CN112408976A - Environment-friendly low-dielectric-loss ceramic dielectric material and preparation method thereof - Google Patents

Environment-friendly low-dielectric-loss ceramic dielectric material and preparation method thereof Download PDF

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CN112408976A
CN112408976A CN202011330582.1A CN202011330582A CN112408976A CN 112408976 A CN112408976 A CN 112408976A CN 202011330582 A CN202011330582 A CN 202011330582A CN 112408976 A CN112408976 A CN 112408976A
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dielectric material
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ceramic dielectric
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黄景林
钟永全
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XIAMEN WANMING ELECTRONICS CO Ltd
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Abstract

The invention relates to an environment-friendly low-dielectric-loss ceramic dielectric material and a preparation method thereof, wherein the environment-friendly low-dielectric-loss ceramic dielectric material consists of a main component and a modified dopant, wherein the chemical formula of the main component is (1-y) Ba1‑xMgxTiO3‑y Y2Ti2O7Wherein x is 0.005-0.01, and y is 0.01-0.05; the modifying dopant is selected from Bi2SnZrO7、Bi2Ti2O7、CeO2、ZrO2、Al2O3、SiO2、Er2O3、Nb2O5、MnCO3Five of CuOOne or more than five. The firing temperature of the prepared ceramic dielectric material is 1330-1390 ℃, the dielectric constant is 3300-3700 adjustable, the dielectric loss is less than or equal to 0.5%, and the dielectric strength is not less than 6KVAcThe temperature characteristic change rate is less than or equal to +/-5% (-55-125 ℃), and the ceramic dielectric capacitor is suitable for manufacturing environment-friendly ceramic capacitors with excellent temperature characteristics.

Description

Environment-friendly low-dielectric-loss ceramic dielectric material and preparation method thereof
Technical Field
The invention relates to a ceramic capacitor preparation technology, in particular to an environment-friendly low-dielectric-loss ceramic dielectric material and a preparation method thereof.
Background
The capacitor is an important passive electronic device, mainly plays the roles of coupling, filtering, resonance, bypass, compensation and the like in a circuit, and is an indispensable device in the electronic, communication and information industries. The capacitor is classified into a ceramic capacitor, an electrolytic capacitor, a thin film capacitor, and the like according to the constituent material. The ceramic capacitor has the characteristics of low dielectric loss, high insulation resistance, high electric strength, high stability and reliability, wide application and the like, and the ceramic dielectric material determines the performance of the ceramic capacitor and is the core material of the ceramic capacitor.
In recent years, with the continuous development of the electronic industry, the ceramic dielectric capacitor is continuously miniaturized, and the quality performance requirement is higher and higher, especially in the smart grid construction and the automotive electronics industry. In order to enable electronic products to be stably and reliably used in a wider environment temperature range, higher requirements are put forward on the temperature characteristic change rate and the dielectric loss of the ceramic dielectric capacitor. However, the dielectric material of X7R ceramic capacitor with a dielectric constant of about 3500 used in the current ceramic capacitor generally has a large variation rate (about ± 10 to 15%) due to its temperature characteristics, and the dielectric loss is high (about 0.9 to 1.5%) and can not meet the use requirements. Therefore, it is very important to develop a preparation technology of a ceramic dielectric capacitor dielectric material with higher electric strength, low dielectric loss, low capacity temperature change rate and high reliability, and to realize industrialization.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an environment-friendly ceramic dielectric material with low dielectric loss, wherein the dielectric constant is 3300-3700, and the ceramic dielectric material has the advantages of lower capacity-temperature change rate, lower dielectric loss, higher electric strength resistance, high reliability and environmental protection. The material meets the market demands of requiring product environmental protection and high quality, especially the demands of intelligent power grid construction and continuous development of automobile electronic industry, and ensures the reliable operation of subsequent products in the application field.
The invention also provides a preparation method of the environment-friendly low-dielectric-loss ceramic dielectric material, which does not introduce lead element and has the advantages of energy conservation and environment protection.
