CN113683413A - Millimeter wave dielectric ceramic - Google Patents

Millimeter wave dielectric ceramic Download PDF

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CN113683413A
CN113683413A CN202110942470.XA CN202110942470A CN113683413A CN 113683413 A CN113683413 A CN 113683413A CN 202110942470 A CN202110942470 A CN 202110942470A CN 113683413 A CN113683413 A CN 113683413A
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millimeter wave
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CN113683413B (en
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陈湘明
丁艺含
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Zhejiang University ZJU
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    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
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Abstract

The invention provides a millimeter wave dielectric ceramic, the general expression of the formula is as follows: xHfO2·yTiO2·zSiO2. Wherein x is more than or equal to 75.0 mol% and less than or equal to 97.0 mol%, y is more than or equal to 3.0 mol% and less than or equal to 25.0 mol%, z is more than or equal to 0 mol% and less than or equal to 5.0 mol%, and x + y + z is equal to 100%. The dielectric constant of the millimeter wave dielectric ceramic provided by the invention is 10-20, the Q value is as high as 5,000-9,000 (at 30GHz), and the temperature coefficient of the near-zero resonance frequency is obtained. The millimeter wave dielectric ceramic provided by the invention can enable microwave components such as dielectric resonators, filters and the like to be suitable for millimeter wave application, and is expected to solve the problem of key materials for future mobile communication. Therefore, the present invention is industrially very valuable.

Description

Millimeter wave dielectric ceramic
Technical Field
The invention relates to the field of millimeter wave communication, in particular to millimeter wave dielectric ceramics for a resonator and a filter.
Background
In recent years, with rapid development of mobile communication and satellite communication technologies, there has been an increasing demand for microwave dielectric ceramics for microwave devices such as dielectric resonators and filters. With the rapid development of mobile communication to millimeter wave band, the requirements for low dielectric constant and ultra-low loss millimeter wave dielectric ceramics are urgent. The basic performance requirements are as follows: dielectric constant εrNo more than 20, quality factor Q of 5,000GHz (at millimeter wave frequency), and temperature coefficient of resonance frequency tauf＝0±10ppm/℃。
The existing Ba-based composite perovskite ceramics and the like have ultra-low loss and near zeroTemperature coefficient of the portrait frequency, however, its dielectric constant is too large (>20) And the requirement of millimeter wave application cannot be met. MgAl2O4,、Mg2SiO4、Zn2SiO4Ceramics and the like have problems that the temperature coefficient of the resonance frequency is too large and the Q value is difficult to control.
On the basis of comprehensively inspecting the existing microwave dielectric ceramic system, the invention finally finds out a new formula of the low-dielectric-constant and ultra-low-loss millimeter wave dielectric ceramic by focusing on the hafnium oxide based solid solution.
Disclosure of Invention
The general expression of the formula of the millimeter wave ceramic provided by the invention is as follows: xHfO2·yTiO2·zSiO2. Wherein x is more than or equal to 75.0 mol% and less than or equal to 97.0 mol%, y is more than or equal to 1.0 mol% and less than or equal to 25.0 mol%, z is more than or equal to 0 mol% and less than or equal to 3.0 mol%, and x + y + z is equal to 100%.
The millimeter wave dielectric ceramic in the formula has x being 0.9, y being 0.09 and z being 0.01.
The millimeter wave dielectric ceramic with the formula has the characteristics of low dielectric constant (10-20), ultra-low loss (Q ═ 5,000-9,000 at 30GHz) and good temperature stability, is used as a key material of a resonator and a filter, and is suitable for the field of millimeter wave communication.
The invention has the advantages of
1. The existing Ba-based composite perovskite ceramics and the like have ultralow loss and near-zero temperature coefficient of fidelity frequency, but the dielectric constant is too large (>20), so that the requirements of millimeter wave application cannot be met. The dielectric ceramic provided by the invention has the characteristic of low dielectric constant (less than or equal to 20) and is suitable for millimeter wave application.
2、MgAl2O4,、Mg2SiO4、Zn2SiO4Ceramics and the like have problems that the temperature coefficient of the resonance frequency is too large and the Q value is difficult to control. The dielectric ceramic provided by the invention has the characteristics of ultra-low loss (Q is 5,000-9,000 at 30GHz) and good temperature stability, and can provide a key base material for future millimeter wave communication
3. The millimeter wave dielectric ceramic provided by the invention is a hafnium oxide-based solid solution, and has good compatibility with semiconductor materials such as silicon and the like.
4、HfO2Small ionic polarizability, resulting in a low dielectric constant. But simple HfO2The microwave performance is not good, so that the microwave and TiO are mixed2After the solid solution is formed, the non-simple harmonic vibration can be effectively reduced, so that the dielectric loss of the material is obviously reduced. At the same time, because of TiO2Has a positive temperature coefficient of resonance frequency, and HfO2The negative resonant frequency temperature coefficients cancel each other out, thereby facilitating obtaining the near-field resonant frequency temperature coefficient. Adding SiO2The purpose of the composition is to further reduce the temperature coefficient of the resonance frequency and improve the densification characteristics of the ceramic.
Detailed Description
Firstly, HfO with a purity of 99.9% or more is added2、TiO2With SiO2Mixing at a certain ratio for 24 hr by wet ball milling (solvent is anhydrous ethanol), adding binder, granulating, and molding under uniaxial pressure at 1000kg/cm2Preparing a ceramic blank with the diameter of 6mm and the thickness of 3-6mm under the pressure, and finally sintering the ceramic blank for 3 hours at 1375-1450 ℃ in an atmospheric atmosphere to prepare the required millimeter wave dielectric ceramic.
The dielectric properties of millimeter waves were evaluated at 30GHz by a high-order mode cylindrical dielectric resonator method.
The relationship between the millimeter wave dielectric properties and the composition of the materials in the examples is shown in table 1. As can be seen from Table 1, in the ceramic system of the present invention, TiO is accompanied by2The content is increased, the dielectric constant of the material tends to increase, and taufMoving towards positive values, while the Q value increases significantly first, then decreases slightly. In all component formulations of this example, HfO2＝90.0mol％，TiO2＝9.0mol％,SiO2The formula of 1.0 mol% has the best millimeter wave dielectric property: epsilonr15, Q8,000 at 30GHz, τf＝-3.5ppm/℃。
TABLE 1 relationship between millimeter wave dielectric properties and composition
Figure BDA0003215632770000031

