CN110156457B - Low-temperature co-fired ceramic dielectric material and preparation method thereof - Google Patents
Low-temperature co-fired ceramic dielectric material and preparation method thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 45
- 239000003989 dielectric material Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 35
- 239000011521 glass Substances 0.000 claims abstract description 34
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 19
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 17
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 17
- 238000000498 ball milling Methods 0.000 claims abstract description 17
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Inorganic materials [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000011230 binding agent Substances 0.000 claims abstract description 4
- 239000000463 material Substances 0.000 claims abstract description 4
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- 238000000227 grinding Methods 0.000 claims description 6
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
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- 238000002156 mixing Methods 0.000 abstract description 15
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- 238000001035 drying Methods 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 6
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- 238000011161 development Methods 0.000 description 4
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- 229910052808 lithium carbonate Inorganic materials 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
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- 239000007772 electrode material Substances 0.000 description 1
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- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
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- 239000002002 slurry Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a low-temperature co-fired ceramic dielectric material and a preparation method thereof, wherein the material comprises the following raw materials in percentage by mass: 5-20% of glass powder and Ca0.95La0.05Cu2.8Zn0.2Ti4O1280-95 percent. The glass powder comprises the following raw materials in percentage by mass: li2CO35‑40％、ZnO 5‑30％、BaCO35‑30％、CaCO35-30% and kaolin 5-30%. The preparation method comprises the following steps: weighing and mixing the raw materials according to the stoichiometric ratio of the general formula to prepare a frit A; mixing 5-20% of glass powder B and 80-95% of frit A according to the mass percentage, ball-milling, adding a binding agent, granulating, keeping the temperature at 800-. The ceramic dielectric material has low sintering temperature, high dielectric constant and low dielectric loss, and can be co-sintered with a silver metal inner electrode with high conductivity.
Description
Technical Field
The invention discloses a low-temperature co-fired ceramic dielectric material and a preparation method thereof, belonging to the technical field of ceramic dielectric materials.
Background
The low-temperature co-fired ceramic technology is characterized by mixing ceramic powder with a lower sintering temperature with a binder, preparing a compact raw ceramic tape with accurate thickness by a tape casting method, then cutting the raw ceramic tape into raw ceramic chips with required size, manufacturing required circuit patterns on the raw ceramic chips by the processes of mechanical punching or laser punching, slurry filling, screen printing and the like, embedding passive elements such as a capacitor, an inductor, a resistor, a coupler, a filter, an impedance converter and the like in the raw ceramic chips, finally laminating a plurality of the raw ceramic chips together, sintering and forming at about 900 ℃ to prepare passive integrated elements or components, and pasting active devices and the like on the surfaces of the raw ceramic chips to prepare different functional modules, thereby realizing high density and miniaturization of a circuit.
With the rapid development of modern electronic information technology, especially products such as digital cameras, notebook computers, mobile phones and the like in consumer electronic products and communication electronic products have more and more functions, the size is smaller and smaller, the packaging density of circuits is higher and higher, and the demand for circuit miniaturization is stronger and stronger. The low-temperature co-fired ceramic technology can embed various passive elements into a multilayer ceramic substrate and form an integrated ceramic component through sintering, so that the space of the component is effectively reduced, and the miniaturization of the component or a circuit module and the miniaturization of an electronic product are realized. Under the promotion of the low-temperature co-fired ceramic technology industry, the development of ceramic materials capable of being co-fired with metallic silver or copper electrodes has become a leading-edge and hot-spot problem, and a plurality of low-temperature sintered ceramic material patents and literature reports exist. At present, most of the research on low-temperature co-fired ceramic materials is focused on low-dielectric-constant ceramic materials, while the research on medium-and high-dielectric-constant low-temperature co-fired ceramic materials is relatively lagged, and the development requirements of modern electronic information technology are difficult to meet. Therefore, from the aspects of material serialization and electronic component size reduction, research and development of ceramic materials with medium and high dielectric constants capable of being co-sintered with electrode materials such as silver and copper at low temperature are of great significance for promoting the development of modern electronic information technology.