In the present invention, the main component has the chemical formula of (1-y) Ba1-xMgxTiO3-y Y2Ti2O7Wherein x is 0.005 to 0.01Y is 0.01 to 0.05; preferably, x is 0.006 ~ 0.009, and y is 0.02 ~ 0.04.
The modified dopant is selected from Bi2SnZrO7 and Bi2Ti2O7、CeO2、ZrO2、Al2O3、SiO2、Er2O3、Nb2O5、MnCO3Or five or more of CuO. Preferably selected from Bi2SnZrO7, Bi2Ti2O7、CeO2、ZrO2、Er2O3、Nb2O5Or MnCO3Five or more than five. More preferably, it is selected from Bi2SnZrO7, Bi2Ti2O7、CeO2、Er2O3、Nb2O5Or MnCO3Five or more of them, wherein Bi2SnZrO7 and Bi2Ti2O7Is a must.
The modified silicon-based alloy comprises, by weight, 84-96% of a main component and 4-16% of a modified dopant. Preferably, the main component accounts for 86-93% of the total weight, and the modifying doping agent accounts for 7-14% of the total weight, and more preferably, the main component accounts for 88-91% of the total weight, and the modifying doping agent accounts for 9-12% of the total weight.
The modified dopant is Bi composed of the following components in percentage by weight relative to the ceramic dielectric material2SnZrO7 2～7％、Bi2Ti2O7 1～4％、CeO2 0.15～0.5％、ZrO2 0.1～1.0％、Al2O3 0～0.4％、SiO2 0～0.4％、Er2O3 0.1～0.9％、Nb2O5 0.5～1.25％、MnCO30.15-0.35% of CuO and 0-0.2% of CuO. Preferably, the modified dopant is Bi composed of the following components in percentage by weight relative to the ceramic dielectric material2SnZrO7 3～6％、Bi2Ti2O7 2～4％、CeO2 0.2～0.4％、ZrO2 0.3～0.5％、Al2O3 0.1～0.3％、SiO2 0.1～0.35％、Er2O3 0.4～0.8％、Nb2O5 1～1.25％、MnCO30.2 to 0.3% of CuO, and 0.1 to 0.2% of CuO. More preferably, the modified dopant is Bi composed of the following components in percentage by weight relative to the ceramic dielectric material2SnZrO7 4～5％、Bi2Ti2O7 3～4％、CeO2 0.3～0.4％、ZrO2 0.3～0.4％、Al2O3 0.1～0.2％、SiO2 0.2～0.3％、Er2O3 0.5～0.7％、Nb2O5 1.1～1.2％、MnCO3 0.2～0.3％、CuO 0.1～0.2％。
In the preparation method of the environment-friendly ceramic dielectric material with low dielectric loss, (1-y) Ba1-xMgxTiO3-y Y2Ti2O7Can be prepared by weighing BaCO according to the stoichiometric ratio3、MgO、Y2O3、TiO2As raw materials, the weighed raw materials are put into a ball milling tank, deionized water is added for grinding for 8-12 hours, and after discharging, drying and crushing, the raw materials are calcined for 3-5 hours at 1250-1350 ℃ to synthesize (1-y) Ba1-xMgxTiO3-y Y2Ti2O7And (7) baking. Wherein the calcination temperature is preferably 1280-1320 ℃, and more preferably 1300 ℃.
Bi used as raw material2SnZrO7And Bi2Ti2O7Can be purchased commercially or made by oneself, and Bi is prepared during the preparation2SnZrO7Obtained by weighing Bi in stoichiometric proportion2O3、SnO2、ZrO2As raw materials, the weighed raw materials are put into a ball milling tank, deionized water is added for grinding for 3-5 hours, and the raw materials are discharged, dried, crushed and calcined at 1050-1150 ℃ for 2-4 hours to synthesize Bi2SnZrO7. Wherein the calcination temperature is preferably 1080-1120 ℃, and more preferably 1000 ℃.
Bi2Ti2O7Obtained by weighing Bi in stoichiometric proportion2O3、TiO2As raw materials, the weighed raw materials are put into a ball milling tank, and deionized water is addedGrinding for 3-5 hours, discharging, drying, crushing, calcining at 950-1150 ℃ for 2-3 hours, and synthesizing Bi2Ti2O7. Wherein the calcination temperature is preferably 980-1120 ℃, and more preferably 1000 ℃.
