JPH11228226A - Piezoelectric ceramic composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a piezoelectric ceramic composition consisting mainly of potassium sodium lithium niobate, having a dielectric constant of <=180 and the resonance frequency coefficient of thickness vibration of >=3,000 Hz.m so as to be suitable for using in high frequency region, and also having such favorable property as to be <=100 ppm in the temperature coefficient of resonance frequency. SOLUTION: This piezoelectric ceramic composition consists mainly of a composition of the formula: (1-n) (K1-x-y Nax Liy )m (Nb1-z Taz )O3 -nM1M2M3O3 (wherein, M1 is a trivalent metal atom such as Bi; M2 is a monovalent metal atom such as K, Na or Li; M3 is a tetravalent metal atom such as Ti, Zr, Sn or Hf; (x)<=0.9; 0.02<=(y)<=0.3; 0.75<=(x+y); 0<=(z)<=0.3; 0.98<=(m)<=1.0; 0<(n)<=0.05).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a piezoelectric ceramic composition, and more particularly to a piezoelectric ceramic composition useful as a material for a piezoelectric ceramic element such as a piezoelectric ceramic filter or a piezoelectric ceramic oscillator.

[0002]

2. Description of the Related Art As a piezoelectric ceramic composition used for the piezoelectric ceramic element such as a piezoelectric ceramic filter, piezoelectric ceramic composition composed mainly of lead zirconate titanate _{(Pb (Ti x Zr 1-} x) O 3) Widely used. Such a piezoelectric ceramic composition containing lead zirconate titanate as a main component usually has a relatively large relative dielectric constant of about 1,000 to 2,000. Therefore, for example, in a high-frequency region exceeding 100 MHz, the impedance is reduced, and it is difficult to use in such a high-frequency region.

On the other hand, lead titanate (PbTi
The piezoelectric ceramic composition mainly composed of O ₃ ) has a relative dielectric constant of 2
Since it is about 00, which is smaller than the piezoelectric ceramic composition containing lead zirconate titanate as a main component, it is known as a piezoelectric ceramic composition that can be used in a higher frequency range. However, considering use in a further high frequency region, it is desirable that the relative dielectric constant is even smaller.

Further, the lead zirconate titanate or the piezoelectric ceramic composition containing lead titanate as a main component has a resonance frequency constant of thickness vibration as small as about 2,000 to 2,500 Hz.m. In addition, the frequency band used is limited due to the problem of flake processing. In contrast, some piezoelectric ceramic compositions containing potassium sodium lithium niobate as a main component represented by a composition formula (K _{1 -xy} Na _x Li _y ) NbO ₃ have a relative dielectric constant of about 100. In addition, the resonance frequency constant of the thickness vibration is as large as about 3000 to 3500 Hz · m, and when considered for use in a high frequency region, it is preferable to use lead zirconate titanate or lead titanate. It is known that some materials have properties that are relatively advantageous.

However, the piezoelectric ceramic composition containing potassium sodium lithium niobate as a main component has a temperature coefficient fr of resonance frequency in thickness vibration, which is an important characteristic as a material for a piezoelectric ceramic filter and a piezoelectric ceramic oscillator. Since TC is as large as about 150 to 300 ppm, it has not yet been widely used as compared with lead zirconate titanate, lead titanate and the like.

[0006] The temperature coefficient fr-TC of the resonance frequency in the thickness vibration described above is calculated by the following equation. fr-TC = fr _max -fr _min / (fr ₂₀ · 100) In the above equation, fr _max is the maximum value of the resonance frequency in the thickness vibration in the range of −20 ° C. to 80 ° C., fr
_min is the minimum value of the resonance frequency in the thickness vibration in the range of −20 ° C. to 80 ° C., and fr ₂₀ is the resonance frequency in the thickness vibration at 20 ° C.

[0007]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems encountered by piezoelectric ceramic compositions containing potassium sodium lithium niobate as a main component, and has a temperature coefficient of resonance frequency fr-TC. It is intended to provide a piezoelectric ceramic composition suitable for use in a high frequency region with a resonance frequency constant of 3000 Hz · m or more having a relative dielectric constant of 180 or less and a dielectric constant of 180 ppm or less. The purpose is.

