JP2005082455A - Dielectric ceramic composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a dielectric ceramic composition having both of an excellent dielectric characteristic and a high temperature characteristic in a GHz band. <P>SOLUTION: The dielectric ceramic composition contains at least one or more kinds of Mn, Y, Yb, Co, Sc, V, Nb, Ta, Bi and W as an element M and is expressed by a formula (Sr<SB>x</SB>Ca<SB>1-x</SB>)<SB>k</SB>(Zr<SB>y</SB>Ti<SB>1-y</SB>)O<SB>3</SB>-aMO (MO is an oxide of the element M). In the formula, x, y and k are controlled respectively to 0.50<x<0.70, 0.00≤y≤0.18 and 0.940<k<1.020 in a molar ratio and (a) is controlled to 0.00<a≤4.00 wt.%. The temperature characteristic is improved while the high dielectric characteristic is kept by incorporating a prescribed quantity of the element M such as Mn in the dielectric ceramic composition. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a dielectric ceramic composition suitable for high-frequency resonators, filters, temperature compensation capacitors, duplexers, and the like.

Dielectric ceramic compositions are widely used as materials for resonators, filters, temperature compensation capacitors, and the like. As a dielectric ceramic composition used for a resonator or the like, one having excellent dielectric characteristics and temperature characteristics is desirable. For this reason, various studies for obtaining a dielectric ceramic composition exhibiting high dielectric characteristics and excellent temperature characteristics have been made (see, for example, Patent Documents 1 to 3).
For example, in Patent Document 1, when expressed as a composition formula (Ca _1-x Sr _x ) _m (Zr _1-y Ti _y ) O ₃ , x, y, and m are in a molar ratio of 0 ≦ x <0.5, With respect to 100 moles of the main component satisfying 0.60 <y ≦ 0.85 and 0.85 <m <1.30, the manganese compound is converted into MnO and the magnesium compound is converted into MgO as subcomponents, respectively. It has been proposed to contain 0.1 to 6 mol, and further to contain a sintering aid such as SiO ₂ .
Further, the composition formula in Patent Document _{2 (Ca 1-x Sr x} ) m (Zr 1-y Ti y) O 3 -zMnO 2 -w
When expressed as SiO ₂ , x, y and m are molar ratios of 0 ≦ x ≦ 1.0, 0 ≦ y ≦ 0.2, 0
. 9 ≦ m ≦ 1.1, and for the main component represented by this composition formula, a (LiO _1/2 -RO)-(1-a) (BO _3/2 -SiO) is further added as an additive. ₂ ) is proposed to be added in a predetermined amount (RO is at least one of SrO, BaO and CaO).
Further, Patent Document 3, a composition formula _{(Sr x, Ca 1-x} ) (Zr y, Ti 1-y) O 3,
0.59 ≦ x ≦ 0.65, 0 <y ≦ 0.1, (Sr _x , Ca _1-x ) (Zr _y , T
It is disclosed that by adding less than 3.0 wt% of SiO ₂ with respect to the weight of i _1-y ) O ₃ , the temperature characteristics of relative permittivity ε _r and resonance frequency are improved.

JP 2000-53466 A (Claims, Examples) JP-A-5-217426 (Claims, Examples) JP-A-4-14704 (Claims, Examples)

The dielectric ceramic composition described in Patent Document 1 described above exhibits the characteristics that the relative dielectric constant ε _{r at} a frequency of 1 kHz is 100 to 140 and the dielectric loss is 1.0% or less. In addition, the dielectric ceramic composition described in Patent Document 2 exhibits characteristics that the dielectric constant ε is 20 or more and the Q value is 3000 or more at a measurement frequency of 1 MHz.
However, in recent years, the frequency band used has shifted to a higher frequency side, and a dielectric ceramic composition exhibiting a higher relative dielectric constant ε _r on the higher frequency side, that is, the gigahertz band (hereinafter referred to as “GHz band”) is desired. It is rare.
On the other hand, according to the dielectric ceramic composition described in Patent Document 3, a dielectric constant ε _r of 200 or more and a Q value of 1000 or more can be obtained in the microwave band. However, Conventional Example 1 in Table 1,
As shown in FIG. 2, in Patent Document 3, the value of the temperature coefficient τ _f25-85 of the resonance frequency is high for a sample exhibiting high dielectric characteristics. On the other hand, the sample in which the temperature coefficient τ _f25-85 of the resonance frequency has reached a small level has a low relative dielectric constant ε _r and Q value.
The present invention has been made based on such a technical problem, and an object thereof is to provide a dielectric ceramic composition having both dielectric properties and temperature properties in the GHz band.

