CN114550977B - 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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- CN114550977B CN114550977B CN202210235218.XA CN202210235218A CN114550977B CN 114550977 B CN114550977 B CN 114550977B CN 202210235218 A CN202210235218 A CN 202210235218A CN 114550977 B CN114550977 B CN 114550977B
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- 239000000919 ceramic Substances 0.000 title claims abstract description 38
- 239000003989 dielectric material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002019 doping agent Substances 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims description 41
- 238000000498 ball milling Methods 0.000 claims description 20
- 238000000926 separation method Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 238000012216 screening Methods 0.000 claims description 6
- 239000012188 paraffin wax Substances 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical group O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 4
- 230000001070 adhesive effect Effects 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 2
- 239000011230 binding agent Substances 0.000 claims 1
- 238000005245 sintering Methods 0.000 abstract description 15
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 2
- 238000001035 drying Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 229910010293 ceramic material Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000003990 capacitor Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 238000007873 sieving Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000008054 signal transmission Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/12—Ceramic dielectrics
- H01G4/1209—Ceramic dielectrics characterised by the ceramic dielectric material
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/495—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on vanadium, niobium, tantalum, molybdenum or tungsten oxides or solid solutions thereof with other oxides, e.g. vanadates, niobates, tantalates, molybdates or tungstates
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3224—Rare earth oxide or oxide forming salts thereof, e.g. scandium oxide
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
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- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
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: ca (Ca) 9 Pr(VO4) 7 70‑90％、TeO 2 5-25%, and 5-20% of dopant. The doping agent comprises the following raw materials in percentage by mass: li (Li) 2 TiO 3 5‑50％、LiF 5‑30％、CaB 4 O 7 5-50% and CaCO 3 5-30%. The ceramic dielectric material has low sintering temperature, high dielectric constant, low dielectric loss and high capacity stability, and can be co-fired 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, and belongs to the technical field of ceramic dielectric materials.
Background
The low temperature co-fired ceramic (LTCC) technology is to prepare a green ceramic chip with accurate and compact thickness from low temperature sintered ceramic powder, obtain a required circuit pattern by carrying out laser drilling or mechanical punching, micropore grouting and screen printing on the green ceramic chip, embed a plurality of passive elements (such as resistor (R), inductor (L), capacitor (C) and the like) into the circuit pattern, laminate, isostatic pressure and cut the circuit pattern to prepare a green body, and then carry out adhesive discharging sintering at 1000 ℃ to prepare the passive integrated group with a three-dimensional structure. The embedded element can save space to a great extent, and the passive-active integrated functional module manufactured by utilizing the LTCC technology is a technology capable of realizing miniaturization and high integration multifunctional design of the electronic component packaging module. On the basis of the LTCC technology, the material with better performance is selected, so that the electronic equipment has better performance, and the realization of industrial production by combining the high-performance ceramic material with the LTCC technology is one of the schemes for meeting the development demands of the current electronic components such as high frequency, miniaturization, high integration and the like.
LTCC technology has high precision requirements and it is generally desirable for materials to meet several key characteristics: (1) The low sintering temperature can be used for sintering together with Ag and Au, the sintering temperature is lower than 950 ℃ in the air atmosphere, the industrial production is more convenient, and the production cost can be reduced; (2) The low dielectric constant is a main way to increase the signal transmission speed, the signal transmission time is proportional to the square root of the dielectric constant, and the smaller the dielectric, the faster the signal transmission speed; (3) The low dielectric loss, in various devices, the number and the size of the embedded elements can influence the insertion loss index of the device, and under the condition of designing the same pattern, the material with the low dielectric loss can effectively reduce the insertion loss of the device; (4) good temperature characteristics, the temperature characteristics include: temperature coefficient of capacitance, thermal conductivity, etc.
The low-temperature cofired ceramic materials reported more at present comprise microcrystalline glass, glass/ceramic composite materials and Bi 2 O 3 -ZnO-Nb 2 O 5 /Ta 2 O 5 、BaO-Ln 2 O 3 -TiO 2 (ln=nd, sm) and Pb 1-x Ca x (Fe 1/2 ，Nb 1/2 )O 3 Dielectric ceramic materials are used, but the ceramic materials have the 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, wherein the ceramic dielectric material has the advantages of low sintering temperature, high dielectric constant, low dielectric loss and high capacity stability, and can be co-fired with a silver metal inner electrode with high conductivity.
