JPS59196504A - High frequency dielectric porcelain composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a dielectric ceramic composition for high frequency use.

In high frequency regions such as microwaves and millimeter waves, dielectric ceramics are widely used for dielectric resonators, dielectric substrates for MIC, and the like.

Conventionally, as this type of dielectric porcelain, for example, Zn 02
Sn 02- TL 02 series material, Ba, Ti10
aa, (Ba, ST) 1- (Zr, TL) Oa monthly interest rate, Ba (Zn, Ta)
Examples include 03 series material r1.

The dielectric constant (ε
, ) is reported to be 20-40, Q is 4000-8000, and the lagoon coefficient (given) of the resonant frequency is reported to be ``C(t with 14 bamboos near l)''.

Among these, Ba (7n, Ta) 03 series It II
is a suitable conventional example of the present invention. This Ra (Zn,
Ta) About the 03 series material, it's 11! S Mimaki! i
A detailed explanation is given in 33!1454@ gazette.

Details 1. According to the explanation, a dielectric Ia vessel is made by baking it in an air for 2 hours at a temperature range of 1360 to 1460°C, and its size is adjusted to ii' + diameter 5 mm, thickness 2 mm, and the resonant frequency vl. (1ffi if 11G I-l
When we measured the dielectric constant (ε?) from the Z) and diameter, and measured the temperature coefficient (τj) of the resonant frequency in the temperature range of -30°C to door 0°C with no load Q using the band fault method, we found that ε. Go to 25/30. 3520-37 for Q
30, τ, exhibits a characteristic of 5 to 20 ppm/°C.

Recently, the following reports have been made regarding this Ba (Zn, Ta) 03-based material.

That is, for Ba (Zn, Ta) Os, dielectric porcelain was fired by the normal firing method, and the firing strip f1 was heated at a maximum temperature of 1650°C and a firing time of 2 to 12
The results are considered in the 0 hour range.

According to the study, porcelain fired for 120 hours showed a Q lid of 14,000 when measured in a waveguide, and when porcelain fired for 2 hours was measured using the same method (1
2G +-17) It is said to exhibit a Q value of 10,000 to 11,000.

The reason for the change in Q value due to firing time is as follows.

First, Ba (ZTly%z) Oa is 'Order
ing in Com-pOIJndS o
f the △ (B, , ;, Ta,
47) 03 Type”, F, c
alasso and J, Pyle, I
nOrCIanfOCMmistry, VO12,N
As introduced in O, 3, P 482-484,
△BO It has a cubic composite velorskite structure consisting of Os, and its crystal structure is composed of ZTl and T
a b< By regular arrangement, hexagonal (t)
ona I) forms a superlattice.

FIG. 1 shows the crystal structure of Ba (7++yJay,)o3, in which the 7η1 and Ta 2 of B:l iM7 are arranged in a 1:2 order. Note that 3 is Ba
, 4 indicates 0.

22 years ago, this Chichi [character (noun) sentence (ma firing article) ('I t
;Secondly, L-c people are very strange. Beat 15, set the CJj sea urchin baking temperature (9) shown in Figure 2 to 1
In X-ray diffraction of porcelain at 350°C (422),
(226) After examining the dependence of the firing time on irregular shapes, it was found that the firing time for the culm degree between 211:li and 211:1 is 7 minutes, and the formation of an ordered arrangement of Tl and Ta is 1201
In the i+7 formation time between 7 and 7η, Ta is sufficiently ordered 1
．． In explanation 1, this is connected to the direction 1 of the Q value (L).

However, maintaining the firing time for 120 hours in order to produce porcelain with a high Q value is a major obstacle to improving the production IJ and leads to an increase in production.

Additionally, operating the kiln at high temperatures for long periods of 120 hours (1') will shorten the life of the kiln.
Yes, this also leads to an increase in product loss.

Recently, however, the frequency range used has become even higher, and there is a demand for a material r1 that can provide a higher Q value.

In view of the above points, the present inventors have conducted intensive research and found that the present inventors have a high dielectric constant in the high frequency range, a high Q value, and a temperature coefficient of Oppm at the resonance frequency, without requiring a long firing time. They have discovered a high-frequency dielectric ceramic composition that can obtain any value around /°C.

That is, the gist of this invention is Bad.

7, r 02.7. n O, Ta 20r, which has the general formula Ba(Zy.

Zn, Ta2) Q, 4.4 (when expressed as -iX,
×, ySZ is 0.02≦×≦0.13.0.28≦y≦
0.33.0.59≦7≦0.65 (However, x + y
+z=1) and in which 70 atom % or less of 2η is substituted with either N1 or G or both, and 0.1 to 1.0 mol % of 102 is added thereto. This is a high frequency dielectric ceramic composition comprising:

where Ba (Zr, Zw, Ta &) Oy, -y-%, x, y.

The reason why 7 is limited to the above-mentioned ranges is as follows.

