CN114550977A - 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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- 239000003989 dielectric material Substances 0.000 title claims abstract description 21
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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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- 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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- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
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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: ca9Pr(VO4)770‑90％、TeO25-25% and 5-20% of a dopant. The dopant comprises the following raw materials in percentage by mass: li2TO35‑50％、LiF 5‑30％、CaB4O75-50% and CaCO35 to 30 percent. The ceramic dielectric material has low sintering temperature, high dielectric constant, low dielectric loss and high capacity stability, 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 (LTCC) technology is that low temperature sintered ceramic powder is made into a green ceramic chip with accurate thickness and compactness, laser punching or mechanical punching and micropore grouting are carried out on the green ceramic chip, conductor slurry is processed through a screen printing mode to obtain a required circuit pattern, a plurality of passive elements (such as a resistor (R), an inductor (L), a capacitor (C) and the like) are embedded into the green ceramic chip, then lamination, isostatic pressing and cutting are carried out to prepare a blank body, and then glue discharging and sintering are carried out at 1000 ℃ to prepare a passive integrated group with a three-dimensional structure. The element is embedded, so that the space can be saved to a great extent, and the passive-active integrated functional module manufactured by utilizing the LTCC technology is a technology capable of realizing the miniaturization and high-integration multifunctional design of the electronic component packaging module. On the basis of the LTCC technology, materials with better performance are selected to enable the electronic equipment to have better performance, and the realization of industrial production by combining high-performance ceramic materials with the LTCC technology is one of the schemes meeting the development requirements of high-frequency, miniaturization, high integration and the like of the electronic components at present.
LTCC technology requires high precision and generally requires materials to meet several key characteristics: (1) the low sintering temperature can be sintered 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 the 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 material can effectively reduce the insertion loss of the device under the condition of designing the same pattern, and the quantity and the size of the embedded elements in various devices can influence the insertion loss index of the device; (4) the temperature characteristics are good, and the temperature characteristics comprise: temperature coefficient of capacitance, thermal conductivity, etc.
At present, the most reported low-temperature co-fired ceramic materials comprise microcrystalline glass, glass/ceramic composite materials and 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: ca9Pr(VO4)770-90％、TeO25-25% and 5-20% of a dopant.
The dopant comprises the following raw materials in percentage by mass: li2TO35-50％、LiF 5-30％、CaB4O75-50% and CaCO35-30％。
A preparation method of a low-temperature co-fired ceramic dielectric material comprises the following steps of:
1) raw material CaCO3、Pr6O11And V2O5According to the general formula Ca9Pr(VO4)7The 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 500-600 ℃, and preserving heat for 2-4 hours to prepare a frit A;
2) mixing Li in percentage by mass2TO35-50％、LiF 5-30％、CaB4O75-50% and CaCO3Ball milling 5-30% for 5 hr, and passing through 120 holes/cm2Separating and sieving, heating to 300 ℃, preserving heat for 2 hours, grinding and sieving to obtain a doping agent B;
3) 5-20% of dopant B and 5-25% of TeO according to mass percentage2And 80-95% of the frit A are subjected to secondary burdening to obtain a burdening C;
4) ball milling the ingredient C for 8 hours, 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.
In the step 2), the temperature is increased from room temperature to 300 ℃ according to the temperature increase rate of 2-4 ℃/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 500 ℃ at 400-10 ℃/min to 850 ℃ at 800-850 ℃.
The adhesive is one of polyvinyl alcohol or paraffin.
Compared with the prior art, the invention has the following beneficial effects: ca of the invention9Pr(VO4)7-TeO2The dielectric ceramic has moderate sintering temperature, generally about 1000 ℃, and high 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. Selection of Ca in the invention9Pr(VO4)7-TeO2The system adopts a method of adding a dopant as a 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-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 coefficients are gradually reduced on the whole, the temperature coefficients are within +/-15%, and high 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: ca9Pr(VO4)770％、TeO225% and 5% of a dopant, wherein the dopant comprises the following raw materials in percentage by mass: li2TO35％、LiF 15％、CaB4O750% and CaCO 330％。
The preparation process comprises the following steps:
1) raw material CaCO3、Pr6O11And V2O5According to the general formula Ca9Pr(VO4)7Mixing, 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 samples, heating to 500 ℃ at the speed of 5 ℃/min, and preserving heat for 3 hours at 500 ℃ to obtain the frit A.
