Claims (5)

(57) [Claims] 1. At least Ba, Zn, N as a metal element
a composite oxide containing b and W, wherein the composition formula based on the molar ratio of these metal elements is aBaO.bZnO.cNb
_When expressed as ₂ O ₅ · dWO ₃ , a, b, c, and d are 0.40 ≦ a ≦ 0.70 0.10 ≦ b ≦ 0.35 0 <c ≦ 0.30 0 <d ≦ 0 .35 0.14 ≦ c + d ≦ 0.36 a + b + c + d = 1.00 2. At least Ba, Zn, N
A composite oxide containing b, W, and Ta, wherein the composition formula based on the molar ratio of these metal elements is aBaO.bZnO.
When expressed as cNb ₂ O ₅ .dWO ₃ .eTa ₂ O ₅ , a, b, c, d, and e are 0.40 ≦ a ≦ 0.70 0.10 ≦ b ≦ 0.35 0 <c ≦ 0.30 0 <d ≦ 0.35 0 <e ≦ 0.30 0.16 ≦ c + e ≦ 0.31 a + b + c + d + e = 1.00 A high frequency dielectric ceramic composition characterized by satisfying the following condition. 3. At least Ba, Zn, N
a composite oxide containing b, Mg, W, and Ta, wherein the composition formula based on the molar ratio of these metal elements is aBaO · bZ
_{nO · cNb 2 O 5 · dMgO} · eWO 3 · fTa 2 O
₅ , a, b, c, d, e, and f are 0.43 ≦ a ≦ 0.68 0.01 ≦ b ≦ 0.30 0 ≦ c ≦ 0.30 0 <d ≦ 0. 35 0 <e ≦ 0.35 0 <f ≦ 0.30 0.50 ≦ (b + d) / (c + e + f) ≦ 1.60 a + b + c + d + e + f = 1.00 The high frequency dielectric ceramic composition is characterized by satisfying the following condition: . 4. At least Ba, Y, N as a metal element
a composite oxide containing b, Mg, W, and Ta, wherein the composition formula based on the molar ratio of these metal elements is aBaO.bY
₂ O ₃ · cNb ₂ O ₅ · dMgO · eWO ₃ · fTa ₂
When expressed as O ₅ , the a, b, c, d, e, and f are 0.40 ≦ a ≦ 0.76 0 <b ≦ 0.26 0 <c ≦ 0.26 0 ≦ d ≦ 0.35 0 ≦ e ≦ 0.35 0 ≦ f ≦ 0.25 0.60 ≦ (b + d) / (c + e + f) ≦ 1.50 d + e + f> 0 a + b + c + d + e + f = 1.00 Composition. 5. At least Ba, Y, Z as a metal element
A composite oxide containing n, Nb, W, and Ta, wherein the composition formula based on the molar ratio of these metal elements is aBaO.bY
₂ O ₃ .cZnO.dNb ₂ O ₅ .eWO ₃ .fTa ₂
When represented as O ₅ , the a, b, c, d, e, and f are 0.40 ≦ a ≦ 0.70 0 <b ≦ 0.30 0 <c ≦ 0.35 0 ≦ d ≦ 0.30. 0 <e ≦ 0.35 0 ≦ f ≦ 0.30 0.20 ≦ (b + c) / (d + e + f) ≦ 1.66 a + b + c + d + e + f = 1.00.