In the present invention, (1-y) Ba obtained in step A1-xMgxTiO3-y Y2Ti2O7The baked lump was used as the main component, and Bi was weighed again2SnZrO7、Bi2Ti2O7、CeO2、ZrO2、Al2O3、SiO2、Er2O3、Nb2O5、MnCO3Or any five or more than five components in CuO are used as a modified doping agent, the weighed materials are put into a ball milling tank, deionized water is added for grinding, and then polyvinyl alcohol solution is added as an adhesive for drying and granulation, so that the environment-friendly low-dielectric-loss ceramic dielectric material is obtained. Furthermore, the ceramic substrate can be obtained by sintering the ceramic dielectric material with environmental protection and low dielectric loss, wherein the sintering temperature of the material is 1330-1390 ℃, the calcination time is 2.5-4.5 hours, and the preferred sintering temperature is 1350-1370 ℃.
The specific scheme is as follows:
an environment-friendly ceramic dielectric material with low dielectric loss, which consists of a main component and a modified dopant, wherein,
the chemical formula of the main component is (1-y) Ba1-xMgxTiO3-y Y2Ti2O7Wherein x is 0.005-0.01, and y is 0.01-0.05;
the modifying dopant is selected from Bi2SnZrO7、Bi2Ti2O7、CeO2、ZrO2、Al2O3、SiO2、Er2O3、Nb2O5、MnCO3And CuO, or five or more thereof.
Furthermore, the main component accounts for 84-96% of the total weight, and the modified doping agent accounts for 4-16% of the total weight.
Further, the main component is selected from 0.98Ba0.99Mg0.01TiO3-0.02 Y2Ti2O7、0.97Ba0.99Mg0.01TiO3-0.03 Y2Ti2O7、0.96Ba0.99Mg0.01TiO3-0.04 Y2Ti2O7、0.98Ba0.991Mg0.009TiO3-0.02 Y2Ti2O7、0.97Ba0.991Mg0.009TiO3-0.03 Y2Ti2O7、0.96Ba0.991Mg0.009TiO3-0.04 Y2Ti2O7、0.98Ba0.992Mg0.008TiO3-0.02 Y2Ti2O7、0.97Ba0.992Mg0.008TiO3-0.03 Y2Ti2O7、0.96Ba0.992Mg0.008TiO3-0.04 Y2Ti2O7、0.98Ba0.993Mg0.007TiO3-0.02 Y2Ti2O7、0.97Ba0.993Mg0.007TiO3-0.03 Y2Ti2O7Or 0.96Ba0.993Mg0.007TiO3-0.04 Y2Ti2O7One or more of them.
Further, the modified dopant is selected from Bi2SnZrO7、Bi2Ti2O7、CeO2、ZrO2、Er2O3、Nb2O5Or MnCO3Five or more than five.
Further, the modified dopant comprises Bi and the ceramic dielectric material is prepared from the following components in percentage by weight2SnZrO7 2～7％、Bi2Ti2O7 1～4％、CeO2 0.15～0.5％、ZrO2 0.1～1.0％、Al2O3 0～0.4％、SiO2 0～0.4％、Er2O3 0.1～0.9％、Nb2O5 0.5～1.25％、MnCO3 0.15～0.35％、CuO 0～0.2％。
Further, the modified dopant comprises Bi and the ceramic dielectric material is prepared from the following components in percentage by weight2SnZrO7 3～6％、Bi2Ti2O7 2～4％、CeO2 0.2～0.4％、ZrO2 0.3～0.5％、Al2O3 0.1～0.3％、SiO2 0.1～0.35％、Er2O3 0.4～0.8％、Nb2O5 1～1.25％、MnCO3 0.2～0.3％、CuO 0.1～0.2％。
The invention also provides a preparation method of the environment-friendly low-dielectric-loss ceramic dielectric material, which is characterized by comprising the following steps of: the method comprises the following steps:
A. according to the formula (1-y) Ba1-xMgxTiO3-y Y2Ti2O7Stoichiometric weighing of BaCO3、MgO、Y2O3、TiO2As raw materials, the weighed raw materials are put into a ball milling tank, deionized water is added for grinding for 8-12 hours, and after discharging, drying and crushing, the raw materials are calcined for 3-5 hours at 1250-1350 ℃ to synthesize (1-y) Ba1-xMgxTiO3-y Y2Ti2O7Baking blocks;
B. obtaining Bi2SnZrO7；
C. Obtaining Bi2Ti2O7；
D. (1-y) Ba obtained in step A1-xMgxTiO3-y Y2Ti2O7The baked lump was used as the main component, and Bi was weighed again2SnZrO7、Bi2Ti2O7、CeO2、ZrO2、Al2O3、SiO2、Er2O3、Nb2O5、MnCO3Or any five or more than five components in CuO are used as modified doping agent, the weighed materials are put into a ball milling tank, deionized water is added for grinding, and polyvinyl alcohol solution is added as adhesive for drying to manufacture the CuO modified doping agentAnd (4) obtaining the environment-friendly low-dielectric-loss ceramic dielectric material.
