CBS-BASED LTCC MATERIAL AND PREPARATION METHOD THEREOF

Abstract

Disclosed is a CBS-based low-temperature co-fired ceramic (LTCC) material, and a preparation method thereof. The material has, as a main component, a sintered phase of low dielectric constant of CaSiO.sub.3 and CaB.sub.2O.sub.4, and comprises CBS and a dopant. The CBS comprises, by weight, 30-40% of CaO, 15-30% of B.sub.2O.sub.3, and 40-50% of SiO.sub.2, and the dopant comprises 0-2% of P.sub.2O.sub.5, 0-2% of nanometer CuO, and 0.5-2% of nanometer V.sub.2O.sub.5. The preparation method comprises mixing oxides including a CBS-based dielectric ceramic as a base and one or two of P.sub.2O.sub.5 and CuO as an initial dopant, and then adding V.sub.2O.sub.5 as a final sintering aid, to prepare the material. In the present invention, a CBS-based LTCC material that is obtained by sintering at a low temperature and has the advantages of low dielectric constant, low loss, and good overall performance is provided.

Claims

1. A CBS-based low-temperature co-fired ceramic material having, as a main component, a sintered phase of low dielectric constant of CaSiO.sub.3 and CaB.sub.2O.sub.4 comprising CBS and a dopant, wherein the CBS comprises, by weight, 30-40% of CaO, 15-30% of B.sub.2O.sub.3, and 40-50% of SiO.sub.2, and the dopant comprises 0-2% of P.sub.2O.sub.5, 0-2% of nanometer CuO, and 0.5-2% of nanometer V.sub.2O.sub.5.

2. A method for preparing a CBS-based LTCC material, comprising: mixing a CBS-based dielectric ceramic as a base with one or two of P.sub.2O.sub.5 and CuO as an initial dopant, and then adding V.sub.2O.sub.5 as a final sintering aid, to prepare the material, wherein the material has, as a main component, a sintered phase of low dielectric constant of CaSiO.sub.3 and CaB.sub.2O.sub.4 comprising CBS and a dopant, wherein the CBS comprises, by weight, 30-40% of CaO, 15-30% of B.sub.2O.sub.3, and 40-50% of SiO.sub.2, and the dopant comprises 0-2% of P.sub.2O.sub.5, 0-2% of nanometer CuO, and 0.5-2% of nanometer V.sub.2O.sub.5.

3. The preparation method according to claim 2, comprising the steps of (1) material mixing weighing the raw materials CaCO.sub.3, H.sub.3BO.sub.3, and SiO.sub.2 based on 30-40% of CaO, 15-30% of B.sub.2O.sub.3, and 40-50% of SiO.sub.2, and doping based on CBS-x wt % P.sub.2O.sub.5-y wt % CuO, where x=0-2 and y=0-2 chemical stoichiometric proportion, mixing and ball milling where the ball milling medium is deionized water and zirconia balls, then drying the CBS mixture in an oven, grinding, and sieving through a 60-mesh screen; (2) pre-sintering pre-sintering the sieved CBS powder obtained in Step (1), holding for a pre-determined period of time, cooling to room temperature, then grinding, and sieving; (3) secondary mixing mixing the sieved pre-sintered powder obtained in Step (2) with V.sub.2O.sub.5 based on (CBS-xwt % P.sub.2O.sub.5-ywt % CuO)-zwt % V.sub.2O.sub.5, where z=0.5-2 chemical stoichiometric proportion, ball milling after mixing where the ball milling medium is deionized water and zirconia balls, then drying the ground powder in an oven, grinding, and sieving through a 60-mesh screen; (4) secondary pre-sintering pre-sintering the sieved final CBS powder obtained in Step (3), holding for a pre-determined period of time, and cooling to room temperature; (5) tertiary grinding subjecting the secondarily pre-sintered CBS powder obtained in Step (4) to ball milling until a desired range of particle sizes is attained, drying the CBS mixture, then grinding, and sieving through a 120-mesh screen; (6) pressing granulating the sieved powder obtained in Step (5) with a granulation solution, sieving, and pressing the fine powder into a green body; (7) glue discharge; and (8) sintering.

4. The preparation method according to claim 3, wherein the doped CuO has an average particle size of 60-100 nm, and the V.sub.2O.sub.5 has an average particle size of 80-100 nm.

5. The preparation method according to claim 3, wherein the desired range of particle sizes described in Step (5) is 0.5-1 m.

6. The preparation method according to claim 3, wherein in the ball milling in Steps (1), (3), and (5), the weight ratio of material:ball:water is 1:2:1; in Step (1), the ball milling time is 3 hrs, and the rotational speed of the ball mill is 250 rpm; in Step (3), the ball milling time is 3 hrs, and the rotational speed of the ball mill is 250 rpm; and in Step (5), the ball milling time is 4 hrs, and the rotational speed of the ball mill is 350 rpm.

7. The preparation method according to claim 3, wherein in Step (2), the pre-sintering occurs at 800 C., and the holding time is 6 hrs.

