KR102023375B1 - Dielectric Ceramics for Resonator Surports and the manufacturing method of the same - Google Patents

Abstract

The present invention is a dielectric ceramic material and that associated with the method of manufacturing the _{same, Zn 1 .9- x M x Si} 1 having the sintering and dielectric characteristics even at a high frequency band for the support of the resonator and a filter used in a wireless communication _{system. 05} O ₄ system to provide a ceramic composition.
As described above, according to the present invention, high dielectric properties can be obtained in the high frequency band, and an effect of realizing uniform and reproducible sintering and dielectric properties can be expected.

Description

Dielectric ceramics for resonator support and its manufacturing method {Dielectric Ceramics for Resonator Surports and the manufacturing method of the same}

The present invention is a dielectric ceramic material, and relates to a method of manufacturing the _{same, Zn 1 .9- x M x Si} 1 having the sintering and dielectric characteristics even at a high frequency band for the support of the resonator and a filter used in a wireless communication _{system. 05} O ₄ -based ceramic material composition to provide.

Recently, as the amount of information increases and the communication frequency band saturates due to the development of wireless communication, the use frequency band is rising to a higher band, and a high quality high frequency transmission / reception component corresponding thereto is urgently required. Therefore, the higher the frequency band, the lower the dielectric constant (ε _r ) and the higher the quality coefficient (Q × f) is needed.

On the other hand, the cavity filter used in the satellite relay or wireless communication relay system in the microwave region is composed of a ceramic dielectric resonator and a ceramic support in the cavity of the metal as shown in FIG. Here, the ceramic support is required to have a low dielectric constant and high quality dielectric properties, for this purpose alumina (Al ₂ O ₃ ) is commonly used. However, other ceramic materials such as Mg ₂ SiO ₄ modified as disclosed in Korean Patent Registration No. 10-1261098 (2013. 05. 02) may be used.

Meanwhile, Zn ₁ , which is the basic composition of the present invention _{. 9} Si _1. As disclosed in Prior Art Document 1, ₀₅ O ₄ has a willemite crystal structure and exhibits excellent high frequency dielectric properties of ε _r = 6.43 and Q × f = 120,000 GHz.

In addition, Zn _{1 . 9} Si _{1 . 05} O ₄ The high frequency dielectric ceramic is sintered Zn _1.8 SiO _3.8 at 1300 ℃ by adjusting the composition ratio of zinc (Zn) and silicon (Si) as disclosed in the prior art document 3 (Korean Patent Registration No. 10-0842855), ε _r = 6.6, Q x f = 127,000 GHz, τ _f = -20 ppm / ℃ to improve the dielectric properties.

In addition, as disclosed in the prior art document 4 (Korean Patent Publication No. 10-2010-0098232), Zn _{1 . 8} SiO _{3 .8} The composition of vanadium oxide (V ₂ O ₅₎ or a bismuth oxide (Bi ₂ O ₃₎ by a sintering at 900 ℃ by addition of an appropriate _{amount, ε r = 7.3, Q ×} f = 17,500 GHz, τ f = A high frequency dielectric ceramic material having improved dielectric properties at about -28 ppm / ° C is disclosed.

Further, according to the prior art document 5 (Korean Patent Registration No. 10-1261098), the modified Mg ₂ SiO ₄ sintered at 1310 ℃ ε _r = 10 or less, Q × f = 15,000 GHz, τ _f = 8 ppm / It is characterized by improving the dielectric properties to about 占 폚.

However, these prior arts are very poor in dielectric properties for the support of the resonator and the filter due to the various compounds added. In particular, there is a problem in that the added materials make the second phase, greatly lowering the quality factor among the dielectric properties.

 Therefore, dielectric ceramics for the support of resonators and filters used in a wireless communication system for high quality high frequency transmission and reception have a dielectric constant and a quality factor so that the shrinkage does not affect the sintering characteristics and the characteristics of the resonator which have a constant shrinkage. It is very important to have uniform dielectric properties.