At present, BaO-TiO is a more reported low-temperature co-fired ceramic material2、Ca(Li1/3Nb2/3)O3-δ、Bi2O3-ZnO-Nb2O5/Ta2O5、BaO-Ln2O3-TiO2(Ln ═ Nd, Sm) and Pb1-xCax(Fe1/2，Nb1/2)O3And the like, but these ceramic materials have problems of high sintering temperature, low dielectric constant, high loss, and the like.
Disclosure of Invention
In order to solve the defects in the prior art, the invention discloses a low-temperature co-fired ceramic dielectric material and a preparation method thereof.
The invention is realized by the following technical scheme:
a low-temperature co-fired ceramic dielectric material comprises the following raw materials in percentage by mass: 5-20% of glass powder and Ca0.95La0.05Cu2.8Zn0.2Ti4O1280-95％。
The glass powder comprises the following raw materials in percentage by mass: li2CO35-40％、ZnO 5-30％、BaCO35-30％、CaCO35-30% and kaolin 5-30%.
A preparation method of a low-temperature co-fired ceramic dielectric material comprises the following steps of:
1) raw material CaCO3、La2O3CuO, ZnO and TiO2According to the general formula Ca0.95La0.05Cu2.8Zn0.2Ti4O12The mixture is weighed according to the stoichiometric ratio, and is subjected to ball milling and then passes through 120-hole/cm and 250-hole/cm2Separating and sieving, heating to 1000-1100 ℃, and preserving heat for 2-4 hours to prepare a frit A;
2) 5-40% of Li by mass2CO35-30% of ZnO and 5-30% of BaCO35-30% of CaCO3Melting and cooling the glass powder and 5-30% of kaolin by water, grinding and sieving to obtain glass powder B;
3) performing secondary batching on 5-20% of glass powder B and 80-95% of frit A according to the mass percentage to obtain a batching C;
4) ball milling the ingredient C, passing through 120-250 holes/cm2And (3) separating a sample, sieving, adding an adhesive accounting for 5-8% of the mixture by mass percent, granulating, pressing into a green body, slowly heating to 800-850 ℃, keeping the temperature for 1 hour, and cooling to obtain the ceramic medium.
The ball milling time in the step 1) is 4-6 hours, and the ball milling medium is zirconia balls with the diameter of 1-2 mm.
The heating rate in the step 1) is 5-10 ℃/min.
The temperature rise process in the step 4) is divided into two stages: the first stage, heating from room temperature to 400-500 ℃ at a heating rate of 2-4 ℃/min; in the second stage, heating from 400-500 ℃ to 800-850 ℃ at a heating rate of 5-15 ℃/min.
The adhesive is one of polyvinyl alcohol or paraffin.
Compared with the prior art, the invention has the following beneficial effects:
ca of the invention0.95La0.05Cu2.8Zn0.2Ti4O12The dielectric ceramic has moderate sintering temperature, generally about 1100 ℃, and has higher dielectric constant because the dielectric ceramic belongs to grain boundary layer capacitor structure ceramic. In addition, the ceramic material also has adjustable capacity temperature coefficient and lower loss, and is a dielectric ceramic material with excellent performance. Selection of Ca in the invention0.95La0.05Cu2.8Zn0.2Ti4O12The system adopts a method of adding glass powder as a sintering aid, so that the sintering temperature is lower than 1000 ℃ and the structure of the system is not damaged, thereby achieving the purposes of low-temperature co-firing and excellent performance.
Drawings
The invention is further described below with reference to the accompanying drawings.
Fig. 1 is a graph showing the test results of temperature coefficients TCC of ceramic dielectric materials obtained in example 1, example 2, example 3 and example 4. As can be seen from the figure: as the temperature rises, the temperature coefficient shows a slow rising trend overall and then gradually falls, but the temperature coefficient is within +/-15%, and higher temperature stability is achieved.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the scope of the present invention is not limited to these examples, and all changes or equivalent substitutions that do not depart from the spirit of the present invention are intended to be included within the scope of the present invention.
