CN114907112B - Low-temperature-coefficient high-dielectric low-loss microwave electronic ceramic material and preparation method thereof - Google Patents

Low-temperature-coefficient high-dielectric low-loss microwave electronic ceramic material and preparation method thereof Download PDF

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CN114907112B
CN114907112B CN202210343512.2A CN202210343512A CN114907112B CN 114907112 B CN114907112 B CN 114907112B CN 202210343512 A CN202210343512 A CN 202210343512A CN 114907112 B CN114907112 B CN 114907112B
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CN114907112A (en
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杨勤
陈建杰
张华峰
赵春美
朱家辉
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CETC 9 Research Institute
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Abstract

The invention discloses a microwave electronic ceramic material with low temperature coefficient, high dielectric constant and low loss, which belongs to the technical field of materials and comprises the following chemical components: 34-36 wt% TiO 2 32 to 35.5 weight percent of Bi 2 O 3 18 to 20 weight percent of Nd 2 O 3 8.5 to 9 weight percent of CaO and 1.8 to 2.2 weight percent of Li 2 O, 0.1-0.13 wt% of Na 2 O, 0.05 to 0.08 weight percent of SiO 2 0.05 to 0.08 weight percent of Nb 2 O 5 ZrO 0.05-0.08 wt% 2 0.05 to 0.09 weight percent of MgO and 0.03 to 0.05 weight percent of Fe 2 O 3 0.01 to 0.02wt% of MoO 3 0.008 to 0.015% of BaO, 100% in total; the ceramic substrate material prepared by the invention: dielectric constant 180-200 @1MHz, dielectric loss 0.17% -0.25% @1MHz, insulation resistance 10 5 MΩ, compressive strength E being greater than or equal to 5 x 10 6 V/mm, Q value @1GHz is 1400-1500, and resonant frequency temperature coefficient τf is-25- +30 ppm/. Degree.C.

