CN112299837A - Low-dielectric microwave dielectric ceramic material and temperature-frequency characteristic regulation and control method thereof - Google Patents
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Abstract
The invention belongs to the technical field of microwave dielectric ceramic, and discloses a low-dielectric microwave dielectric ceramic material and a temperature-frequency characteristic regulating and controlling method thereof, wherein the chemical general formula of the main crystal phase of the low-dielectric microwave dielectric ceramic material is CaO-SnO2‑xSiO2‑yGeO2Wherein x is more than or equal to 0 and less than or equal to 1.0, y is more than or equal to 0 and less than or equal to 1.0, the main crystal phase is a maleic stone phase, the microwave dielectric ceramic material is a low-dielectric microwave dielectric ceramic material, and the relative dielectric constant epsilon isr10.37 to 11.7. According to the microwave dielectric ceramic material obtained by correspondingly regulating the molar ratio of Ca to Sn to Si to Ge to be 1:1: x: y, the relative dielectric constant can be as low as 10.37-11.7, and the temperature coefficient tau of the resonant frequency can be obtained under the condition of avoiding using Ti elementfThe self-adjustable low-dielectric microwave dielectric ceramic material effectively widens the selection range of the low-dielectric constant microwave dielectric ceramic material. And, by regulating SiO2、GeO2The ratio of (a) to (b),by utilizing ion substitution, the resonant frequency temperature coefficient tau of the microwave dielectric ceramic material can be regulated and controlledf。
Description
Technical Field
The invention belongs to the technical field of microwave dielectric ceramics, and particularly relates to a low-dielectric microwave dielectric ceramic material and a temperature-frequency characteristic regulating and controlling method thereof.
Background
The microwave dielectric ceramic is a ceramic material which is used as a medium in a microwave frequency band (300 MHz-300 GHz) circuit. With the arrival of the 5G era and the continuous improvement of the operating frequency of communication equipment, the signal delay phenomenon becomes more obvious, the system loss and the heat productivity are increased, and the system stability is gradually deteriorated. The low dielectric constant can reduce the cross coupling loss between the material and the electrode, and can improve the transmission rate of the electric signal, the high quality factor can effectively improve the frequency selection characteristic and reduce the loss, and the near-zero temperature coefficient of the resonant frequency is beneficial to the stable work of the device. Therefore, the research on the microwave dielectric ceramic with low dielectric constant, high quality factor and near-zero temperature coefficient of resonance frequency is particularly important.
For microwave dielectric ceramics with low dielectric constant, the polarization form is mainly ion displacement polarization, when the temperature rises, ionic bonds gradually extend, the polarization distance gradually increases, the ion polarization gradually increases, and the dielectric constant shows the trend of gradually increasing along with the temperature rise, so for most microwave dielectric ceramics with low dielectric constant, the temperature coefficient of the resonant frequency tends to be negative, and the adjustment of the negative temperature coefficient of the resonant frequency tends to adopt the addition of a Ti base (TiO) with a positive temperature coefficient of the resonant frequency (TiO)2、CaTiO3、SrTiO3) The material is prepared by the method, but the addition of the Ti-based material can cause the increase of the dielectric constant, the reduction of the quality factor and the increase of the temperature of the Ti-based materialThe price is easy to change. Therefore, it is important to develop a method for adjusting and controlling the resonant frequency temperature coefficient of the low-dielectric microwave dielectric ceramic by changing the chemical structure through ion substitution.
Therefore, the development of a microwave dielectric ceramic material containing no Ti element, having low dielectric constant, high quality factor and temperature coefficient of near-zero resonant frequency is imminent.