For this purpose, the present invention provides M elements such as Mn, Y, Yb, Co, Sc, Sn, V,
Nb, Ta, Bi, a dielectric ceramic composition comprising at least one or more of _{W, (Sr x Ca 1-} x) k (Zr y Ti 1-y) O 3 -aMO (MO is M In the formula represented by (element oxide), x, y, and k are molar ratios of 0.50 <x <0.70, 0.00 ≦ y ≦ 0.18, 0.940 <k <1.020. The dielectric ceramic composition is characterized in that 0.00 <a ≦ 4.00 wt%. This is based on the knowledge that the temperature characteristics can be improved while maintaining high dielectric characteristics by containing a predetermined amount of M element such as Mn in the dielectric ceramic composition.
In the dielectric ceramic composition of the present invention, with respect to _{(Sr x Ca 1-x)} k (Zr y Ti 1-y) weight 100 O _3, less than further 3.00 wt% of SiO ₂ (where 0 (Not included) can be added. By adding SiO ₂ within a range of less than 3.00 wt%, the relative dielectric constant ε _r and the temperature characteristics are improved.
The dielectric ceramic composition of the present invention has a relative dielectric constant ε _r of 20 at a measurement frequency of 2 GHz.
It exhibits excellent characteristics in which the absolute value of the temperature coefficient τ _f25-85 of the resonance frequency is 0 ppm or less and 0 ppm or less.
Furthermore, according to the dielectric ceramic composition of the present invention, the Qf in the GHz band (Qf is the product of the Q value and the frequency f) can be 2500 or more. Here, in the present invention, Q is a quality factor and is the reciprocal of the loss tangent tan δ (Q = 1 / tan δ).

  ADVANTAGE OF THE INVENTION According to this invention, the dielectric ceramic composition which can have a high dielectric characteristic and temperature characteristic in GHz band can be obtained.

Hereinafter, the dielectric ceramic composition of the present invention will be described in detail.
The dielectric ceramic composition of the present invention contains at least one of Mn, Y, Yb, Co, Sc, Sn, V, Nb, Ta, Bi, and W as the M element, and the following formula ( It has the composition shown in 1).

_{(Sr x Ca 1-x)} k (Zr y Ti 1-y) O 3 -aMO ··· Equation (1)
In formula (1),
x, y and k are molar ratios;
0.50 <x <0.70,
0.00 ≦ y ≦ 0.18,
0.940 <k <1.020 and 0.00 <a ≦ 4.00 (wt%).

First, the reasons for limiting x, y, k, and a in Equation (1) will be described.
x is in the range of 0.50 <x <0.70. When x is 0.50 or less, the firing density is lowered and the temperature characteristics are deteriorated. On the other hand, when x is 0.70 or more, the Ca content is relatively reduced, the Qf in the GHz band is lowered, and the temperature characteristics are also deteriorated. A desirable range of x is 0.55 ≦ x ≦ 0.65, and a more desirable range of x is 0.58 ≦ x ≦ 0.62.