The invention is realized by the following technical scheme:
the low-temperature co-fired ceramic dielectric material comprises the following raw materials in percentage by mass: ca (Ca) 9 Pr(VO 4 ) 7 70-90％、TeO 2 5-25%, and 5-20% of dopant.
The doping agent comprises the following raw materials in percentage by mass: li (Li) 2 TiO 3 5-50％、LiF 5-30％、CaB 4 O 7 5-50% and CaCO 3 5-30％。
The preparation method of the low-temperature co-fired ceramic dielectric material comprises the following steps in sequence:
1) CaCO as raw material 3 、Pr 6 O 11 And V 2 O 5 According to the general formula Ca 9 Pr(VO 4 ) 7 Is weighed into a mixture according to the stoichiometric ratio, ball-milled and then passed through 120-250 holes/cm 2 Sample separation and screening, heating to 500-600 ℃, and preserving heat for 2-4 hours to obtain a frit A;
2) Li is added according to mass percent 2 TiO 3 5-50％、LiF 5-30％、CaB 4 O 7 5-50% and CaCO 3 Ball milling 5-30% for 5 hr, and passing through 120 holes/cm 2 Sample separation screening, heating to 300 ℃, preserving heat for 2 hours, grinding and screening to obtain a doping agent B;
3) 5 to 20 percent of doping agent B and 5 to 25 percent of TeO according to mass percent 2 Secondary batching is carried out on 80-95% of the frit A to obtain a batching C;
4) Ball milling the mixture C for 8 hours, and passing through 120-250 holes/cm 2 And (3) a sample separating sieve, adding an adhesive with the mass percentage of 5-8% of the ingredients, granulating, pressing into a green body, slowly heating to 800-850 ℃, preserving heat 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 rising process in the step 2) is carried out at a temperature rising rate of 2-4 ℃/min, and the temperature is heated to 300 ℃ from the room temperature.
The heating 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; and in the second stage, heating from 400-500 ℃ to 800-850 ℃ at a heating rate of 5-10 ℃/min.
The adhesive is one of polyvinyl alcohol or paraffin wax.
Compared with the prior art, the invention has the following beneficial effects: ca according to the present invention 9 Pr(VO 4 ) 7 -TeO 2 The dielectric ceramic has moderate sintering temperature, generally about 1000 ℃, and higher dielectric constant. In addition, the ceramic material also has adjustable capacity temperature coefficient and lower loss, and is a dielectric ceramic material with excellent performance. The invention selects Ca 9 Pr(VO 4 ) 7 -TeO 2 The system adopts a method of adding the doping agent as the sintering aid, so that the sintering temperature is lower than 900 ℃ and the structure of the system is not damaged, thereby achieving the purposes of low-temperature co-sintering and excellent performance.
Drawings
The invention is further described below with reference to the accompanying drawings.
FIG. 1 is a graph showing the results of the temperature coefficient TCC test for the ceramic dielectric materials prepared in example 1, example 2, example 3 and example 4. As can be seen from the figure: along with the temperature rise, the temperature coefficient is gradually trend on the whole, and is within +/-15%, so that higher temperature stability is achieved.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the invention is not limited to these embodiments, and all changes and equivalents that do not depart from the spirit of the invention are intended to be included in the scope of the invention.
Example 1
The low-temperature co-fired ceramic dielectric material comprises the following raw materials in percentage by mass: ca9Pr (VO) 4 ) 7 70％、TeO 2 25% of a doping agent and 5% of a doping agent, wherein the doping agent comprises the following raw materials in percentage by mass: li (Li) 2 TiO 3 5％、LiF 15％、CaB 4 O 7 50%, and CaCO 3 30％。
The preparation process is as follows:
1) CaCO as raw material 3 、Pr 6 O 11 And V 2 O 5 According to the general formula Ca 9 Pr(VO 4 ) 7 Proportioning, ball milling for 6 hours on a ball mill with the rotating speed of 400r/min, drying in a common oven with the speed of 3.3kw at the temperature of 100 ℃, and passing through 250 holes/cm 2 The sample separation sieve is heated to 500 ℃ at a speed of 5 ℃/min, and is kept at 500 ℃ for 3 hours, so as to obtain the frit A.