8. The preparation method according to claim 3, wherein in Step (4), the pre-sintering occurs at 800 C., and the holding time is 4 hrs.

9. The preparation method according to claim 3, wherein in Step (6), the sieved powder obtained in Step (5) is granulated with a 5 wt % solution of polyvinyl alcohol in water, and sieved through a 120-mesh screen, and the fine powder is pressed into a green body, wherein the press pressure is 260 MPa, and the press time is 20 s.

10. The preparation method according to claim 3, wherein in Step (7), the green body obtained in Step (6) is placed in a muffle furnace, heated to 500 C. at a ramp rate of 1.5 C./min, and held for 2 hrs, to discharge the organics; and in Step (8), the green body after glue discharge obtained in Step (7) is placed in a muffle furnace, sintered by heating to 850-900 C. at a ramp rate of 5 C./min, and held for 2 hrs, and then naturally cooled to room temperature with the furnace.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0038] The present disclosure will become more fully understood from the detailed description given herein below for illustration only, and thus are not limitative of the present invention, and wherein:

[0039] FIG. 1 is a curve showing the change of the dielectric constant with the dopant content and the sintering temperature in Examples 1-3 and Comparative Examples 1-4.

[0040] FIGS. 2A to 2D are respectively the micrographs at the cross section of the samples of CBS-based LTCC materials prepared in Comparative Example 3-2, Comparative Example 4-2, Example 2-2, and Example 3-2 after being sintered at 875 C. for 2 hrs.

[0041] FIG. 3 shows the dielectric constant and dielectric loss of Example 2-2 within 100 GHz.

DETAILED DESCRIPTION

[0042] The present disclosure is described in further detail below with reference to embodiments and the accompanying drawings. It should be noted that the following description is merely exemplary and is not intended to limit the scope of the present application.

[0043] In an embodiment, a CBS-based low-temperature co-fired ceramic material has, as a main component, a sintered phase of low dielectric constant of CaSiO.sub.3 and CaB.sub.2O.sub.4, and comprises CBS and a dopant, where the CBS comprises, by weight, 30-40% of CaO, 15-30% of B.sub.2O.sub.3, and 40-50% of SiO.sub.2, and the dopant comprises 0-2% of P.sub.2O.sub.5, 0-2% of nanometer CuO, and 0.5-2% of nanometer V.sub.2O.sub.5.

[0044] A method for preparing a CBS-based LTCC material comprises mixing a CBS-based dielectric ceramic as a base with one or two of P.sub.2O.sub.5 and CuO as an initial dopant, and then adding V.sub.2O.sub.5 as a final sintering aid, to prepare the material. The material has, as a main component, a sintered phase of low dielectric constant of CaSiO.sub.3 and CaB.sub.2O.sub.4, comprising CBS and a dopant, where the CBS comprises, by weight, 30-40% of CaO, 15-30% of B.sub.2O.sub.3, and 40-50% of SiO.sub.2, and the dopant comprises 0-2% of P.sub.2O.sub.5, 0-2% of nanometer CuO, and 0.5-2% of nanometer V.sub.2O.sub.5.

[0045] In a specific embodiment, a method for preparing a CBS-based LTCC material of low dielectric constant and loss comprises the steps of:

[0046] (1) material mixing

[0047] weighing the raw materials CaCO.sub.3, H.sub.3BO.sub.3, and SiO.sub.2 based on 30-40% of CaO, 15-30% of B.sub.2O.sub.3, and 40-50% of SiO.sub.2, and doping based on CBS-x wt % P.sub.2O.sub.5-y wt % CuO, where x=0-2 and y=0-2 chemical stoichiometric proportion, mixing, and ball milling in a ball mill jar where the ball milling medium is deionized water and zirconia balls and the weight ratio of material:ball:water is 1:2:1, then drying the CBS mixture in an oven at 100 C., grinding in an agate mortar, and sieving through a 60-mesh screen;

[0048] (2) pre-sintering

[0049] placing the sieved CBS powder obtained in Step (1) in a crucible, compacting, covering, sealing, pre-sintering and holding in a muffle furnace at 800 C. for 6 hrs, then naturally cooling to room temperature with the furnace, grinding in an agate mortar, and sieving through a 60-mesh screen;

[0050] (3) secondary mixing

[0051] mixing the sieved pre-sintered powder obtained in Step (2) with V.sub.2O.sub.5 based on (CBS-xwt % P.sub.2O.sub.5-ywt % CuO)-zwt % V.sub.2O.sub.5, where z=0.5-2 chemical stoichiometric proportion, ball milling in a ball mill jar after mixing where the ball milling medium is deionized water and zirconia balls, and the weight ratio of material:ball:water is 1:2:1, then drying the ground powder in an oven at 100 C., grinding in an agate mortar, and sieving through a 60-mesh screen;

[0052] (4) Secondary pre-sintering

[0053] placing the sieved final CBS powder obtained in Step (3) in a crucible, compacting, covering, sealing, pre-sintering and holding in a muffle furnace at 800 C. for 4 hrs, and then naturally cooling to room temperature with the furnace;