y is in the range of 0.00 ≦ y ≦ 0.18. The inclusion of Zr is effective for improving Qf. However, when y exceeds 0.18, the temperature characteristics are deteriorated as Qf is smaller than when Zr is not contained (y = 0.00). Here, the dielectric ceramic composition of the present invention is characterized by containing a predetermined amount of M element in the composition, and even when it does not contain Zr as shown in the examples described later, The temperature characteristics can be greatly improved as compared with the conventional dielectric ceramic composition. Moreover, the M element does not harm the dielectric properties. Therefore, in the present invention, the inclusion of Zr is optional. A desirable range of y is 0.00 ≦ y ≦ 0.12, and a more desirable range of y is 0.03 ≦ y ≦ 0.09.

k is in the range of 0.940 <k <1.020. When k is 0.940 or less, the relative dielectric constant ε _r
Becomes less than 200, and the temperature characteristics deteriorate. On the other hand, when k is 1.020 or more, the temperature characteristics deteriorate and the firing density decreases. A desirable range of k is 0.950 ≦ k ≦ 1.015, and a more desirable range of k is 0.960 ≦ k ≦ 1.010.

“A” indicating the amount of the oxide MO of the M element is in the range of 0.00 <a ≦ 4.00 (wt%). By containing a predetermined amount of M element in the composition, the temperature characteristics can be improved without harming the dielectric characteristics. In addition, by including a predetermined amount of M element in the composition, even when Zr is not included in the composition (y = 0.00), it is possible to have both high dielectric characteristics and temperature characteristics. . However, if a exceeds 4.00 wt%, the temperature characteristics deteriorate. The desirable range of a is 0.00 <a ≦ 3.00 (wt%), the more desirable range of a is 0.00 <a ≦ 2.00 (wt%), and the even more desirable range of a is 0.00 < a ≦ 0.50 (wt%).
Here, as the M element, one or more of Mn, Y, Yb, Co, Sc, Sn, V, Nb, Ta, Bi, and W are selected, and desirable contents for each element will be described later. .

In the dielectric ceramic composition of the present invention having the above-described composition, it is desirable to further add SiO ₂ as a subcomponent. In the case of adding SiO ₂ , the amount added is less than 3.00 wt% (however, not including 0) as shown in the following formula (2).

_{(Sr x Ca 1-x)} k (Zr y Ti 1-y) O 3 -aMO-bSiO 2 ··· (2)
In formula (2),
0.00 <b <3.00 (wt%).

By adding SiO ₂ within a range of less than 3.00 wt%, the relative dielectric constant ε _r and the temperature characteristics are improved. However, when the SiO ₂ amount is 3.00 wt% or more, the temperature characteristics tend to deteriorate. A desirable range of b is 0.02 ≦ b ≦ 2.80 (wt%), and a more desirable range of b is 0.05 ≦ b ≦ 2.50 (wt%).

The reason for limiting the composition of the dielectric ceramic composition of the present invention has been described above. Next, the M element which is an essential element in the dielectric ceramic composition of the present invention will be described.
As described above, the temperature characteristics can be improved by containing a predetermined amount of the M element in the composition. As the M element, one or more of Mn, Y, Yb, Co, Sc, Sn, V, Nb, Ta, Bi, and W are selected. Among these, Mn, Y, V, and Nb are preferable as the M element. Further desirable M elements are Mn and Y.
Here, when Bi or W is selected as the M element, the temperature characteristics can be improved without harming the relative dielectric constants ε _r and Qf. When any one of Co, Sn, Nb, and Ta is selected as the M element, the temperature characteristics and Qf can be improved. When any one of Yb, Sc, and V is selected as the M element, temperature characteristics and relative dielectric constant ε _r
Can be improved. When Mn or Y is selected, in addition to the effect of improving the temperature characteristics, the effect of improving Qf and relative dielectric constant ε _r can also be enjoyed.