Description

Low-temperature-coefficient high-dielectric low-loss microwave electronic ceramic material and preparation method thereof
Technical Field
The invention relates to the technical field of materials, in particular to a low-temperature coefficient high-dielectric low-loss microwave electronic ceramic material and a preparation method thereof.
Background
Along with the rapid development of the communication industry, the demands for high-reliability chip capacitors with stable content values and high Q values in a large temperature variation range are increasing, the applicable temperature demands are in the range of-55 to +130 ℃, the size demands for the capacitors are smaller and smaller, and meanwhile, certain thickness of the chip capacitors is required to be ensured so as to reduce the manufacturing cost of the chip capacitors and ensure the reliability of the capacitors. The capacitance capacity of the chip can be improved and the volume of the capacitor can be reduced by improving the dielectric constant of the microwave dielectric material. Commercial high dielectric ceramic materials (+ -30 ppm) have dielectric constants of about 130, but the dielectric constants of the ceramic materials are not disclosed. The analysis of the related literature shows that the high dielectric materials of the current porcelain mainly comprise barium lanthanum titanium series and barium neodymium titanium series, and reference can be made to the preparation of barium lanthanum titanium series ceramic powder for multilayer ceramic capacitors, but the dielectric constant of the corresponding materials is about 85; meanwhile, new material systems, such as the perovskite high-dielectric ceramics mentioned in the 201911261807. X patent, are being developed at home, but the temperature coefficient of the ceramics is poor.
Under the demand of increasingly miniaturized chip capacitors, miniaturization can be realized only by thinning the thickness of the chip capacitors by means of the current ceramic materials, which brings adverse effects to the cost and reliability of the capacitors, and the improvement of the dielectric constants of the ceramic materials is a technical problem to be solved in the field.
Disclosure of Invention
One of the objectives of the present invention is to provide a microwave electronic ceramic material with low temperature coefficient, high dielectric constant and low loss, so as to solve the above problems.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: a microwave electronic ceramic material with low temperature coefficient, high dielectric constant and low loss comprises the following chemical components: 34-36 wt% TiO 2 32 to 35.5 weight percent of Bi 2 O 3 18 to 20 weight percent of Nd 2 O 3 8.5 to 9 weight percent of CaO and 1.8 to 2.2 weight percent of Li 2 O, 0.1-0.13 wt% of Na 2 O, 0.05 to 0.08 weight percent of SiO 2 0.05 to 0.08 weight percent of Nb 2 O 5 ZrO 0.05-0.08 wt% 2 0.05 to 0.09 weight percent of MgO and 0.03 to 0.05 weight percent of Fe 2 O 3 0.01 to 0.02wt% of MoO 3 0.008-0.015% of BaO, and the sum of the percentages of the components is 100%.
The invention provides a bismuth neodymium titanium-based ceramic substrate material, which realizes the improvement of the dielectric constant of the material through ion regulation and composition, and simultaneously maintains the corresponding temperature stability through material secondary firing and annealing.
As a preferable technical scheme, the chemical composition of the material comprises the following components in percentage by weight: tiO (titanium dioxide) 2 35.4%，Bi 2 O 3 33.1%，Nd 2 O 3 19.9%，CaO 9%，Li 2 O 2.1%，Na 2 O 0.128%，SiO 2 0.075%，Nb 2 O 5 0.075%，ZrO 2 0.071%，MgO 0.081%，Fe 2 O 3 0.046%，MoO 3 0.012% of BaO 0.012%. By adopting the proportion, the comprehensive performance can be optimized.
The second purpose of the invention is to provide a preparation method of the microwave electronic ceramic material with low temperature coefficient, high dielectric constant and low loss, which adopts the technical scheme that the microwave electronic ceramic material is prepared by mixing, ball milling, drying, mechanical forming, presintering, crushing, fine grinding, isostatic pressing, sintering and annealing chemically pure raw materials according to the proportion.
As a preferable technical scheme: during ball milling, TZP zirconium balls with the granularity of 0.2-1.0 mm are adopted for grinding, and the grinding time is 12-16 h.
As a preferable technical scheme: and in the presintering process, presintering is carried out at 1200-1300 ℃ in an inert gas environment.
As a preferable technical scheme: the annealing is performed in an oxygen environment for 4-6 h.
Compared with the prior art, the invention has the advantages that: the index performance of the ceramic substrate material prepared by the invention is as follows: dielectric constant 195@1MHz, dielectric loss within the range of 0.17% -0.25% @1MHz, insulation resistance 10 5 MΩ, compressive strength E being greater than or equal to 5 x 10 6 V/mm, Q value @1GHz is 1400-1500, and resonant frequency temperature coefficient τf is-25- +30 ppm/DEG C; the chip capacitor prepared by the ceramic substrate has the capacitance size of 1.5mm 0.9mm 0.22mm, the capacitance capacity of 12pF@1MHz, the dissipation factor DF value of 180-200@1MHz, the withstand voltage of more than 125V, and the performance stability in an environment of minus 40 to +125 ℃, can be suitable for the chip capacitor required by the Sub-6 frequency band in the 5G communication field, can realize the high dielectric constant ceramic for the chip capacitor with the temperature coefficient of minus 25 to +30 ppm/DEGC, and can be applied to the miniaturized manufacture of the chip capacitor for communication.
Detailed Description
The invention will be further illustrated with reference to examples.
Example 1:
a microwave electronic ceramic material with low temperature coefficient, high dielectric constant and low loss comprises the following chemical components: tiO (titanium dioxide) 2 35.4%，Bi 2 O 3 33.1%，Nd 2 O 3 19.9%，CaO 9%，Li 2 O 2.1%，Na 2 O 0.128%，SiO 2 0.075%，Nb 2 O 5 0.075%，ZrO 2 0.071%，MgO 0.081%，Fe 2 O 3 0.046%，MoO 3 0.012% of BaO 0.012%. Adding chemically pure raw materials into deionized water according to a formula to mix; grinding by adopting TZP zirconium balls with the granularity of 0.5mm, drying after grinding for 15 hours, and then mechanically forming; pre-sintering at 1260 ℃ in helium environment; crushing by a crusher, and finely grinding by adopting TZP zirconium balls with the diameter of 0.1 mm; carrying out isostatic compaction after fine grinding, and sintering in the furnace chamber atmosphere with air, wherein the sintering temperature is 1200 ℃; annealing for 5 hours in an oxygen environment after sintering is completed, wherein the annealing temperature is 1120 ℃;
the index performance of the prepared ceramic substrate material is as follows: dielectric constant 195@1MHz, dielectric loss 0.17% @1MHz, insulation resistance 10 5 MΩ, compressive strength E being greater than or equal to 5 x 10 6 V/mm, Q value @1GHz is 1496, and resonant frequency temperature coefficient τf is +25ppm/°C; the chip capacitor with the size of 1.5mm 0.9mm 0.22mm manufactured by adopting the ceramic substrate manufactured in the embodiment 1 has the capacitance capacity of 12pF@1MHz, the dissipation factor DF value of 180-200@1MHz and the withstand voltage of more than 125V, and is used for stabilizing the performance in the environment of minus 40 to +125 ℃.
Example 2:
a microwave electronic ceramic material with low temperature coefficient, high dielectric constant and low loss comprises the following chemical components: tiO (titanium dioxide) 2 36%，Bi 2 O 3 32.4%，Nd 2 O 3 20%，CaO 8.9%，Li 2 O 2.2%，Na 2 O 0.121%，SiO 2 0.08%，Nb 2 O 5 0.08%，ZrO 2 0.071%，MgO 0.07%，Fe 2 O 3 0.043%，MoO 3 0.02% of BaO 0.015%. Adding chemically pure raw materials into deionized water according to a formula to mix; grinding by adopting TZP zirconium balls with the granularity of 0.5mm, drying after grinding for 15 hours, and then mechanically forming; pre-sintering at 1300 ℃ in helium environment; crushing by a crusher, and finely grinding by adopting TZP zirconium balls with the diameter of 0.1 mm; carrying out isostatic compaction after fine grinding, and sintering in the furnace chamber atmosphere with air, wherein the sintering temperature is 1250 ℃; annealing for 5 hours in an oxygen environment after sintering is completed, wherein the annealing temperature is 1150 ℃;
the index performance of the prepared ceramic substrate material is as follows: dielectric constant 200@1MHz, dielectric loss 0.2% @1MHz, insulation resistance 10 5 M omega resistanceThe compressive strength E is more than or equal to 5 x 10 6 V/mm, Q value @1GHz is 1400, and resonant frequency temperature coefficient τf is +30ppm/. Degree.C; the chip capacitor with the size of 1.8mm and 0.9mm and 0.2mm manufactured by adopting the ceramic substrate manufactured in the embodiment 2 has the capacitance of 14.3pF@1MHz, the dissipation factor DF value of 200-230@1MHz, the withstand voltage of more than 125V, and stable performance in the environment of minus 40-125 ℃ but larger loss than that of the embodiment 1.
Example 3:
a microwave electronic ceramic material with low temperature coefficient, high dielectric constant and low loss comprises the following chemical components: tiO (titanium dioxide) 2 4.5%，Bi 2 O 3 35.2%，Nd 2 O 3 19.28%，CaO 8.6%，Li 2 O 1.9%，Na 2 O 0.12%，SiO 2 0.08%，Nb 2 O 5 0.067%，ZrO 2 0.08%，MgO 0.09%，Fe 2 O 3 0.05%，MoO 3 0.018%, baO 0.015%. Adding chemically pure raw materials into deionized water according to a formula to mix; grinding by adopting TZP zirconium balls with the granularity of 0.5mm, drying after grinding for 15 hours, and then mechanically forming; pre-sintering at 1260 ℃ in helium environment; crushing by a crusher, and finely grinding by adopting TZP zirconium balls with the diameter of 0.1 mm; carrying out isostatic compaction after fine grinding, and sintering in the air in the furnace chamber atmosphere at the sintering temperature of 1220 ℃; annealing for 5 hours in an oxygen environment after sintering is completed, wherein the annealing temperature is 1100 ℃;
the index performance of the prepared ceramic substrate material is as follows: dielectric constant 185@1MHz, dielectric loss 0.16% @1MHz, insulation resistance 10 5 MΩ, compressive strength E being greater than or equal to 5 x 10 6 V/mm, Q value @1GHz is 1500, and resonant frequency temperature coefficient τf is +22 ppm/. Degree.C; the capacitance obtained by adopting the chip capacitor with the size of 1.5mm 0.9mm 0.22mm manufactured by the ceramic substrate manufactured in the embodiment 1 is 11pF@1MHz, the dissipation factor DF value is 180-190@1MHz, the withstand voltage is larger than 125V, and the ceramic substrate is stable in performance in an environment of minus 40 ℃ to +125 ℃, but the dielectric constant is slightly lower than that of the embodiment 1, and the manufactured capacitance is smaller.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.