[0008]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned technical problems by the general formula: (1-n) (K _{1-
xy Na x Li y) m (} Nb 1-z Ta z) O 3 -nM1
As a main component a composition represented by M2M3O _3, a piezoelectric ceramic composition, in the above general formula, M1 is made of trivalent metal elements, M2 consists monovalent metal element, M
3 is a tetravalent metal element, and x, y, z, m,
And n are x ≦ 0.9, 0.02 ≦ y ≦ 0.3, 0.75 ≦ x + y, 0 ≦ z ≦ 0.3, 0.98 ≦ m ≦ 1.0, and 0 <n, respectively. It satisfies the condition of ≦ 0.05.

The reasons for limiting the ranges of x, y, z, m and n described above are as follows. For x and y, x ≦ 0.9 and 0.02 ≦ y ≦ 0.3, respectively.
The reason for this is that a good sintered body cannot be obtained if it is out of these ranges. Also, 0.75 ≦
The reason for setting x + y is that when 0.75> x + y, the relative dielectric constant becomes larger than 180, and the advantage in use in a high frequency region is lost.

With respect to z, 0 ≦ z ≦ 0.3 is set so that when the value is out of this range, the Curie point is lowered to 200 ° C. or less, and the temperature stability of the element constituted by the piezoelectric ceramic composition is reduced. This is because a problem arises in the point. Also, m
The reason why 0.98 ≦ m ≦ 1.0 is that if it is out of this range, the polarization treatment becomes difficult.

[0011] Further, with respect to n, the condition of 0 <n ≦ 0.05 is that when n is larger than 0.05, the Curie point is lowered to 200 ° C. or less and the piezoelectric ceramic composition is constituted. This is because a problem occurs in the temperature stability of the device. In the present invention, preferably, M1 in the above general formula is composed of Bi, M2 is composed of at least one selected from the group consisting of K, Na, and Li, and M3 is composed of Ti, It is composed of at least one selected from the group consisting of Zr, Sn, and Hf.

[0012]

EXAMPLE First, K was used as a starting material._TwoCO_Three, Na_Two
CO_Three, Li_TwoCO_Three, Nb_TwoO _Five, Ta_TwoO_Five, Bi
_TwoO_Three, TiO_Two, And ZrO_TwoPrepare these
The raw material is represented by the general formula: (1-n) (K_1-xyNa_xLi_y)
_m(Nb_1-zTa_z) O_Three-NM1M2M3O_Threesmell
And weigh them so that they have the composition shown in Tables 1 and 2.
And wet mixing in alcohol for about 4 hours using a ball mill.
After drying the obtained mixture,
It was calcined at a temperature of ° C. The dried mixture is then
After crushing, add an appropriate amount of organic binder and use a ball mill
4 hours by wet grinding and granulation through a 40 mesh sieve
The degree was adjusted.

Next, the powder whose particle size has been adjusted is 1000 kg.
After molding into a disk having a diameter of 12 mm and a thickness of 1.2 mm at a pressure of / cm ² , firing was performed at a temperature of 1050 ° C. to 1300 ° C. using a normal firing method to obtain a disk-shaped porcelain. . Next, a silver paste is applied and baked on both main surfaces of these porcelain disks by a usual method to form silver electrodes, and then 2 to 10 kV / in an insulating oil at 50 ° C. to 150 ° C.
A DC voltage of 10 mm was applied for 10 to 30 minutes to perform polarization treatment, and a piezoelectric ceramic disk as a sample was obtained.

[0014]

[Table 1]

[0015]

[Table 2]

For each of the samples shown in Tables 1 and 2, the relative dielectric constant, the electromechanical coupling coefficient K _{t in} the thickness vibration, the resonance frequency constant N in the thickness vibration, the temperature coefficient fr-TC of the resonance frequency in the thickness vibration, And the Curie point was measured. The results are shown in Tables 3 and 4.