When Mn is selected as the M element, a desirable content is 0.01 to 0.30 wt% in terms of MnO, and a more desirable content is 0.02 to 0.20 wt%.
A desirable content when selecting Y as the M element is 0.20 to 2.00 wt% in terms of Y ₂ O ₃ , and a more desirable content is 0.50 to 1.50 wt%.
When Yb is selected as the M element, a desirable content is 0.50 to 4.00 wt% in terms of Yb ₂ O ₃ , and a more desirable content is 1.50 to 2.50 wt%.
When Co is selected as the M element, a desirable content is 0.20 to 2.00 wt% in terms of Co ₃ O ₄ , and a more desirable content is 0.50 to 1.50 wt%.
Desired content when selecting Sc as the element M, 0.20～2.00Wt% by Sc ₂ O ₃ in terms of further desirable content is 0.50~1.50wt%.
Desirable content when Sn is selected as the M element is 0.01 to 0.00 in terms of SnO ₂ .
20 wt%, and a more desirable content is 0.05 to 0.10 wt%.
When V is selected as the M element, a desirable content is 0.005 to 0.500 wt% in terms of V ₂ O ₅ , and a more desirable content is 0.01 to 0.10 wt%.
When Nb is selected as the M element, a desirable content is 0.10 to 3.00 wt% in terms of Nb ₂ O ₃ , and a more desirable content is 0.50 to 2.00 wt%.
When Ta is selected as the M element, a desirable content is 0.05 to 1.00 wt% in terms of Ta ₂ O ₅ , and a more desirable content is 0.10 to 0.60 wt%.
Desired content when selecting Bi as the element M, 0.10～2.00Wt% in terms of Bi ₂ O _3, more preferable content is 0.20~0.80wt%.
Desirable content when W is selected as the M element is 0.005 to 0.1 in terms of WO _3.
00 wt%, and a more desirable content is 0.010 to 0.060 wt%.

The dielectric ceramic composition of the present invention has a relative dielectric constant ε _r of 200 or more in the GHz band and a Qf of 2
The characteristics that the absolute value of the temperature coefficient τ _f25-85 of 500 or more and the resonance frequency is 250 ppm / ° C. or less can be combined. Furthermore, by appropriately selecting the above-described composition, the Qf in the GHz band can be set to 2800 or more, and the absolute value of the temperature coefficient τ _f25-85 of the resonance frequency can be set to 200 ppm / ° C. or less. Furthermore, the relative permittivity εr in the GHz band is 200 or more, Qf is 3000 or more, and the absolute value of the temperature coefficient τ _f25-85 of the resonance frequency is 150 ppm / ° C. or less.
In addition to these characteristics, the dielectric ceramic composition of the present invention can have a specific resistance ρ at 20 ° C. of ρ> 10 ¹³ Ωcm and a firing density of 4.5 g / cm ³ or more.

Next, a production method suitable for the dielectric ceramic composition according to the present invention will be described.
<Raw material powder, weighing>
As a raw material of the main component, an oxide or a powder of a compound that becomes an oxide by heating is used. Specifically, SrCO ₃ powder, CaCO ₃ powder, TiO ₂ powder, ZrO ₂ powder and the like can be used. Each raw material powder is weighed so as to have the composition of formula (1). Thereafter, a predetermined amount of a powder of a compound containing M element as an accessory component (for example, MnCO ₃ powder) is added to the total weight of each weighed powder so as to have the composition of formula (1). Then, based on the total weight of the raw material powder of each principal component is weighed and added SiO ₂ powder in a range of less than 3.00 wt% as an auxiliary component. What is necessary is just to select suitably the average particle diameter of each raw material powder in the range of 0.1-3.0 micrometers.
In addition, not only the raw material powder mentioned above but it is good also considering the powder of the complex oxide containing 2 or more types of metals as raw material powder.
<Calcination>
After the raw material powder is wet-mixed by, for example, a ball mill, calcination is performed in a range of 900 to 1300 ° C. for a predetermined time. The atmosphere at this time may be N ₂ or air. What is necessary is just to select suitably the holding time of calcination in the range of 0.5 to 5.0 hours. After the calcination, the calcined body is pulverized, for example, to an average particle size of about 0.5 to 2.0 μm.
After mixing the main component raw material powder (SrCO ₃ powder, CaCO ₃ powder, TiO ₂ powder, ZrO ₂ powder) and the subcomponent raw material powder (compound containing M element, SiO ₂ powder), Although the case where both are subjected to calcination has been shown, the timing of adding the raw material powder of the accessory component is not limited to that described above. For example, first, only the main component powder is weighed, mixed, calcined, and pulverized. And you may make it add and mix a predetermined amount of raw material powder of a subcomponent with the powder of the main component obtained after calcining pulverization.