Disclosure of Invention
In view of the above defects or improvement requirements of the prior art, the present invention aims to provide a low dielectric microwave dielectric ceramic material and a temperature-frequency characteristic control method thereof, wherein CaO-SnO is controlled2-xSiO2-yGeO2The molar ratio of the Ca to the Sn to the Si to the Ge is 1:1: x: y, particularly the ratio of the Si to the Ge is x: y, and the microwave dielectric ceramic material obtained correspondingly can obtain the microwave dielectric ceramic material with the relative dielectric constant as low as 10.37-11.7 and the temperature coefficient tau of resonant frequency under the condition of avoiding the use of Ti elementfThe self-adjustable low-dielectric microwave dielectric ceramic material effectively widens the selection range of the low-dielectric constant microwave dielectric ceramic material. Moreover, the microwave dielectric ceramic material is particularly suitable for obtaining a corresponding temperature-frequency characteristic regulation method by regulating SiO2、GeO2The octahedron torsion degree in the microwave dielectric ceramic material is regulated and controlled by utilizing ion substitution, so that the resonant frequency temperature coefficient tau of the microwave dielectric ceramic material is regulated and controlledf。
In order to achieve the above object, according to one aspect of the present invention, there is provided a low dielectric microwave dielectric ceramic material characterized in that the main crystal phase has a chemical formula of CaO-SnO2-xSiO2-yGeO2Wherein x is more than or equal to 0 and less than or equal to 1.0, y is more than or equal to 0 and less than or equal to 1.0, x + y is 1, the main crystal phase is a maleic stone phase, the microwave dielectric ceramic material is a low-dielectric microwave dielectric ceramic material, and the relative dielectric constant epsilonr＝10.37～11.7。
In a further preferred embodiment of the present invention, the low dielectric microwave dielectric ceramic material has a quality factor of qxf 37900 to 64200GHz and a temperature coefficient of resonance frequency τfSatisfying the requirement of tau being less than or equal to minus 77.8 ppm/DEG Cf≤+62.5ppm/℃。
As the inventionFurther preferably, the SnO in the microwave dielectric ceramic material can be regulated and controlled by regulating and controlling x and y and utilizing ion substitution6Octahedron torsion degree, thereby regulating and controlling the resonant frequency temperature coefficient tau of the microwave dielectric ceramic materialf。
As a further preferable aspect of the present invention, x is 0. ltoreq. x.ltoreq.1.0, y is 0. ltoreq. y.ltoreq.0.7, and the temperature coefficient of resonance frequency tau of the microwave dielectric ceramic materialfPositive values.
In a further preferred embodiment of the present invention, x is 0.3 and y is 0.7, and the temperature coefficient of resonance frequency τ of the microwave dielectric ceramic materialf+5.2 ppm/deg.c, and the quality factor Q × f 37900 GHz.
According to another aspect of the present invention, the present invention provides a method for preparing the low dielectric microwave dielectric ceramic material, which is characterized by comprising the following steps:
(1) weighing CaCO according to nominal stoichiometric ratio3、SnO2、GeO2And SiO2Then, ball-milling the raw materials by a wet method, drying the raw materials after ball milling, and then presintering the raw materials to obtain presintering ceramic powder;
(2) and (2) performing wet ball milling treatment on the pre-sintered ceramic powder obtained in the step (1), drying, adding a binder for granulation, tabletting and sintering to obtain the low-dielectric microwave dielectric ceramic material.
In a further preferred embodiment of the present invention, in the step (1), the pre-sintering temperature is 1100-.
As a further preferable mode of the invention, in the step (2), the binder is PVA or paraffin wax, and the mass fraction of the binder added is 5% -10%; preferably, the binder is PVA, and the mass fraction of the added binder is 5%.
As a further preferred aspect of the present invention, in the step (2), the sintering temperature is 1450 ℃ to 1500 ℃, and the sintering time is 5 to 10 hours; preferably, after sintering, the temperature is reduced to 1000 ℃ at the speed of 1 ℃/min, then the temperature is reduced to 800 ℃ at the speed of 2 ℃/min, and then the temperature is reduced along with the furnace.