Claims (3)

1. The millimeter wave dielectric ceramic is characterized in that the formula is as follows: xHfO2·yTiO2·zSiO2(ii) a Wherein x is more than or equal to 75.0 mol% and less than or equal to 97.0 mol%, y is more than or equal to 3.0 mol% and less than or equal to 25.0 mol%, z is more than or equal to 0 mol% and less than or equal to 5.0 mol%, and x + y + z is equal to 100%.
2. The millimeter wave dielectric ceramic of claim 1, wherein x is 0.9, y is 0.09, and z is 0.01.
3. The millimeter wave dielectric ceramic according to claim 1 or 2, wherein the millimeter wave dielectric ceramic is used as a key material for millimeter wave resonators and filters in the field of millimeter wave communication.
CN202110942470.XA 2021-08-17 2021-08-17 Millimeter wave dielectric ceramic Active CN113683413B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3938064A (en) * 1973-09-04 1976-02-10 Bell Telephone Laboratories, Incorporated Devices using low loss dielectric material
CN1697789A (en) * 2003-01-31 2005-11-16 株式会社村田制作所 Dielectric ceramic, process for producing the same and laminate ceramic capacitor
CN1765820A (en) * 2005-09-09 2006-05-03 华中科技大学 Low dielectric constant microwave dielectric ceramic material
CN111430228A (en) * 2020-04-26 2020-07-17 上海师范大学 Preparation method of dielectric film with ultrahigh dielectric constant

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3938064A (en) * 1973-09-04 1976-02-10 Bell Telephone Laboratories, Incorporated Devices using low loss dielectric material
CN1697789A (en) * 2003-01-31 2005-11-16 株式会社村田制作所 Dielectric ceramic, process for producing the same and laminate ceramic capacitor
CN1765820A (en) * 2005-09-09 2006-05-03 华中科技大学 Low dielectric constant microwave dielectric ceramic material
CN111430228A (en) * 2020-04-26 2020-07-17 上海师范大学 Preparation method of dielectric film with ultrahigh dielectric constant

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
S. POKHRIYAL ET AL.: ""Effects of Ti Doping on the Dielectric Properties of HfO2 Nanoparticles"", 《AIP CONFERENCE PROCEEDINGS》 *
胡成西: ""氧化硅基陶瓷的湿化学制备与微波介电性能研究"", 《中国优秀博硕士学位论文全文数据库(博士) 工程科技Ⅰ辑》 *

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