In the future, due to the beginning of 5th generation communication, dielectric ceramic materials used for duplexers, DMB / DAB, satellite LNB, oscillator, repeaters, and bandpass filters in the tens of GHz frequency band are high frequency dielectric ceramics. It is increasingly necessary to have high dielectric properties with low dielectric constant (ε _r ) and high quality coefficient (Q × f) for high quality high frequency transmission and reception with a resonator.

Journal of the Korean Institute of Electrical and Electronic Material Engineers, Vol.38, No.7, pp428 432 (2005.07.) Republic of Korea Patent Registration No. 10-1261098 (2013.05.02.) Republic of Korea Patent Registration No. 10-0842855 (2008.06.25.) Republic of Korea Patent Publication No. 10-2010-0098232 (2010.09.05.)

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art, and an object of the present invention is to provide a dielectric ceramic material for a resonator support having a uniform sinterability and dielectric properties in a high frequency band and a method of manufacturing the same.

Dielectric ceramics for the support of the resonator and filter used in the wireless communication system for high-quality high-frequency transmission and reception, so that the difference in size does not occur after sintering, that is, the reproducibility is excellent and does not affect the characteristics of the sintering and resonator constant shrinkage rate so that the dielectric constant and quality factor is important to have uniform dielectric properties, and the elements or additives that _{Zn 1 .9-x M x Si} 1.05 O 4 based sinterability and dielectric characteristics of the high frequency dielectric ceramic material is substituted in each spot Therefore, the use of high purity raw materials is essential for this purpose, and it is also important to select an appropriate additive and add an appropriate amount in consideration of the size and valence of the substitution element. In short, the present invention is significant in that the sintering and dielectric properties are uniform while maintaining the dielectric properties as much as possible.

The present invention, in order to achieve the above object, in the formula represented by the formula Zn _1.9-x M _x Si _1.05 O ₄ , M is +2 is a metal, x is 0.05 to 0.4, the dielectric for the resonator support Provide ceramic material.

M is preferably at least one selected from magnesium (Mg), nickel (Ni), cobalt (Co), and manganese (Mn).

The ceramic material is preferably produced by sintering in the range of 1325 ℃ to 1400 ℃.

As described above, according to the present invention, high dielectric properties can be obtained in the high frequency band, and an effect of realizing uniform and reproducible sintering and dielectric properties can be expected. In particular, in the present invention, by dissolving Mg, Ni and the like in a fixed amount in the Zn position, the formation of the second phase is suppressed and the deterioration of the quality factor is prevented.

In addition, the present invention can obtain a uniform dielectric properties and shrinkage rate in a wide sintering temperature range, it can be expected the effect of process improvement.

In addition, the present invention can expect the effect of high-quality high-frequency transmission and reception in the tens of GHz frequency band.

1 shows the structure of a typical cavity filter.
2 is M _x Zn _{1 .9- 0} in accordance with one embodiment of the present _{invention. 1} Si _{1 . It} is a graph showing the change of shrinkage rate according to sintering temperature of ₀₅ O ₄ series dielectric ceramic material
3 is Zn, according to one embodiment of the present invention _{1 .9- x} M _{0. 1} Si _{1 . This} graph shows the change of dielectric constant according to the sintering temperature of ₀₅ O ₄ series dielectric ceramic material.
4 is a Zn _{1 .9-} M _{x 0,} according to one embodiment of the present _{invention. 1} Si _{1 . 05 This} graph shows the change of quality factor according to sintering temperature of O ₄ series dielectric ceramic material.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. In addition, in describing the present invention, when it is determined that the detailed description of the related well-known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted.

In the description of the present invention, terms defined are defined in consideration of functions in the present invention, which may vary according to the intention or custom of a person skilled in the art and the definitions are based on the contents throughout this specification. Will have to be lowered.