Example 1
A low-temperature co-fired ceramic dielectric material comprises the following raw materials in percentage by mass: 5% of glass powder and Ca0.95La0.05Cu2.8Zn0.2Ti4O1295 percent, wherein the glass powder comprises the following raw materials in percentage by mass: li2CO35％、ZnO 30％、BaCO 330％、CaCO 330% and kaolin 5%.
The preparation process comprises the following steps:
1) raw material CaCO3、La2O3CuO, ZnO and TiO2According to the general formula Ca0.95La0.05Cu2.8Zn0.2Ti4O12Mixing, ball milling for 6 hours in a ball mill with the rotating speed of 400r/min, drying in a common oven with the temperature of 3.3kw and the temperature of 100 ℃, and then passing through 250 holes/cm2And (4) screening, heating to 1100 ℃ at the speed of 5 ℃/min, and preserving heat at 1100 ℃ for 3 hours to obtain the frit A.
2) Weighing Li2CO35g、ZnO 30g、BaCO330g、CaCO330g and 5g of kaolin, mixing, melting, cooling by water, grinding and sieving to obtain the glass powder B.
3) And (3) carrying out secondary burdening, weighing the frit A and the glass powder B according to the mass ratio of 95% of the frit A to 5% of the glass powder B, and uniformly mixing. Adding deionized water, ball milling for 8 hr in a ball mill at 400r/min, drying at 120 deg.C, and sieving with 250 pores/cm2And (3) separating a sample, sieving, adding 8 wt% of paraffin wax for granulation, pressing into a green body, heating to 450 ℃ according to the heating rate of 2 ℃/min, heating to 850 ℃ according to the heating rate of 10 ℃/min, sintering, keeping the temperature for 1 hour, and cooling to obtain the ceramic medium.
The ceramic dielectric prepared in this example was tested for dielectric properties at a frequency of 1KHz, with the results shown in table 1 and fig. 1.
TABLE 1
| Firing temperature (. degree. C.) | Incubation time (h) | Dielectric constant ε | Loss tan delta | |
| Example 1 | 850 | 1 | 2410 | 0.02 |
Example 2
A low-temperature co-fired ceramic dielectric material comprises the following raw materials in percentage by mass: glass powder 10%, Ca0.95La0.05Cu2.8Zn0.2Ti4O1290%, the glass powder comprises the following raw materials in percentage by mass: li2CO35％、ZnO 5％、BaCO 330％、CaCO 330% and 30% kaolin.
The preparation process comprises the following steps:
1) raw material CaCO3、La2O3CuO, ZnO and TiO2According to the general formula Ca0.95La0.05Cu2.8Zn0.2Ti4O12Mixing, ball milling for 6 hours in a ball mill with the rotating speed of 400r/min, drying in a common oven with the temperature of 3.3kw and the temperature of 100 ℃, and then passing through 250 holes/cm2And (4) screening, heating to 1100 ℃ at the speed of 5 ℃/min, and preserving heat at 1100 ℃ for 2 hours to obtain the frit A.
2) Weighing Li2CO35g、ZnO 5g、BaCO330g、CaCO330g of kaolin and 30g of kaolin, and the glass powder B is prepared by mixing, melting, cooling, grinding and sieving.
3) And (3) carrying out secondary burdening, weighing the frit A and the glass powder B according to the mass ratio of 90% of the frit A to 10% of the glass powder B, and uniformly mixing. Adding deionized water, ball milling for 8 hr in a ball mill at 400r/min, drying at 120 deg.C, and sieving with 250 pores/cm2And (3) separating a sample, sieving, adding 8 wt% of paraffin wax for granulation, pressing into a green body, heating to 450 ℃ according to the heating rate of 2 ℃/min, heating to 840 ℃ according to the heating rate of 15 ℃/min, sintering, keeping the temperature for 1 hour, and cooling to obtain the ceramic medium.
The ceramic dielectric prepared in this example was tested for dielectric properties at a frequency of 1KHz, with the results shown in table 2 and fig. 1.