<Granulation / Molding>
The pulverized powder is granulated into granules in order to smoothly execute the subsequent molding process. At this time, it is desirable to add a small amount of an appropriate binder such as polyvinyl alcohol (PVA) to the pulverized powder. The particle size of the obtained granules is preferably about 80 to 200 μm.
The granulated powder is pressure-molded at a pressure of 200 to 300 MPa to obtain a molded body having a desired shape.

<Baking>
After removing the binder added during molding, the molded body is heated and held for a predetermined time within a range of 1250 to 1430 ° C. to obtain a sintered body. The atmosphere at this time may be N ₂ or air. The heating and holding time may be appropriately selected within a range of 2 to 6 hours. In order to sufficiently bring out the effect of the dielectric ceramic composition of the present invention, it is desirable to fire in the range of 1300 to 1400 ° C. The dielectric ceramic composition according to the present invention can obtain a firing density of 4.4 g / cm ³ or more, and further 4.5 g / cm ³ or more.

Through the above steps, the dielectric ceramic composition according to the present invention can be obtained. The dielectric ceramic composition according to the present invention has a relative dielectric constant ε _r of 200 to 300 at 2 GHz, Qf
_{Of 2000 to 6000} , the absolute value of the temperature coefficient τ _f25-85 of the resonance frequency is 250 ppm / ° C. or less, the specific resistance ρ at 20 ° C. is ρ> 10 ¹³ Ωcm, and the firing density is 4.5 g / cm ³ or more. Prepare. The dielectric ceramic composition according to the present invention having such excellent characteristics is suitable as a material for a high-frequency resonator, particularly a microwave resonator, a filter, a temperature compensation capacitor, a duplexer and the like.

Hereinafter, the present invention will be described based on specific examples.
In Example 1, Mn was selected as the M element, a dielectric ceramic composition was prepared under the following conditions, and its characteristics were evaluated.

As raw material powders, SrCO ₃ powder, CaCO ₃ powder, TiO ₂ powder, ZrO ₂ powder, MnCO ₃ powder and SiO ₂ powder were prepared. In addition, the average particle diameter of each raw material powder is 0.1-1.0 micrometer.
First, in the above-described formula (2), x, y, and k are weighed so that the molar ratios are the values shown in Tables 1 to 5, respectively, and then a and b are wt% so that the values shown in Tables 1 to 5 are obtained. Then, wet mixing was performed for 16 hours using a ball mill. After the obtained slurry was sufficiently dried, calcining was performed in the air at 1100 ° C. for 2 hours to obtain a calcined body. After finely pulverizing with a ball mill until the calcined body had an average particle size of 1.0 μm, the finely pulverized powder was dried. Next, an appropriate amount of PVA (polyvinyl alcohol) was added as a binder, granulated, molded, and then fired at 1370 ° C. for 4 hours to obtain a dielectric ceramic composition having a diameter of 10 mm and a thickness of 5 mm.

Using the obtained dielectric ceramic composition, dielectric characteristics, temperature characteristics, specific resistance, and firing density were measured. The result is combined with Tables 1-5, and is shown. As a comparative example, a dielectric ceramic composition having a composition outside the composition range of the present invention was produced under the same conditions as described above. The characteristics of the dielectric ceramic compositions of those comparative examples are also shown in Tables 1 to 5.
Five dielectric ceramic compositions were prepared for each sample shown in Tables 1 to 5, and each characteristic was measured for each sample, and an average value was calculated (each of Tables 1 to 5). The value of the characteristic is the calculated average value).