2) Weighing Li 2 TiO 3 5g、LiF 15g、CaB 4 O 7 50g, and CaCO 3 30g, mixing, ball milling for 5 hours, passing through 120 holes/cm 2 Sample separating sieve, heating from room temperature to 300 ℃ at a heating rate of 2 ℃/min, preserving heat for 2 hours, grinding and sieving to obtain the doping agent B.
3) Secondary batching was carried out according to 5% dopant B, 25% TeO 2 And weighing 70% of the frit A in a mass ratio, and uniformly mixing. Adding deionized water, ball milling for 8 hr in a ball mill with rotation speed of 400r/min, drying at 120deg.C, and passing through 250 holes/cm 2 And (3) a sample separating sieve, adding 8wt% of paraffin wax for granulating, pressing into a green body, heating to 400 ℃ at a heating rate of 2 ℃/min, heating to 800 ℃ at a heating rate of 5 ℃/min, sintering, preserving heat for 1 hour, and cooling to obtain the ceramic medium.
The ceramic dielectric media prepared in this example were tested for dielectric properties at a frequency of 1GHz and the results are shown in table 1 and fig. 1.
TABLE 1
| Firing temperature (. Degree. C.) | Time of thermal insulation (h) | Dielectric constant epsilon | Loss tan delta | |
| Example 1 | 800 | 1 | 20 | 0.0001 |
Example 2
The low-temperature co-fired ceramic dielectric material comprises the following raw materials in percentage by mass: ca (Ca) 9 Pr(VO 4 ) 7 80％、TeO 2 15% and 5% of a dopant, wherein the dopant comprises the following raw materials in percentage by mass: li (Li) 2 TiO 3 50％、LiF 30％、CaB 4 O 7 10%, and CaCO 3 10％。
The preparation process is as follows:
1) CaCO as raw material 3 、Pr 6 O 11 And V 2 O 5 According to the general formula Ca 9 Pr(VO 4 ) 7 Proportioning, ball milling for 5 hours on a ball mill with the rotating speed of 400r/min, drying in a common oven with the speed of 3.3kw at the temperature of 100 ℃, and passing through 120 holes/cm 2 The sample separation sieve is heated to 600 ℃ at the speed of 10 ℃/min, and the temperature is kept at 600 ℃ for 2 hours, so as to obtain the frit A.
2) Weighing Li 2 TiO 3 50g、LiF 30g、CaB 4 O 7 10g, and CaCO 3 10g, mixing, ball milling for 5 hours, passing through 120 holes/cm 2 Sample separating sieve, heating from room temperature to 300 ℃ at a heating rate of 4 ℃/min, preserving heat for 2 hours, grinding and sieving to obtain the doping agent B.
3) Secondary batching is carried out according to 5 percent of doping agent B and 15 percent of TeO 2 And weighing the materials according to the mass ratio of 80% of the frit A, and uniformly mixing. Adding deionized water, ball milling for 8 hr in a ball mill with rotation speed of 400r/min, drying at 120deg.C, and passing through 250 holes/cm 2 Sample separating sieve, adding 8wt% paraffin wax, granulating, pressing to obtain green body, heating to 400 deg.C at 2 deg.C/min, heating to 810 deg.C at 5 deg.C/min, sintering, and maintaining the temperatureAnd (3) cooling for 1 hour to obtain the ceramic medium.
The ceramic dielectric media prepared in this example were tested for dielectric properties at a frequency of 1GHz and the results are shown in table 2 and fig. 1.