TABLE 2
| Firing temperature (. degree. C.) | Incubation time (h) | Dielectric constant ε | Loss tan delta | |
| Example 2 | 840 | 1 | 2420 | 0.015 |
Example 3
A low-temperature co-fired ceramic dielectric material comprises the following raw materials in percentage by mass: 15% of glass powder and Ca0.95La0.05Cu2.8Zn0.2Ti4O1285%, wherein the glass powder comprises the following raw materials in percentage by mass: li2CO340％、ZnO 20％、BaCO320％、CaCO 310% and kaolin 10%.
The preparation process comprises the following steps:
1) raw material CaCO3、La2O3CuO, ZnO and TiO2According to the general formula Ca0.95La0.05Cu2.8Zn0.2Ti4O12Mixing, ball milling for 6 hours in a ball mill with the rotating speed of 400r/min, drying in a common oven with the temperature of 3.3kw and the temperature of 100 ℃, and then passing through 250 holes/cm2And (4) screening, heating to 1100 ℃ at the speed of 8 ℃/min, and preserving the temperature for 4 hours at 1100 ℃ to obtain the frit A.
2) Weighing Li2CO340g、ZnO 20g、BaCO320g、CaCO310g of kaolin and 10g of kaolin, mixing, melting, cooling by water, grinding and sieving to obtain the glass powder B.
3) And (3) carrying out secondary burdening, weighing the frit A and the glass powder B according to the mass ratio of 85% of the frit A to 15% of the glass powder B, and uniformly mixing. Adding deionized water, ball milling for 8 hr in a ball mill at 400r/min, drying at 120 deg.C, and sieving with 250 pores/cm2And (3) separating a sample, sieving, adding 8 wt% of paraffin wax for granulation, pressing into a green body, heating to 450 ℃ at the heating rate of 2 ℃/min, heating to 830 ℃ at the heating rate of 5 ℃/min, sintering, keeping the temperature for 1 hour, and cooling to obtain the ceramic medium.
The ceramic dielectric prepared in this example was tested for dielectric properties at a frequency of 1KHz, with the results shown in table 3 and fig. 1.
TABLE 3
| Firing temperature (. degree. C.) | Incubation time (h) | Dielectric constant ε | Loss tan delta | |
| Example 3 | 830 | 1 | 2430 | 0.016 |
Example 4
A low-temperature co-fired ceramic dielectric material comprises the following raw materials in percentage by mass: glass powder 10%, Ca0.95La0.05Cu2.8Zn0.2Ti4O1290%, the glass powder comprises the following raw materials in percentage by mass: li2CO335％、ZnO 10％、BaCO320％、CaCO 315% and kaolin 20%.
The preparation process comprises the following steps:
1) raw material CaCO3、La2O3CuO, ZnO and TiO2According to the general formula Ca0.95La0.05Cu2.8Zn0.2Ti4O12Mixing, ball milling for 6 hours in a ball mill with the rotating speed of 400r/min, drying in a common oven with the temperature of 3.3kw and the temperature of 100 ℃, and then passing through 250 holes/cm2And (4) screening, heating to 1100 ℃ at the speed of 5 ℃/min, and preserving heat at 1100 ℃ for 3 hours to obtain the frit A.
2) Weighing Li2CO335g、ZnO 10g、BaCO320g、CaCO315g of kaolin and 20g of kaolin, mixing, melting, cooling by water, grinding and sieving to obtain the glass powder B.
3) And (3) carrying out secondary burdening, weighing the frit A and the glass powder B according to the mass ratio of 80% of the frit A to 20% of the glass powder B, and uniformly mixing. Adding deionized water, ball milling for 8 hr in a ball mill at 400r/min, drying at 120 deg.C, and sieving with 250 pores/cm2And (3) screening samples, adding 8 wt% of paraffin wax for granulation, pressing into a green body, heating to 500 ℃ at the heating rate of 3 ℃/min, heating to 800 ℃ at the heating rate of 10 ℃/min, sintering, keeping the temperature for 1 hour, and cooling to obtain the ceramic medium.