<Relative permittivity ε _r , Q value, resonance frequency>
The relative dielectric constant ε _r , Q value, and resonance frequency were measured by the Hakki-Coleman method. Dielectric constant ε _r
At the time of measurement, a frequency characteristic is measured by oscillating a high frequency from one probe of a network analyzer (Hured Packard 8510C), and the relative dielectric constant ε is calculated from the obtained TE01δ mode resonance frequency peak and the sample size. sought _r . The measurement frequency is 2 GHz
It was.
<Temperature coefficient τ _{f of} resonance frequency>
The resonance frequency at 20 ° C. and 85 ° C. was measured, and the temperature coefficient τ _{f (20-85)} of the resonance frequency was obtained. The values of τ _{f (20-85)} shown in Tables 1 to 5 are absolute values of the temperature coefficient τ _{f (20-85)} of the resonance frequency. Hereinafter, the “temperature coefficient τ _{f (20-85) of the} resonance frequency” is simply referred to as τ _f .
<Resistivity>
The insulation resistance was measured by applying a DC voltage of 100 V for 40 seconds at 20 ° C. to determine the specific resistance.

First, using Table 1, the variation in characteristics associated with the M element content is confirmed.
In Table 1, Sample No. 1 and sample no. 2 is Sample No. Except for the point that 2 contains M element (Mn), it has the same composition. Sample No. 3 and sample no. 4 and sample no. 5 and sample no. 6 is sample No. 6 respectively. 1 and sample no. 2 is the same relationship.
As shown in Table 1, the temperature characteristics are greatly improved by containing Mn. 2, 4, and 6 all show values of τ _f of 250 ppm / ° C. or less. Mn
Sample No. containing Samples Nos. 2, 4, and 6 have a relative dielectric constant ε _r of 200 or more and a Qf of 3000 or more, and no sample No. Dielectric characteristics equivalent to or better than 1, 3, 5 are obtained.
From the above results, it was found that the inclusion of the M element is effective in obtaining a dielectric ceramic composition having high dielectric characteristics and temperature characteristics. Further, it was confirmed that the inclusion of the M element did not adversely affect the specific resistance and the firing density.

  Next, using Table 2, the fluctuation of characteristics accompanying the fluctuation of x is confirmed.

From Table 2, it can be seen that the relative permittivity ε _r , Qf, τ _f, and the firing density vary as x varies. When x is 0.50, which is less than the range of the present invention (Sample No. 7)
) Has a large τ _{f and a} low firing density. When x is 0.70, which is larger than the range of the present invention (Sample No. 8), τ _f is as high as 1311 ppm / ° C.
On the other hand, the sample No. x is 0.58 to 0.62. 2, 4 and 6 show high dielectric characteristics and τ _f is as good as 200 ppm / ° C. or less. Therefore, in the present invention, x is 0.50 <x <0.70 in terms of molar ratio. A desirable x value is 0.55 ≦ x ≦ 0.65, and a more desirable x value is 0.58 ≦ x ≦ 0.62.

  Next, using Table 3, the variation in characteristics accompanying the variation in y is confirmed.

From Table 3, it can be seen that the relative permittivity ε _r , Qf, and τ _f vary as y varies.
Sample No. with y being 0.00 to 0.10. Nos. 4 and 9 to 14 show high dielectric properties and τ _f is 250 ppm / ° C. or lower, and 200 ppm / ° C. or lower. However, when y exceeds 0.10 (sample No. 14) and becomes 0.20 (sample No. 15), the temperature coefficient τ _f significantly increases. Furthermore, when y becomes 0.40 (sample No. 16),
In addition to the deterioration of temperature characteristics, the dielectric characteristics also deteriorate.
Therefore, in the present invention, y is 0.00 ≦ y ≦ 0.18 in terms of molar ratio. A desirable y value is 0.00 ≦ y ≦ 0.12, and a more desirable y value is 0.03 ≦ y ≦ 0.09.

  Next, using Table 4, the variation in characteristics accompanying the variation in k is confirmed.