TABLE 2
| Firing temperature (. Degree. C.) | Time of thermal insulation (h) | Dielectric constant epsilon | Loss tan delta | |
| Example 2 | 810 | 1 | 24 | 0.0001 |
Example 3
The low-temperature co-fired ceramic dielectric material comprises the following raw materials in percentage by mass: ca (Ca) 9 Pr(VO 4 ) 7 90％、TeO 2 5% of a doping agent and 5% of the doping agent, wherein the doping agent comprises the following raw materials in percentage by mass: li (Li) 2 TiO 3 5％、LiF 30％、CaB 4 O 7 50%, and CaCO 3 15％。
The preparation process is as follows:
1) CaCO as raw material 3 、Pr 6 O 11 And V 2 O 5 According to the general formula Ca 9 Pr(VO 4 ) 7 Proportioning, ball milling for 4 hours on a ball mill with the rotating speed of 400r/min, drying in a common oven with the speed of 3.3kw at the temperature of 100 ℃, and passing through 200 holes/cm 2 The sample separation sieve is heated to 600 ℃ at the speed of 8 ℃/min, and the temperature is kept at 600 ℃ for 4 hours, so as to obtain the frit A.
2) Weighing Li 2 TiO 3 5g、LiF 30g、CaB 4 O 7 50g, and CaCO 3 15g, mixing, ball milling for 5 hours, passing through 120 holes/cm 2 Sample separating sieve, heating from room temperature to 300 ℃ at a heating rate of 2 ℃/min, preserving heat for 2 hours, grinding and sieving to obtain the doping agent B.
3) Secondary batching is carried out according to 5 percent of doping agent B and 5 percent of TeO 2 And weighing the materials and the mass ratio of 90% of the frit A, and uniformly mixing. Adding deionized water, ball milling for 8 hr in a ball mill with rotation speed of 400r/min, drying at 120deg.C, and passing through 200 holes/cm 2 And (3) a sample separating sieve, adding 8wt% of paraffin wax for granulating, pressing into a green body, heating to 500 ℃ at a heating rate of 4 ℃/min, heating to 820 ℃ at a heating rate of 10 ℃/min, sintering, preserving heat for 1 hour, and cooling to obtain the ceramic medium.
The ceramic dielectric media prepared in this example were tested for dielectric properties at a frequency of 1GHz and the results are shown in table 3 and fig. 1.
TABLE 3 Table 3
| Firing temperature (. Degree. C.) | Time of thermal insulation (h) | Dielectric constant epsilon | Loss tan delta | |
| Example 3 | 820 | 1 | 23 | 0.00012 |
Example 4
The low-temperature co-fired ceramic dielectric material comprises the following raw materials in percentage by mass: ca (Ca) 9 Pr(VO 4 ) 7 70％、TeO 2 10% and 20% of a dopant, wherein the dopant comprises the following raw materials in percentage by mass: li (Li) 2 TiO 3 25％、LiF25％、CaB 4 O 7 25%, and CaCO 3 25％。
The preparation process is as follows:
1) CaCO as raw material 3 、Pr 6 O 11 And V 2 O 5 According to the general formula Ca 9 Pr(VO 4 ) 7 Proportioning, ball milling for 4 hours on a ball mill with the rotating speed of 400r/min, drying in a common oven with the speed of 3.3kw at the temperature of 100 ℃, and passing through 200 holes/cm 2 The sample sieve is heated to 550 ℃ at the speed of 8 ℃/min, and is kept at 550 ℃ for 4 hours, so as to obtain the frit A.
2) Weighing Li 2 TiO 3 25g、LiF 25g、CaB 4 O 7 25g, and CaCO 3 25g, mixing, ball milling for 5 hours, passing through 120 holes/cm 2 Sample separating sieve, heating from room temperature to 300 ℃ at a heating rate of 2 ℃/min, preserving heat for 2 hours, grinding and sieving to obtain the doping agent B.
3) Secondary batching is carried out according to 20 percent of doping agent B and 10 percent of TeO 2 And weighing 70% of the frit A in a mass ratio, and uniformly mixing. Adding deionized water, ball milling for 8 hr in a ball mill with rotation speed of 400r/min, drying at 120deg.C, and passing through 200 holes/cm 2 Sample separating sieve, adding 8wt% polyvinyl alcohol to granulate, pressing to obtain green body, heating to 450 deg.C at a heating rate of 3 deg.C/minHeating to 850 ℃ at a heating rate of 8 ℃/min, sintering, preserving heat for 1 hour, and cooling to obtain the ceramic medium.
The ceramic dielectric media prepared in this example were tested for dielectric properties at a frequency of 1GHz and the results are shown in table 4 and fig. 1.