The ceramic dielectric prepared in this example was tested for dielectric properties at a frequency of 1KHz, with the results shown in table 4 and fig. 1.
TABLE 4
| Firing temperature (. degree. C.) | Incubation time (h) | Dielectric constant ε | Loss tan delta | |
| Example 4 | 800 | 1 | 2400 | 0.019 |
Examples 1-4 measurement of dielectric properties, the test methods and test equipment used were as follows:
a. measurement of dielectric constant ε and loss tan. delta
The capacitance C and the dielectric loss tan delta (test frequency 1KHz) of the capacitor were measured using a HEWLETT PACKARD 4278A capacitance tester, and the dielectric constant ε was calculated by the following equation:
in the formula: c-capacitance of the sample, in pF; d-thickness of the sample piece, unit cm; d-diameter of the sintered D-sample piece in cm.
b. Test of temperature coefficient TCC (-55 ℃ to 150 ℃)
The capacitance temperature coefficient (the testing frequency is 1KHz) of the capacitor is obtained by measuring the capacitance variation of the sample with temperature by using a model 6425 WAYKERR bridge, a GZ-ESPEC MC-710F high-low temperature box and a special tester for the C-T/V characteristic of the HM27002 type capacitor, and the calculation formula is as follows:
in the formula: the reference temperature is 25 ℃, C0At a temperature of 25 ℃ in volume, C1Is a temperature t1The capacity of (c).
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention. The present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (5)
1. The low-temperature co-fired ceramic dielectric material is characterized by comprising the following raw materials in percentage by mass: 5-20% of glass powder and Ca0.95La0.05Cu2.8Zn0.2Ti4O1280-95%, wherein the glass powder comprises the following raw materials in percentage by mass: li2CO35-40％、ZnO 5-30％、BaCO35-30％、CaCO35-30% of kaolin and 5-30% of kaolin, comprising the following steps which are carried out in sequence:
1) raw material CaCO3、La2O3CuO, ZnO and TiO2According to the general formula Ca0.95La0.05Cu2.8Zn0.2Ti4O12The mixture is weighed according to the stoichiometric ratio, and is subjected to ball milling and then passes through 120-hole/cm and 250-hole/cm2Separating the sample, heating to 1000-Heating for 2-4 hours to prepare a frit A;
2) 5-40% of Li by mass2CO35-30% of ZnO and 5-30% of BaCO35-30% of CaCO3Melting and cooling the glass powder and 5-30% of kaolin by water, grinding and sieving to obtain glass powder B;
3) performing secondary batching on 5-20% of glass powder B and 80-95% of frit A according to the mass percentage to obtain a batching C;
4) ball milling the ingredient C, passing through 120-250 holes/cm2And (3) separating a sample, sieving, adding a binder accounting for 5-8% of the mixture by mass percent, granulating, pressing into a green body, slowly heating to 800-850 ℃, preserving heat for 1 hour, and cooling to obtain the ceramic medium.
2. The low-temperature co-fired ceramic dielectric material as claimed in claim 1, wherein the ball milling time in step 1) is 4-6 hours, and the ball milling medium is zirconia balls with a diameter of 1-2 mm.
3. The low temperature co-fired ceramic dielectric material of claim 1, wherein the temperature rise rate in step 1) is 5-10 ℃/min.
4. The low-temperature co-fired ceramic dielectric material as claimed in claim 1, wherein the temperature raising process in the step 4) is divided into two stages: the first stage, heating from room temperature to 400-500 ℃ at a heating rate of 2-4 ℃/min; in the second stage, heating from 400-500 ℃ to 800-850 ℃ at a heating rate of 5-15 ℃/min.
5. The material of claim 1, wherein the binder is one of polyvinyl alcohol or paraffin wax.
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| CN102272064A (en) * | 2008-11-10 | 2011-12-07 | Hoya株式会社 | Method for producing glass, optical glass, glass material for press molding, optical element and methods for producing same |
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