From Table 4, it can be seen that the relative permittivity ε _r , Qf, τ _f, and the firing density vary as k varies.
When k is 0.940, which is less than the range of the present invention (sample No. 17), τ _f is large.
On the other hand, when k is 1.020 or more, which is larger than the range of the present invention (Sample Nos. 24 to 26), τ _f is as large as 300 ppm / ° C.
Therefore, in the present invention, k is 0.940 <k <1.020 in terms of molar ratio. A desirable value of k is 0.950 ≦ k ≦ 1.015, and a more desirable value of k is 0.960 ≦ k ≦ 1.010.

  Next, Table 5 is used to examine a desirable value of a.

From Table 5, it can be seen that the relative dielectric constant ε _r increases with increasing a indicating the amount of MO (oxide of M element). Here, it is as shown in Table 1 that the temperature characteristics can be improved by containing Mn as the M element. However, τ _f tends to gradually increase as a indicating MO amount increases. Therefore, when Mn is selected as the M element in the present invention, a is set to 0.00 <a ≦ 0.30 in wt%. When Mn is selected as the M element, a desirable value of a is 0.00 <a ≦ 0.20, and a more desirable value of a is 0.02 ≦ a ≦ 0.15.

A dielectric ceramic composition was prepared in the same procedure as in Example 1 except that the addition amount of SiO ₂ was varied as shown in Table 6. And each characteristic was measured on the conditions similar to Example 1. FIG. Table 6 shows the measurement results.

From Table 6, it can be seen that the relative permittivity ε _r , Qf and τ _f vary with the variation of b indicating the amount of SiO ₂ .
When SiO ₂ is not contained in the composition (sample No. 29) and when b is 3.00 wt% and more than the range of the present invention (sample No. 31), the relative dielectric constant ε _r is less than 200, and τ _{f is} also large.
Therefore, in the present invention, b is defined as 0.00 <b <3.00 in wt%. A desirable value of b is 0.02 ≦ b ≦ 2.80 (wt%), and a more desirable value of b is 0.05 ≦ b ≦ 2.50 (wt%).

In Examples 1 and 2 above, Mn was selected as the M element. Example 3 shows an example in which Y, Yb, Co, Sc, Sn, V, Nb, Ta, Bi, and W are selected as the M element.
Dielectric porcelain composition in the same procedure as in Example 1 except that Mn element (Y, Yb, Co, Sc, Sn, V, Nb, Ta, Bi, W) was contained under the conditions shown in Table 7. Was made. And each characteristic was measured on the conditions similar to Example 1. FIG. Table 7 shows the measurement results.

As shown in Table 7, Y, Yb, Co, Sc, Sn, V, Nb, Ta, Bi as M elements
, W was selected, the relative dielectric constant ε _r was 200 or more, Qf was 2000 or more, and τ _f was 250 ppm / ° C. or less.

Claims (4)

A dielectric ceramic composition containing at least one of Mn, Y, Yb, Co, Sc, Sn, V, Nb, Ta, Bi, and W as an M element,
Wherein _{(Sr x Ca 1-x)} k (Zr y Ti 1-y) O 3 -aMO (MO is the M oxides of the elements) represented by,
x, y and k are molar ratios;
0.50 <x <0.70,
0.00 ≦ y ≦ 0.18,
0.940 <k <1.020, and
0.00 <a ≦ 4.00 (wt%)
A dielectric porcelain composition comprising: The _{(Sr x Ca 1-x)} k (Zr y Ti 1-y) with respect to the weight 100 of the O _3, was added to SiO ₂ of b wt%, b is 0.00 <b <3.00 (wt %)). The dielectric ceramic composition according to claim 1, wherein: _3. The dielectric ceramic composition according to claim 1, wherein the relative dielectric constant ε _{r at a} measurement frequency of 2 GHz is 200 or more and the absolute value of the temperature coefficient τ _{f25 -85} of the resonance frequency is 250 ppm / ° C. or less. .   The dielectric ceramic composition according to any one of claims 1 to 3, wherein a Qf in the GHz band (Qf is a product of a Q value and a frequency f) is 2500 or more.