Immediately, set X to 0.02~. The reason for the range of 0.13 is that
If is less than 0.02, Q will decrease, and 0,
If it exceeds 13, the temperature coefficient of the oscillation frequency becomes sharper on the positive side.

■ is 0.28 = 0.33 because this is 0.2
If the value exceeds 33, sintering becomes difficult.

7 is set to 0.59 to 0.65 because 7 is less than 0.59 <2, and 0, 6! If i is exceeded, t) sintering becomes difficult, so there is C.

In addition, when replacing Zn in Ha (Zr, Zn, TaJ 0y-y4-+3) with either N5 or both, the amount of substitution is set to 70 atomic % or less.
This is because if the temperature coefficient of the resonance frequency exceeds 1°, the temperature coefficient of the resonance frequency becomes too large on the Ω side.
The reason why it is specified as 1 to 1.0 mol % is that if it is 0.1 mol % or less, there is no effect of increasing the Q value, and if it is 1.0 mol % or more, the dielectric constant and Q value decrease.

This invention will be explained in detail below with reference to Examples.

Example l1it High purity BaCo3, Zy as Fl
02, ZnO, Ta2 iron, NjO, C, o203,
Using Mn0p, porcelain having the composition ratio shown in Table 1 was obtained. J: The sea urchin was hung on a scale, and the scale skewer was placed in a rubber-lined ball mill together with agate stone and pure water, and mixed in a groove for 2 hours. Next, this mixture was dehydrated and dried, and then
The calcined product was calcined at ℃ for 2 hours, and the calcined product was placed in a ball mill together with agate, pure water, and an organic binder, and groove-pulverized for 2 hours.

Next, this pulverized product was dried, then granulated through a 50-mesh mesh, and the solidified powder was molded into a disk with dimensions of 12 mmφ x 6 mmj at a pressure of 2 (lookc+J).The disk was further heated at 1450°C for 4 hours. A porcelain specimen was obtained by firing under the following conditions.

For the obtained ceramic sample r1, the dielectric constant <εr) at a frequency of 7 GHz and the temperature coefficient of the resonance frequency (given)
was measured using the dielectric resonator method, and the results are shown in Table 1.

In addition, the first person: I: The mark is outside the sheath of this invention, and everything else is within the scope of this invention). 1.49. ! i2,
55 has a composition in which a part of 710 is replaced with one or both of Ni, 09, and 09, and
It is outside the scope of this invention.

In addition, trial 11 number 8 is an example in which the replacement period for N5 and G exceeded 701 Kyoko%, and the resonant frequency (τ,) is thick on the negative side (i
However, it is excluded from the scope of this invention.
).

Trial 1” 1st mouth 1, 2, 3. 10. 16. 17, 23, 2
0,30.36,42,43゜49,52,5 r
l is added with Mn 02 f, which is an example and outside the scope of this invention.

Next, test 11 numbers 9, 15, 22, 28, 35, 41.4
8 is 10° with 1.0 mill% or more addition 111'l 1. This is an example of 1) excluded from the scope of the present invention because the dielectric constant and Q value are lowered.

Furthermore, Exam II M No. 4!1-. 57 is Ba (Zr, Z
n, Ta2) 0-4-1. - The values of ×, ■, and 7 are outside the scope of the present invention, and sintering is difficult or the properties are deteriorated.

Trial 1'II M Pi 49,50,52. ! Regarding i3, the characteristics are not shown because sufficiently sintered porcelain could not be obtained and the characteristics could not be measured.

As described in detail below, according to the present invention, a dielectric ceramic composition for high frequencies can be produced which has a high dielectric constant and exhibits a high Q value which could not be obtained conventionally by adding MnOe. Part of NL,C.

By appropriately selecting G to be substituted with either or both of them, the 'tA degree coefficient of the resonant frequency can also have arbitrary values on the 1 side and the negative side around Oppm/°C.

Therefore, according to the present invention, it is possible to provide a high frequency dielectric ceramic composition useful for applications such as dielectric resonators, dielectric adjustment rods, and dielectric substrates for MIC.

[Brief explanation of drawings]

Figure 1 is a diagram showing the crystal structure of Ba (Zr+, 4Ta3) 03, and Figure 2 is an X-ray diffraction diagram of Ba (7η, TI-Os) shown in relation to firing time. Patent applicant: Co., Ltd. murata manufacturing

Claims (1)

[Claims] It consists of BaO, ZrO2, zTlO1Ta2Cs, and when expressed as the general formula Ba (Z-ZηaTa-0%-2-calculation), x, ylZ is 0.02 ≦x ≦0.13,
]28≦y≦0.33.0.59≦7≦0.65
(However, X-1 + Z = 1), and the main component is one in which 70 atomic % or less of Zn is substituted with N5, co, or both, and I''In○2
A high frequency dielectric ceramic composition comprising 0.1 to 1.0 mol% of the following.