According to yet another aspect of the present invention, the present inventionThe method is characterized in that the method regulates and controls SnO in the microwave dielectric ceramic material by regulating and controlling x and y and utilizing ion substitution6Octahedron torsion degree, thereby regulating and controlling the resonant frequency temperature coefficient tau of the microwave dielectric ceramic materialf。
Compared with the prior art, the microwave dielectric ceramic material CaO-SnO is prepared by the technical scheme of the invention2-xSiO2-yGeO2(x is more than or equal to 0 and less than or equal to 1.0, y is more than or equal to 0 and less than or equal to 1.0, and x + y is equal to 1), the dielectric constant is between 10.37 and 11.7, the quality factor Qxf is 37900-64200 GHz, and the temperature coefficient tau of the resonant frequency isfThe range of (A) is as follows: -77.8 ppm/. degree.C.ltoreq.taufLess than or equal to +62.5 ppm/DEG C, and simultaneously avoids the use of Ti element. Specifically, the present invention can achieve the following advantageous effects:
(1) the invention adopts the chemical general formula of CaO-SnO2-xSiO2-yGeO2The compound is used for preparing the microwave dielectric ceramic material, and the novel microwave dielectric ceramic has the advantages of low dielectric constant, excellent quality factor, adjustable resonant frequency temperature coefficient, single phase component, low loss, near-zero resonant frequency temperature coefficient and wide sintering temperature range.
(2) The invention provides a method for directionally changing the chemical structure of a material by ion substitution so as to regulate and control the resonant frequency temperature coefficient of the material, the resonant frequency temperature coefficient can be regulated and controlled by changing the oxygen octahedron tortuosity of the material, and a low-dielectric microwave dielectric ceramic material with the resonant frequency temperature coefficient of a positive value or near zero and excellent quality factor is prepared under the condition of not adding a regulating agent. The invention adjusts the temperature-frequency characteristic of the material by modifying the chemical structure, and regulates and controls SnO by ion substitution6Octahedral twist, which can be measured in degrees of taufValue regulation to anomalous positive taufThe value (different from the common negative value in the prior art) or near zero can be especially taken as a novel taufValue modulating agents. For example, when x is 0.3 and y is 0.7, a near-zero temperature coefficient of resonance frequency, τ, can be achievedf+5.2 ppm/c, close to 0.
(3) The invention improves the stability of the maleimide phase by utilizing the characteristic that the radius of Ge ions is larger than that of Si ions and compressing Sn-O bonds connected with Si/Ge-O bonds in the maleimide phase, thereby improving the quality factor Qxf of the maleimide phase.
In conclusion, the microwave dielectric ceramic has stable low dielectric constant, excellent quality factor and self-adjustable resonant frequency temperature coefficient. The chemical general formula of the invention is CaO-SnO2-xSiO2-yGeO2(x is 0. ltoreq. x.ltoreq.1.0, y is 0. ltoreq. y.ltoreq.1.0, and x + y is 1) low-dielectric-constant (ε)r10.37-11.7), excellent quality factor (Q multiplied by f is 37900-64200 GHz) and wider sintering temperature range (1450-1500 ℃), and the microwave dielectric ceramic especially has adjustable resonant frequency temperature coefficient (-77.8 ppm/DEG C ≦ tau ≦ 1500 ≦fLess than or equal to +62.5 ppm/DEG C). Its excellent quality factor represents lower dielectric loss; the tau can be regulated and controlled by regulating and controlling the oxygen octahedron torsion degreefValue (e.g., τ can be directionally modulatedfTo near zero) is a potential microwave dielectric material which can be applied to the field of 5G communication.
Drawings
FIG. 1 shows CaO-SnO according to the present invention2-xSiO2-yGeO2(x is more than or equal to 0 and less than or equal to 1.0, y is more than or equal to 0 and less than or equal to 1.0, and x + y is equal to 1) phase XRD pattern of the low dielectric microwave dielectric ceramic.
FIG. 2 shows CaO-SnO according to the present invention2-xSiO2-yGeO2(x is more than or equal to 0 and less than or equal to 1.0, y is more than or equal to 0 and less than or equal to 1.0, and x + y is equal to 1) surface hot corrosion SEM image of the low dielectric microwave dielectric ceramic. In FIG. 2, (a), (b), (c), (d), (e), (f), (g) and (h) correspond to y values of 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.9 and 1.0, respectively; the scales in the figure all represent 5 μm.
FIGS. 3-11 show CaO-SnO of the present invention under different x and y value combinations2-xSiO2-yGeO2Low-temperature dielectric temperature spectrum of low-dielectric microwave dielectric ceramic. By substituting Si ions with Ge ions, the dielectric constant abnormal peak at low temperature can be shifted to near room temperature, the shift of the dielectric constant abnormal peak can well explain the change of the temperature coefficient of the resonant frequency, and CaO-SnO2-xSiO2-yGeO2(x is 0.3 and y is 0.7) the dielectric temperature spectrum is nearly flat near the room temperature, and can well correspond to near-zero CaO-SnO2-xSiO2-yGeO2(x is 0.3 and y is 0.7).