In order to solve the above-mentioned problems, the present invention relates to magnesium (Mg), nickel (Ni), cobalt (Co), and manganese (Zg) in place of zinc (Zn) in Zn _1.9-x M _x Si _1.05 O ₄ having excellent high frequency dielectric properties. Mn) of the addition to some of the substitution element such as, relates to a high dielectric ceramic composition having a stable sinterability and dielectric properties, represented by the formula the formula the formula _{Zn 1 .9-x M x Si} 1.05 O 4 of, M is the elements listed above, and is added so that x satisfies 0.05 to 0.4.

Such a composition of the present invention can be prepared by the following production method.

The composition of the present invention is ZnO, MgO, NiO, Co ₂ O ₃ manufactured by Kodoundo Chem. Lab. Co., Ltd. And SiO ₂ were used as starting materials.

Having a uniform degree of sintering and dielectric properties _{Zn 1 .9- x M x Si 1} . _{In the 05} O ₄ -based dielectric ceramic material, raw material powders corresponding to the respective compositions were weighed as shown in Table 1 below, and were mixed with zirconia ball and ethyl alcohol in a polyethylene container and mixed for 24 hours.

After drying, the mixed powder was placed in a metal mold having a diameter of 25 mm, uniaxially press-molded, and calcined at 1100 ° C. for 10 hours. The calcined molded body was again ball milled by the above mixing method, placed in an oven, and dried at 110 to 120 ° C. for 24 to 48 hours.

After drying, the calcined powder was placed in a metal mold having a diameter of 15 mm, uniaxially press-molded at a pressure of 50 MPa, and then sintered at 1325 to 1400 ° C. for 2 hours, and the temperature rising rate was 5 ° C./min. .

X-ray diffraction analysis (D / MAX-2500V / PC, Rigaku, Japan) was performed on the powder obtained by crushing the sintered compact, and the powder obtained by pulverizing the sintered compact. And the temperature coefficient (τ _f ) was measured by the cavity method, and the dielectric constant was measured by the Network Analyzer using the Hakki-Coleman method.

The temperature coefficient was measured using model name R3767CG (Advantest, Japan), and the quality factor and dielectric constant were measured using model name E5071C (Keysight, U.S.A.).

Hereinafter, the configuration and effects of the present invention through the embodiments will be described in more detail. These examples are only for illustrating the present invention, but the scope of the present invention is not limited by these examples.

<Example>

Embodiments of the production method for preparing the composition of the present invention are as described above.

In the present invention Zn _{1 . 9} Si _{1 .} By replacing part of Zn with +2 metal in ₀₅ O ₄ , uniformity of sintering characteristics and dielectric properties could be ensured, and the content was 0.05 to 0.4 mol. If the upper limit of the above range is exceeded, the sinter shrinkage change and the dielectric property change become too large. If the upper limit is exceeded, Zn _{1 . 9} Si _{1 . Since} the intrinsic properties of ₀₅ O ₄ may be lost, the value is of critical significance in the above range.

Comparative Example

In order to examine the substitution effect of the +2 valence metal element in the present invention, Zn ₁ without addition of other components as shown in Table 1 below _{. 9} Si _{1 . 05} O ₄ specimens were prepared in the same manner as in the above examples and evaluated for their characteristics.