Further, Bi in step B2SnZrO7Obtained by weighing Bi in stoichiometric proportion2O3、SnO2、ZrO2As raw materials, the weighed raw materials are put into a ball milling tank, deionized water is added for grinding for 3-5 hours, and the raw materials are discharged, dried, crushed and calcined at 1050-1150 ℃ for 2-4 hours to synthesize Bi2SnZrO7；
In step C, Bi2Ti2O7Obtained by weighing Bi in stoichiometric proportion2O3、TiO2As raw materials, the weighed raw materials are put into a ball milling tank, deionized water is added for grinding for 3-5 hours, and the raw materials are discharged, dried, crushed and calcined at 950-1150 ℃ for 2-3 hours to synthesize Bi2Ti2O7。
The invention also protects a ceramic substrate, wherein the ceramic substrate is obtained by sintering the environment-friendly low-dielectric-loss ceramic dielectric material at a high temperature of 1330-1390 ℃ for 2.5-4.5 hours.
The invention also protects a ceramic electric element comprising the ceramic substrate.
Has the advantages that:
the ceramic dielectric capacitor dielectric material adopts a solid-phase reaction synthesis technology, has good reproducibility, meets the environmental protection requirement, and is prepared by adjusting (1-y) Ba1-xMgxTiO3-y Y2Ti2O7In which x and y are the same as Bi2SnZrO7、Bi2Ti2O7、CeO2、ZrO2、Al2O3、SiO2、Er2O3、Nb2O5、MnCO3Or the content of the CuO modified dopant is changed, the dielectric constant of the ceramic dielectric material can be continuously adjusted between 3300-3700, the ceramic dielectric material can meet the manufacturing requirements of ceramic dielectric capacitors with different specifications in a certain range, has higher electric strength resistance and proper dielectric constant, has lower capacity temperature change rate, and can be used forThe dielectric material has the characteristics of high reliability and environmental protection, and is a ceramic dielectric capacitor dielectric material with excellent performance.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available. In the following examples, "%" means weight percent, unless otherwise specified.