2) Weighing Li2TO35g、LiF 15g、CaB4O750g, and CaCO330g, mixed, ball milled for 5 hours, and then filtered through 120 holes/cm2And (3) separating a sample, sieving, heating from room temperature to 300 ℃ according to the heating rate of 2 ℃/min, preserving heat for 2 hours, grinding and sieving to obtain the dopant B.
3) Carrying out secondary batching according to 5 percent of doping agent B and 25 percent of TeO2And 70% of frit A by mass, 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 400 ℃ at the heating rate of 2 ℃/min, heating to 800 ℃ 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 1GHz and the results are shown in table 1 and fig. 1.
TABLE 1
| Firing temperature (. degree. C.) | Incubation time (h) | Dielectric constant ε | Loss tan delta | |
| Example 1 | 800 | 1 | 20 | 0.0001 |
Example 2
A low-temperature co-fired ceramic dielectric material comprises the following raw materials in percentage by mass: ca9Pr(VO4)780％、TeO 215% and 5% of a dopant, wherein the dopant comprises the following raw materials in percentage by mass: li2TO350％、LiF 30％、CaB4O710% and CaCO 310％。
The preparation process comprises the following steps:
1) raw material CaCO3、Pr6O11And V2O5According to the general formula Ca9Pr(VO4)7Mixing, ball milling for 5 hours in a ball mill with the rotation speed of 400r/min, drying in a common oven with the temperature of 3.3kw and the temperature of 100 ℃, and then passing through 120 holes/cm2And (4) screening, heating to 600 ℃ at the speed of 10 ℃/min, and preserving heat at 600 ℃ for 2 hours to obtain the frit A.
2) Weighing Li2TO350g、LiF 30g、CaB4O710g, and CaCO310g, mixing, ball milling for 5 hours, and passing through 120 holes/cm2Separating sample, sieving, heating from room temperature to 300 deg.C at a heating rate of 4 deg.C/min, holding for 2 hr, grinding, and sieving to obtain dopantB。
3) Carrying out secondary material preparation according to 5 percent of doping agent B and 15 percent of TeO2And 80% of the frit A by mass, 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 400 ℃ at the heating rate of 2 ℃/min, heating to 810 ℃ 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 1GHz, the results of which are shown in Table 2 and FIG. 1.
TABLE 2
| Firing temperature (. degree. C.) | Incubation time (h) | Dielectric constant ε | Loss tan delta | |
| Example 2 | 810 | 1 | 24 | 0.0001 |
Example 3
A low-temperature co-fired ceramic dielectric material comprises the following raw materials in percentage by mass: ca9Pr(VO4)790％、TeO 25% and 5% of a dopant, wherein the dopant comprises the following raw materials in percentage by mass: li2TO35％、LiF 30％、CaB4O750% and CaCO 315％。
The preparation process comprises the following steps:
1) raw material CaCO3、Pr6O11And V2O5According to the general formula Ca9Pr(VO4)7Mixing, ball milling for 4 hours in a ball mill with the rotation speed of 400r/min, drying in a common oven with the temperature of 3.3kw and the temperature of 100 ℃, and passing through 200 holes/cm2And (4) separating a sample, sieving, heating to 600 ℃ at the speed of 8 ℃/min, and preserving heat at 600 ℃ for 4 hours to obtain the frit A.
2) Weighing Li2TO35g、LiF 30g、CaB4O750g, and CaCO315g, mixing, ball milling for 5 hours, and passing through 120 holes/cm2And (3) separating a sample, sieving, heating from room temperature to 300 ℃ according to the heating rate of 2 ℃/min, preserving heat for 2 hours, grinding and sieving to obtain the dopant B.
3) Carrying out secondary material mixing according to 5 percent of doping agent B and 5 percent of TeO2And 90% of the frit A by mass, 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 200 pores/cm2And (3) separating a sample, sieving, adding 8 wt% of paraffin wax for granulation, pressing into a green body, heating to 500 ℃ at the heating rate of 4 ℃/min, heating to 820 ℃ 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 1GHz, the results of which are shown in Table 3 and FIG. 1.