_{Zn 1 .9- x M x Si 1} . ₀₅ Sinterability and Dielectric Properties of O _{4 Based} Dielectric Ceramics number       Composition (mol) Sintering Temperature (℃) Shrinkage (%) ε _r Q × f (GHz) Remarks ZnO M ₂ O ₃ SiO ₂ Comparative Example 1 1.9 - 0 1.05 1325 20.60 6.08 107857 Comparative Example 2 1.9 - 0 1.05 1350 21.47 6.07 118871 Comparative Example 3 1.9 - 0 1.05 1375 21.80 6.21 127409 Comparative Example 4 1.9 - 0 1.05 1400 22.13 6.39 129435 Example 1 1.8 Mg 0.1 1.05 1325 22.80 6.31 122791 Example 2 1.8 Mg 0.1 1.05 1350 22.67 6.33 126957 Example 3 1.8 Mg 0.1 1.05 1375 22.67 6.3 126156 Example 4 1.8 Mg 0.1 1.05 1400 22.80 6.37 129019 Example 5 1.8 Ni 0.1 1.05 1325 22.80 6.41 123679 Example 6 1.8 Ni 0.1 1.05 1350 22.93 6.45 129850 Example 7 1.8 Ni 0.1 1.05 1375 22.67 6.39 130529 Example 8 1.8 Ni 0.1 1.05 1400 22.73 6.4 128527 Example 9 1.8 Co 0.1 1.05 1325 22.07 6.4 128612 Example 10 1.8 Co 0.1 1.05 1350 22.67 6.4 128970 Example 11 1.8 Co 0.1 1.05 1375 22.27 6.38 126139 Example 12 1.8 Co 0.1 1.05 1400 22.07 6.48 124954 Example 13 1.85 Mg 0.05 1.05 1350 22.33 6.43 123845 Example 14 1.7 Mg 0.2 1.05 1350 22.53 6.35 121925 Example 15 1.5 Mg 0.4 1.05 1350 23.00 6.33 123202 Example 16 1.85 Ni 0.05 1.05 1350 23.20 6.43 122776 Example 17 1.7 Ni 0.2 1.05 1350 23.20 6.46 129318 Example 18 1.5 Ni 0.4 1.05 1350 23.73 6.48 122810 Example 19 1.85 Co 0.05 1.05 1350 23.00 6.49 122066 Example 20 1.85 Mn 0.05 1.05 1350 23.53 6.45 120026

Having a uniform degree of sintering and dielectric properties _{Zn 1 .9- x M x Si 1} . ₀₅ O ₄ based dielectric shrinkage of the ceramic material are shown in Table 1 and shown +2 is a slight difference, but the 22% level to 23% range sufficient sintering shrinkage, except for Example 21 in accordance with the substitution amount of the metal element, as in the 2 This is stable and it can be seen that the change of the shrinkage rate with the sintering temperature is not large. However, when +2 is not substituted for the metal element, sintering shrinkage occurs well, but since the change of shrinkage rate with the sintering temperature is relatively large, it is difficult to manufacture a support of uniform size, and post-processing such as polishing is inevitable. A problem was found.

On the other hand, as shown in Table 1 and Figs. 3 and _{4 Zn 1 .9- x M x Si} 1. _In the high frequency dielectric properties of O ₄ -based dielectric ceramic materials, the dielectric constant does not differ as large as about 6.3 to 6.5 when +2 is substituted for the metal element, and the quality factor is higher than 120,000 GHz in most compositions depending on the sintering temperature. It shows a high value and the change width is very small. However, when +2 is not substituted for the metal element, the change of dielectric properties according to the sintering temperature is very large, and when used as a support of the resonator, it affects the resonator characteristics and deteriorates the characteristics of the wireless communication system for high quality high frequency transmission and reception. Becomes

These results Zn _{1 .9- x} M _x Si ₁ having a sintering property and dielectric properties uniformly _{from. In} order to manufacture the O ₄ -based dielectric ceramic material, it is very important to select an appropriate + 2-valent metal element and to substitute an appropriate amount. According to the present invention, magnesium (Mg), nickel (Ni) and cobalt ( When Co) is substituted in the range of 0.05 to 0.4, it can be seen that it is possible to manufacture an excellent dielectric ceramic material for the resonator support having stable sinterability and dielectric properties.

Claims (3)

In the formula represented by the formula Zn _1.9-x M _x Si _1.05 O ₄ , M is +2 a metal, x is 0.05 to 0.4, and M is magnesium (Mg), nickel (Ni), cobalt (Co), A dielectric ceramic material for a resonator support, characterized in that it is at least one selected from manganese (Mn). delete The method of claim 1,
The ceramic material is a dielectric ceramic material for the resonator support, characterized in that the sintering is produced in the range of 1325 ℃ to 1400 ℃.

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