Claims (6)

1. The microwave electronic ceramic material with low temperature coefficient, high dielectric constant and low loss is characterized by comprising the following chemical components: 34-36 wt% TiO 2 32 to 35.5 weight percent of Bi 2 O 3 18 to 20 weight percent of Nd 2 O 3 8.5 to 9 weight percent of CaO and 1.8 to 2.2 weight percent of Li 2 O, 0.1-0.13 wt% of Na 2 O, 0.05 to 0.08 weight percent of SiO 2 0.05 to 0.08 weight percent of Nb 2 O 5 ZrO 0.05-0.08 wt% 2 0.05 to 0.09 weight percent of MgO and 0.03 to 0.05 weight percent of Fe 2 O 3 0.01 to 0.02wt% of MoO 3 0.008-0.015% of BaO, and the sum of the percentages of the components is 100%.
2. The low temperature coefficient high dielectric low loss microwave electronic ceramic material according to claim 1, wherein the chemical composition comprises the following components in percentage by weight: tiO (titanium dioxide) 2 35.4%，Bi 2 O 3 33.1%，Nd 2 O 3 19.9%，CaO 9%，Li 2 O 2.1%，Na 2 O 0.128%，SiO 2 0.075%，Nb 2 O 5 0.075%，ZrO 2 0.071%，MgO 0.081%，Fe 2 O 3 0.046%，MoO 3 0.012%，BaO 0.012%。
3. The method for preparing the low-temperature coefficient high-dielectric low-loss microwave electronic ceramic material according to claim 1 or 2, which is characterized in that the chemically pure raw materials are mixed, ball-milled, dried, mechanically molded, presintered, crushed, finely ground, isostatically molded, sintered and annealed according to the proportion to obtain the microwave electronic ceramic material.
4. A method according to claim 3, characterized in that: during ball milling, TZP zirconium balls with the granularity of 0.2-1.0 mm are adopted for grinding, and the grinding time is 12-16 h.
5. A method according to claim 3, characterized in that: and in the presintering process, presintering is carried out at 1200-1300 ℃ in an inert gas environment.
6. A method according to claim 3, characterized in that: the annealing is performed for 4-6 hours in an oxygen environment at 1000-1200 ℃.
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