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention provides a low dielectric microwave dielectric ceramic material with a chemical formula of CaO-SnO2-xSiO2-yGeO2(x is more than or equal to 0 and less than or equal to 1.0, y is more than or equal to 0 and less than or equal to 1.0, and x + y is equal to 1), and the ceramic can be particularly applied as microwave dielectric ceramic
The microwave dielectric ceramic has low dielectric constant, excellent quality factor (Q multiplied by f is 37900-64200 GHz) and controllable temperature coefficient of resonance frequency (minus 77.8 ppm/DEG C ≦ tau)fLess than or equal to +62.5 ppm/DEG C), the relative dielectric constant is relatively stable, and when the values of x and y are changed, the relative dielectric constant of the corresponding microwave dielectric ceramic is between 10.37 and 11.7.
The preparation method of the microwave dielectric ceramic can comprise the following steps:
(1) CaO-SnO according to a chemical expression2-xSiO2-yGeO2Weighing CaCO in stoichiometric ratio3、SnO2、GeO2And SiO2Weighing, performing wet ball milling treatment, drying after ball milling, and then pre-sintering to obtain pre-sintered ceramic powder;
(2) and (2) performing secondary wet ball milling treatment on the pre-sintered ceramic powder obtained in the step (1), drying, adding a binder for granulation, tabletting and sintering to obtain the microwave dielectric ceramic.
Preferably, the temperature of the pre-sintering in the step (1) can be 1100-.
Preferably, the binder in the step (2) is PVA or paraffin, and the mass fraction of the added binder can be 5-10%.
Preferably, the sintering temperature in the step (2) is 1450-1500 ℃, the sintering time is 5 hours, after the heat preservation for 5 hours is finished, the temperature is reduced to 1000 ℃ at the speed of 1 ℃/min, then the temperature is reduced to 800 ℃ at the speed of 2 ℃/min, and then the temperature is reduced along with the furnace.
In some embodiments, the dispersant used in the wet ball milling step is deionized water.
The following are examples:
examples 1 to 11
The preparation method of the microwave dielectric ceramic comprises the following steps:
(1) will analyze the pure CaCO3、SiO2And SnO with purity of not less than 99.9%2And GeO2Respectively mixing according to a stoichiometric proportion, taking zirconium balls as a ball milling medium and deionized water as a dispersing agent, and mixing and stirring the powder for 5 hours by using a ball mill at the rotating speed of 360 r/min; drying the obtained slurry, and then presintering for 5 hours at 1150 ℃ to obtain presintering ceramic powder;
(2) performing wet ball milling treatment on the pre-sintered ceramic powder obtained in the step (1), drying the dispersant by using deionized water, adding 8 wt% of polyvinyl alcohol (PVA) adhesive into the dried powder for granulation, and pressing the powder into a cylindrical green compact sample with the thickness-to-diameter ratio of 0.4-0.6 under the pressure of 150 MPa; and (3) sintering the pressed ceramic in air at 1450-1500 ℃ for 5 hours to obtain the microwave dielectric ceramic shown in the table 1.
TABLE 1 examples 1 to 11, sintering temperatures and microwave dielectric Properties
As can be seen from examples 1 to 11, the novel microwave dielectric ceramic material has a low dielectric constant and an excellent quality factor, wherein the dielectric constant is 10.37 to 11.7, the quality factor is 37900 to 64200GHz, the temperature coefficient of resonance frequency is-77.8 to +62.5 ppm/DEG C, and CaO-SnO is arranged at a position where x is 0.72-xSiO2-yGeO2Ceramics exhibit excellent quality factors and near-zero temperature coefficients of resonant frequencies.
CaO-SnO2-xSiO2-yGeO2The chemical structure parameters of the microwave dielectric ceramic are shown in Table 2.