[0017]

[Table 3]

[0018]

[Table 4]

In Tables 1 to 4, samples marked with * are out of the scope of the present invention. In Tables 1 and 2, x ≦ 0.9, 0.02 ≦ y ≦ 0.
3, 0.75 ≦ x + y, 0 ≦ z ≦ 0.3, 0.98 ≦ m
As for the samples satisfying all the conditions of ≦ 1.0 and 0 <n ≦ 0.05, that is, the samples according to the examples of the present invention in which * is not added to the sample numbers, as shown in Tables 3 and 4, , All have a relative dielectric constant of 180 or less, a resonance frequency constant of thickness vibration of 3000 Hz · m or more, and a temperature coefficient of resonance frequency of 100 ppm or less,
Furthermore, it shows good characteristics such as a Curie point exceeding 200 ° C.

On the other hand, x ≦ 0.9 or 0.02
Samples 1, 19 and 3 that do not satisfy the condition of ≦ y ≦ 0.3
In No. 2, poor sintering occurred. Also, 0.75 ≦ x +
In the case of the sample 45 that does not satisfy y, the relative dielectric constant is 210, and a relative dielectric constant of 180 or less cannot be achieved. Also, 0 ≦
In the sample 54 not satisfying z ≦ 0.3, the Curie point is 1
The temperature is 65 ° C., and a Curie point exceeding 200 ° C. cannot be realized.

Further, the sample 63 which does not satisfy the condition of 0.98 ≦ m ≦ 1.0 cannot achieve the desired polarization. Further, among the samples that do not satisfy the condition of 0 <n ≦ 0.05,
Samples 5, 10, 14, 18, 2 where n is greater than 0.05
3, 27, 31, 36, 40, 44, 49, 53, 5
8, 62, 66 and 69, the Curie point is 200 ° C.
It has dropped below. In addition, samples 2, 6, in which n becomes 0,
11, 15, 20, 24, 28, 33, 37, 41, 4
In 6, 50, 55 and 59, the temperature coefficient of the resonance frequency greatly exceeds 100 ppm.

Although the present invention has been described with reference to the embodiments, the piezoelectric ceramic composition within the scope of the present invention is not limited to such embodiments, but departs from the spirit of the present invention. The composition can be variously changed within a range not to do. For example, in the embodiment described above, M1 is Bi
Is used, and Na or Li is used as M2,
Although Ti or Zr was used as M3, the same effect can be obtained for M2 even when K is used, and when M3 is Sn and / or Hf. Has been confirmed. For M1, another trivalent metal element may be used, for M2, another monovalent metal element may be used, and for M3, another tetravalent metal element may be used.

[0023]

As described above, according to the present invention, the relative dielectric constant is 180 or less and the resonance frequency constant of the thickness vibration is 300.
A piezoelectric ceramic composition suitable for use in a high frequency range of 0 Hz · m or more and exhibiting good characteristics such as a resonance frequency temperature coefficient fr-TC of 100 ppm or less and a Curie point exceeding 200 ° C. Using this piezoelectric ceramic composition, a piezoelectric ceramic element such as a piezoelectric ceramic filter or a piezoelectric ceramic oscillator can be advantageously produced.

Claims (2)

[Claims] 1. The general formula: (1-n) (K _1-xy Na _x L)
i _y ) _m (Nb ₁ -z T _az ) O ₃ -nM1M2M3O ₃
A piezoelectric ceramic composition comprising a composition represented by the following formula: Here, M1 is a trivalent metal element, M2 is a monovalent metal element,
M3 is a tetravalent metal element, x ≦ 0.9 0.02 ≦ y ≦ 0.3 0.75 ≦ x + y 0 ≦ z ≦ 0.3 0.98 ≦ m ≦ 1.0 0 <n ≦ 0.05 . 2. The M1 is Bi, and the M2 is K, N
and at least one member selected from the group consisting of Ti, Zr, Sn and Hf, wherein M3 is at least one member selected from the group consisting of a and Li.
3. The piezoelectric ceramic composition according to item 1.