Example 1
The ceramic dielectric material is prepared by the following steps:
A. according to the formula 0.98Ba0.99Mg0.01TiO3-0.02Y2Ti2O7Stoichiometric ratio of (B) weighing electronic grade BaCO3、MgO、Y2O3、TiO2As raw materials, the weighed raw materials are put into a ball milling tank, a proper amount of deionized water and zirconia balls are added for grinding for 10 hours, and the mixture is calcined for 4 hours at 1300 ℃ after being discharged, dried and crushed to synthesize 0.98Ba0.99Mg0.01TiO3-0.02Y2Ti2O7(BT for short) baking;
B. according to the structural formula Bi2SnZrO7Stoichiometric ratio of (B) to (B) of electronic grade Bi2O3、SnO2、ZrO2As raw materials, the weighed raw materials are put into a ball milling tank, a proper amount of deionized water and zirconia balls are added for grinding for 4 hours, and the materials are calcined for 3 hours at 1100 ℃ after being discharged, dried and crushed to synthesize Bi2SnZrO7Baking (BSZ baking for short);
C. according to the structural formula Bi2Ti2O7Stoichiometric ratio of (B) to (B) of electronic grade Bi2O3、TiO2As raw materials, the weighed raw materials are put into a ball milling tank, and a proper amount of deionized water and oxygen are addedGrinding zirconium balls for 4 hours, discharging, drying, crushing, calcining at 1000 ℃ for 3 hours to synthesize Bi2Ti2O7Firing block (BIT for short);
D. according to the formula 0.98Ba0.99Mg0.01TiO3-0.02Y2Ti2O7The baked lump was used as the main component, and Bi was weighed again2SnZrO7、Bi2Ti2O7、CeO2、ZrO2、Al2O3、SiO2、Er2O3、Nb2O5、MnCO3Or CuO as a modifying doping agent, the total amount is 100 percent, and the dosage of each raw material is shown in the table 1. Putting the weighed materials into a ball milling tank, adding a proper amount of deionized water and zirconia balls for grinding into slurry, then adding the slurry into an ultrafine sand mill for grinding, adding a polyvinyl alcohol solution as an adhesive for drying and granulating to obtain the ceramic dielectric material, performing dry pressing and sintering on the material, wherein the sintering process is that the temperature is increased to 1350 ℃ for 8 hours, preserving the heat for 3 hours to obtain a ceramic substrate, brushing silver paste on the fired ceramic substrate, firing at 810 ℃ for 15 minutes to obtain a silver electrode, and testing various electrical properties, wherein the test results are shown in Table 2.
Examples 2 to 12
The materials were prepared according to the methods in the examples, the amounts of the respective substances are shown in Table 1, and the test results are shown in Table 2.
Table 1: ceramic capacitor dielectric material composition meter
Figure BDA0002795671210000081
Table 2: ceramic capacitor dielectric material performance table
Figure BDA0002795671210000082
Figure BDA0002795671210000091
As can be seen from Table 2, the dielectric constant of the prepared ceramic dielectric material is 3300-3700 adjustable, the dielectric loss is less than or equal to 0.5%, and the dielectric strength is greater than or equal to 6KVAcThe temperature characteristic change rate is less than or equal to +/-5% (-55-125 ℃), and the ceramic dielectric capacitor is suitable for manufacturing environment-friendly ceramic capacitors with excellent temperature characteristics.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims (10)

1. An environment-friendly low-dielectric-loss ceramic dielectric material is characterized in that: the environment-friendly ceramic dielectric material with low dielectric loss consists of a main component and a modified dopant, wherein,
the chemical formula of the main component is (1-y) Ba1-xMgxTiO3-y Y2Ti2O7Wherein x is 0.005-0.01, and y is 0.01-0.05;
the modifying dopant is selected from Bi2SnZrO7、Bi2Ti2O7、CeO2、ZrO2、Al2O3、SiO2、Er2O3、Nb2O5、MnCO3And CuO, or five or more thereof.
2. The environmentally friendly low dielectric loss ceramic dielectric material of claim 1, wherein: the main component accounts for 84-96% of the total weight, and the modified dopant accounts for 4-16% of the total weight.
3. The environmentally friendly low dielectric loss ceramic dielectric material of claim 1, wherein: the main component is selected from 0.98Ba0.99Mg0.01TiO3-0.02Y2Ti2O7、0.97Ba0.99Mg0.01TiO3-0.03Y2Ti2O7、0.96Ba0.99Mg0.01TiO3-0.04Y2Ti2O7、0.98Ba0.991Mg0.009TiO3-0.02Y2Ti2O7、0.97Ba0.991Mg0.009TiO3-0.03Y2Ti2O7、0.96Ba0.991Mg0.009TiO3-0.04Y2Ti2O7、0.98Ba0.992Mg0.008TiO3-0.02Y2Ti2O7、0.97Ba0.992Mg0.008TiO3-0.03Y2Ti2O7、0.96Ba0.992Mg0.008TiO3-0.04Y2Ti2O7、0.98Ba0.993Mg0.007TiO3-0.02Y2Ti2O7、0.97Ba0.993Mg0.007TiO3-0.03Y2Ti2O7Or 0.96Ba0.993Mg0.007TiO3-0.04Y2Ti2O7One or more of them.