TABLE 2 CaO-SnO2-xSiO2-yGeO2Chemical structure parameter of microwave dielectric ceramic
-R: average bond length; δ: oxygen octahedral tortuosity; P.F: bulk density; v: a bond price; r isc: the ratio of covalent bonds;
as can be seen from Table 2, as the content of Ge increased, the bond length of Si/Ge-O bond increased gradually, and the growth of Si/Ge-O bond adversely affected the bond length of Sn-O bond and SnO via bridging oxygen bonding6Octahedral twist, SnO6The octahedron torsion degree is gradually increased along with the increase of the substitution amount, and the increased octahedron torsion degree can reduce CaO-SnO2-xSiO2-yGeO2The temperature coefficient of the resonant frequency of the microwave dielectric ceramic.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A low-dielectric microwave dielectric ceramic material is characterized in that the chemical general formula of the main crystal phase is CaO-SnO2-xSiO2-yGeO2Wherein x is more than or equal to 0 and less than or equal to 1.0, y is more than or equal to 0 and less than or equal to 1.0, x + y is 1, the main crystal phase is a maleic stone phase, the microwave dielectric ceramic material is a low-dielectric microwave dielectric ceramic material, and the relative dielectric constant epsilonr＝10.37～11.7。
2. The low dielectric microwave dielectric ceramic material as claimed in claim 1, wherein the low dielectric microwave dielectric ceramic material has a quality factor of Qxf 37900-64200 GHz and a temperature coefficient of resonance frequency τfSatisfying the requirement of tau being less than or equal to minus 77.8 ppm/DEG Cf≤+62.5ppm/℃。
3. The low dielectric microwave dielectric ceramic material as claimed in claim 1, wherein SnO in the microwave dielectric ceramic material can be controlled by controlling x and y and utilizing ion substitution6Octahedron torsion degree, thereby regulating and controlling the resonant frequency temperature coefficient tau of the microwave dielectric ceramic materialf。
4. The low dielectric microwave dielectric ceramic material as claimed in claim 3, wherein x is 0. ltoreq. x.ltoreq.1.0, y is 0. ltoreq. y.ltoreq.0.7, and the temperature coefficient of resonance frequency τ of the microwave dielectric ceramic materialfPositive values.
5. A low dielectric microwave dielectric ceramic material as claimed in claim 4, wherein x is 0.3 and y is 0.7, and the microwave dielectric ceramic material has a temperature coefficient of resonance frequency τf+5.2 ppm/deg.c, and the quality factor Q × f 37900 GHz.
6. A method of preparing a low dielectric microwave dielectric ceramic material as claimed in any of claims 1 to 5, comprising the steps of:
(1) weighing CaCO according to nominal stoichiometric ratio3、SnO2、GeO2And SiO2Then ball-milling the raw materials by a wet method, drying the raw materials after ball milling, and then pre-millingSintering to obtain pre-sintered ceramic powder;
(2) and (2) performing wet ball milling treatment on the pre-sintered ceramic powder obtained in the step (1), drying, adding a binder for granulation, tabletting and sintering to obtain the low-dielectric microwave dielectric ceramic material.
7. The method as claimed in claim 6, wherein in the step (1), the pre-sintering temperature is 1100-1150 ℃ and the pre-sintering time is 5-10 hours.
8. The method of claim 6, wherein in the step (2), the binder is PVA or paraffin wax, and the mass fraction of the added binder is 5-10%; preferably, the binder is PVA, and the mass fraction of the added binder is 5%.
9. The method according to claim 6, wherein in the step (2), the sintering temperature is 1450-1500 ℃, and the sintering time is 5-10 hours; preferably, after sintering, the temperature is reduced to 1000 ℃ at the speed of 1 ℃/min, then the temperature is reduced to 800 ℃ at the speed of 2 ℃/min, and then the temperature is reduced along with the furnace.
10. The method for regulating the temperature-frequency characteristics of a low dielectric microwave dielectric ceramic material as claimed in any one of claims 1 to 5, wherein the method comprises regulating SnO in the microwave dielectric ceramic material by regulating x and y and utilizing ion substitution6Octahedron torsion degree, thereby regulating and controlling the resonant frequency temperature coefficient tau of the microwave dielectric ceramic materialf。
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