TABLE 4 Table 4
| Firing temperature (. Degree. C.) | Time of thermal insulation (h) | Dielectric constant epsilon | Loss tan delta | |
| Example 4 | 850 | 1 | 22 | 0.00015 |
The dielectric properties of examples 1-4 were tested using the following test methods and test equipment:
a. testing of dielectric constant ε and loss tan delta
The capacitance C and the dielectric loss tan δ (test frequency was 1 GHz) of the capacitor were measured using a HEWLETT PACKARD 4278A capacitance tester, and the dielectric constant epsilon was calculated by the following formula:
wherein: capacitance of the C-sample, unit pF; d-thickness of the sample piece, unit cm; d-diameter of sintered sample piece, unit cm.
b. Test of temperature coefficient TCC (-55 ℃ -150 ℃)
The capacitance temperature coefficient (test frequency is 1 GHz) of the capacitor is obtained by measuring the change condition of the capacitance of a sample along with the temperature by using a 6425 type WAYKERR bridge, a GZ-ESPEC MC-710F high-low temperature box and an HM27002 type capacitor C-T/V characteristic special tester, and the calculation formula is as follows:
wherein: the reference temperature is 25 ℃, C 0 For a capacity of 25℃C 1 At a temperature t 1 T, T 0 At a temperature of 25 ℃, T 1 For the test temperature, TCC units are ppm/DEG C.
The foregoing has described exemplary embodiments of the invention, it being understood that any simple variations, modifications, or other equivalent arrangements which would not unduly obscure the invention may be made by those skilled in the art without departing from the spirit 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 (7)
1. The low-temperature co-fired ceramic dielectric material is characterized by comprising the following raw materials in percentage by mass: ca (Ca) 9 Pr(VO 4 ) 7 70-90％、TeO 2 5-25% and 5-20% of doping agent, wherein the doping agent comprises the following raw materials in percentage by mass: li (Li) 2 TiO 3 5-50％、LiF 5-30％、CaB 4 O 7 5-50% and CaCO 3 5-30％。
2. The preparation method of the low-temperature co-fired ceramic dielectric material is characterized by comprising the following steps of:
1) CaCO as raw material 3 、Pr 6 O 11 And V 2 O 5 According to the general formula Ca 9 Pr(VO 4 ) 7 Is weighed into a mixture according to the stoichiometric ratio, ball-milled and then passed through 120-250 holes/cm 2 Sample separation and screening, heating to 500-600 ℃, and preserving heat for 2-4 hours to obtain a frit A;
2) Li is added according to mass percent 2 TiO 3 5-50％、LiF 5-30％、CaB 4 O 7 5-50% and CaCO 3 Ball milling 5-30% for 5 hr, and passing through 120 holes/cm 2 Sample separation screening, heating to 300 ℃, preserving heat for 2 hours, grinding and screening to obtain a doping agent B;
3) 5 to 20 percent of doping agent B and 5 to 25 percent of TeO according to mass percent 2 Secondary batching is carried out on 70-90% of the frit A to obtain a batching C;
4) Ball milling the mixture C for 8 hours, and passing through 120-250 holes/cm 2 And (3) a sample separating sieve, adding an adhesive with the mass percentage of 5-8% of the ingredients, granulating, pressing into a green body, slowly heating to 800-850 ℃, preserving heat for 1 hour, and cooling to obtain the ceramic medium.
3. The method for preparing the low-temperature co-fired ceramic dielectric material according to claim 2, wherein 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.
4. The method for preparing a low-temperature co-fired ceramic dielectric material according to claim 2, wherein the heating rate in the step 1) is 5-10 ℃/min.
5. The method for preparing a low-temperature co-fired ceramic dielectric material according to claim 2, wherein the heating process in the step 2) heats from room temperature to 300 ℃ at a heating rate of 2-4 ℃/min.
6. A low temperature co-fired ceramic dielectric according to claim 2The preparation method of the material is characterized in that the heating 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; a second stage of heating from 400-500 ℃ to 800 at a heating rate of 5-10 ℃/min - 850℃。
7. The method for preparing a low temperature co-fired ceramic dielectric material according to claim 2, wherein the binder is one of polyvinyl alcohol or paraffin wax.
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