4. The environmentally friendly low dielectric loss ceramic dielectric material of any one of claims 1-3, wherein: the modified dopant is selected from Bi2SnZrO7 and Bi2Ti2O7、CeO2、ZrO2、Er2O3、Nb2O5Or MnCO3Five or more than five.
5. According to claim 1-3, wherein the ceramic dielectric material with environmental protection and low dielectric loss is characterized in that: the modified dopant is Bi composed of the following components in percentage by weight relative to the ceramic dielectric material2SnZrO7 2～7％、Bi2Ti2O7 1～4％、CeO2 0.15～0.5％、ZrO2 0.1～1.0％、Al2O30～0.4％、SiO2 0～0.4％、Er2O3 0.1～0.9％、Nb2O5 0.5～1.25％、MnCO30.15～0.35％、CuO 0～0.2％。
6. The environmentally friendly low dielectric loss ceramic dielectric material of claim 5, wherein: the modified dopant is Bi composed of the following components in percentage by weight relative to the ceramic dielectric material2SnZrO73～6％、Bi2Ti2O7 2～4％、CeO2 0.2～0.4％、ZrO2 0.3～0.5％、Al2O3 0.1～0.3％、SiO20.1～0.35％、Er2O3 0.4～0.8％、Nb2O51～1.25％、MnCO3 0.2～0.3％、CuO 0.1～0.2％。
7. A method for preparing the environment-friendly low-dielectric-loss ceramic dielectric material as defined in any one of claims 1 to 6, wherein: the method comprises the following steps:
A. according to the formula (1-y) Ba1-xMgxTiO3-y Y2Ti2O7The method comprises the following steps of weighing BaCO3, MgO, Y2O3 and TiO2 as raw materials according to the stoichiometric ratio, filling the weighed raw materials into a ball milling tank, adding deionized water to grind for 8-12 hours, discharging, drying, crushing, calcining at 1250-1350 ℃ for 3-5 hours, and synthesizing (1-Y) Ba1-xMgxTiO3-y Y2Ti2O7Baking blocks;
B. obtaining Bi2SnZrO7；
C. Obtaining Bi2Ti2O7；
D. (1-y) Ba obtained in step A1-xMgxTiO3-y Y2Ti2O7The baked lump was used as the main component, and Bi was weighed again2SnZrO7、Bi2Ti2O7、CeO2、ZrO2、Al2O3、SiO2、Er2O3、Nb2O5、MnCO3Or any five or more than five components in CuO are used as a modified doping agent, the weighed materials are put into a ball milling tank, deionized water is added for grinding, and then polyvinyl alcohol solution is added for drying and granulation, so that the environment-friendly low-dielectric-loss ceramic dielectric material is obtained.
8. The method for preparing the environment-friendly ceramic dielectric material with low dielectric loss according to claim 7, wherein the method comprises the following steps: in step B Bi2SnZrO7Obtained by weighing Bi in stoichiometric proportion2O3、SnO2、ZrO2As raw materials, the weighed raw materials are put into a ball milling tank, deionized water is added for grinding for 3-5 hours, and the raw materials are discharged, dried, crushed and calcined at 1050-1150 ℃ for 2-4 hours to synthesize Bi2SnZrO7；
In step C, Bi2Ti2O7Obtained by weighing Bi in stoichiometric proportion2O3、TiO2As raw materials, the weighed raw materials are put into a ball milling tank, deionized water is added for grinding for 3-5 hours, and the raw materials are discharged, dried, crushed and calcined at 950-1150 ℃ for 2-3 hours to synthesize Bi2Ti2O7。
9. A ceramic substrate, characterized by: the ceramic substrate is obtained by sintering the environment-friendly ceramic dielectric material with low dielectric loss according to any one of claims 1 to 6 or the environment-friendly ceramic dielectric material with low dielectric loss prepared by the preparation method according to claim 7 or 8 at a high temperature of 1330-1390 ℃ for 2.5-4.5 hours.
10. A ceramic electrical component comprising the ceramic substrate of claim 9.
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