TABLE 3
| Firing temperature (. degree. C.) | Incubation time (h) | Dielectric constant ε | Loss tan delta | |
| Example 3 | 820 | 1 | 23 | 0.00012 |
Example 4
A low-temperature co-fired ceramic dielectric material comprises the following raw materials in percentage by mass: ca9Pr(VO4)770％、TeO210% and 20% of a dopant, wherein the dopant comprises the following raw materials in percentage by mass: li2TO325％、LiF 25％、CaB4O725% and CaCO325％。
The preparation process comprises the following steps:
1) raw material CaCO3、Pr6O11And V2O5According to the general formula Ca9Pr(VO4)7Mixing, ball milling for 4 hours in a ball mill with the rotation speed of 400r/min, drying in a common oven with the temperature of 3.3kw and the temperature of 100 ℃, and passing through 200 holes/cm2And (4) screening samples, heating to 550 ℃ at the speed of 8 ℃/min, and preserving heat for 4 hours at 550 ℃ to obtain the frit A.
2) Weighing Li2TO325g、LiF 25g、CaB4O725g, and CaCO325g, mixing, ball milling for 5 hours, and passing through 120 holes/cm2Separating sample, sieving, heating from room temperature to 300 deg.C at a heating rate of 2 deg.C/min, holding for 2 hr, grinding, and sieving to obtain dopantB。
3) Performing secondary material mixing according to 20 percent of doping agent B and 10 percent of TeO2And 70% of frit A by mass, and uniformly mixing. Adding deionized water, ball milling in a ball mill at 400r/min for 8 hr, drying at 120 deg.C, and sieving with 200 holes/cm2And (3) separating a sample, sieving, adding 8 wt% of polyvinyl alcohol for granulation, pressing into a green body, heating to 450 ℃ according to the heating rate of 3 ℃/min, heating to 850 ℃ according to the heating rate of 8 ℃/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 1GHz, the results of which are shown in Table 4 and FIG. 1.
TABLE 4
| Firing temperature (. degree. C.) | Incubation time (h) | Dielectric constant ε | Loss tan delta | |
| Example 4 | 850 | 1 | 22 | 0.00015 |
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 δ (test frequency 1GHz) of the capacitor were measured using a HEWLETT PACKARD 4278A capacitance tester, and the dielectric constant ∈ was calculated by the following formula:
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 test frequency is 1GHz) of the capacitor is obtained by measuring the capacitance variation of the sample with temperature by using a WAYKERR bridge model 6425, a GZ-ESPEC MC-710F high-low temperature box and a special C-T/V characteristic tester of the capacitor model HM27002, 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 t1Capacity of (T)0At a temperature of 25 ℃ T1TCC is expressed in ppm/deg.C as the test temperature.
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 (8)
1. The low-temperature co-fired ceramic dielectric material is characterized by comprising the following raw materials in percentage by mass: ca9Pr(VO4)770-90％、TeO25-25% and 5-20% of a dopant.
2. The low-temperature co-fired ceramic dielectric material as claimed in claim 1, wherein the dopant comprises the following raw materials by mass percent: li2TO35-50％、LiF 5-30％、CaB4O75-50% and CaCO35-30％。
3. A preparation method of a low-temperature co-fired ceramic dielectric material is characterized by comprising the following steps of:
1) raw material CaCO3、Pr6O11And V2O5According to the general formula Ca9Pr(VO4)7The mixture is weighed according to the stoichiometric ratio, and is processed by ball milling through 120-250 holes/cm2Separating and sieving, heating to 500-600 ℃, and preserving heat for 2-4 hours to prepare a frit A;
2) mixing Li in percentage by mass2TO35-50％、LiF 5-30％、CaB4O75-50% and CaCO3Ball milling 5-30% for 5 hr, and passing through 120 holes/cm2Separating and sieving, heating to 300 ℃, preserving heat for 2 hours, grinding and sieving to obtain a doping agent B;
3) 5-20% of dopant B and 5-25% of TeO according to mass percentage2And 80-95% of the frit A are subjected to secondary burdening to obtain a burdening C;
4) ball milling the ingredient C for 8 hours, 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.
4. The method for preparing a low-temperature co-fired ceramic dielectric material according to claim 3, 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.
5. The method for preparing a low-temperature co-fired ceramic dielectric material as claimed in claim 3, wherein the temperature rise rate in the step 1) is 5-10 ℃/min.
6. The method for preparing a low-temperature co-fired ceramic dielectric material according to claim 3, wherein the temperature rise process in the step 2) is carried out at a temperature rise rate of 2-4 ℃/min from room temperature to 300 ℃.
7. The method for preparing a low-temperature co-fired ceramic dielectric material according to claim 3, wherein the temperature rising 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, the temperature is heated from 400-500 ℃ to 800-850 ℃ at the heating rate of 5-10 ℃/min.
8. The method according to claim 3, wherein the binder is one of polyvinyl alcohol or paraffin wax.
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