[0054] (5) tertiary grinding

[0055] subjecting the secondarily pre-sintered CBS powder obtained in Step (4) to ball milling in a ball mill jar until a desired range of particle sizes is attained, where the weight ratio of material:ball:water is 1:4:1, drying the CBS mixture in an oven at 100 C., grinding in an agate mortar, and sieving through a 60-mesh screen;

[0056] (6) pressing

[0057] granulating the sieved powder obtained in Step (5) with a 5 wt % solution of polyvinyl alcohol in water, sieving through a 120-mesh screen, and pressing the fine powder into a green body;

[0058] (7) glue discharge

[0059] placing the green body obtained in Step (6) in a muffle furnace, heating to 500 C. at a ramp rate of 1.5 C./min, and holding for 2 hrs, to discharge the organics;

[0060] (8) sintering

[0061] placing the green body after glue discharge obtained in Step (7) in a muffle furnace, sintering by heating to 850-900 C. at a ramp rate of 5 C./min, holding for 2 hrs, and then naturally cooling to room temperature with the furnace; and

[0062] (9) microwave performance test

[0063] Standing the dielectric ceramic sintered in Step (8) for 12 hrs at room temperature, and testing for the .sub.r and tan by using Agilent E5071C network analyzer.

[0064] In Step (1), the raw materials comprise CaCO.sub.3, H.sub.3BO.sub.3, SiO.sub.2, P.sub.2O.sub.5, CuO, and V.sub.2O.sub.5, the nanometer CuO has an average particle size of 60-100 nm, and the nanometer V.sub.2O.sub.5 has an average particle size of 80-100 nm.

[0065] In Step (1), the ball milling time is 3 hrs, and the rotational speed of the ball mill is 250 rpm.

[0066] In Step (3), the ball milling time is 3 hrs, and the rotational speed of the ball mill is 250 rpm.

[0067] In Step (5), the ball milling time is 4 hrs, and the rotational speed of the ball mill is 350 rpm.

[0068] The desired range of particle sizes described in Step (5) is 0.5-1 m.

[0069] In Step (6), the press pressure is 260 MPa, and the press time is 20 s.

[0070] In Step (6), the pressed green body is a cylindrical body having a diameter of 14 mm, and a thickness of 6-7 mm.

[0071] In Step (9), the CBS-based LTCC material of low-dielectric loss has the properties of r=5.8-6.2 and Tan <0.2%.

[0072] The dopant contents in various specific examples and comparative examples are shown in Table 1.

TABLE-US-00001 TABLE 1 Dopant contents in examples and comparative examples x y z Remark Example 1 1 0 1.2 Sintered at 850 C., 875 C., and 900 C., and designated as Examples 1-1, 1-2, and 1-3 respectively Example 2 0 1 1.2 Sintered at 850 C., 875 C., and 900 C., and designated as Examples 2-1, 2-2, and 2-3 respectively Example 3 1 1 1.2 Sintered at 850 C., 875 C., and 900 C., and designated as Examples 3-1, 3-2, and 3-3 respectively Comparative 0 0 0 Sintered at 850 C., 875 C., and 900 C., Example 1 and designated as Comparative Examples 1-1, 1-2, and 1-3 respectively Comparative 1 0 0 Sintered at 850 C., 875 C., and 900 C., Example 2 and designated as Comparative Examples 2-1, 2-2, and 2-3 respectively Comparative 0 1 0 Sintered at 850 C., 875 C., and 900 C., Example 3 and designated as Comparative Examples 3-1, 3-2, and 3-3 respectively Comparative 0 0 1.2 Sintered at 850 C., 875 C., and 900 C., Example 4 and designated as Comparative Examples 4-1, 4-2, and 4-3 respectively

[0073] The test results of the appearance after sintering, the shrinkage, the density, the dielectric constant, and the loss of the examples and comparative examples are listed in Table 2.

TABLE-US-00002 TABLE 2 Sintering performance of the examples and comparative examples Appearance Density 12 GHZ Overall after sintering Shrinkage (g/cm.sup.3) .sub.r tan performance Example 1-1 Smooth surface 15% 0.5 2.54 5.81 0.17% Accepted Example 1-2 Smooth surface 16% 0.5 2.56 5.92 0.16% Accepted Example 1-3 Smooth surface 16% 0.5 2.58 6.02 0.15% Accepted Example 2-1 Smooth surface 15% 0.5 2.60 5.91 0.18% Accepted Example 2-2 Smooth surface 16% 0.5 2.65 6.17 0.13% Accepted Example 2-3 Smooth surface 15% 0.5 2.63 6.08 0.15% Accepted Example 3-1 Smooth surface 15% 0.5 2.61 6.00 0.15% Accepted Example 3-2 Smooth surface 16% 0.5 2.67 6.10 0.12% Accepted Example 3-3 Smooth surface 15% 0.5 2.67 6.16 0.14% Accepted Comparative Rough surface Less than 2.00 3.89 0.30% Not accepted Example 1-1 3% Comparative Rough surface Less than 2.01 3.90 0.30% Not accepted Example 1-2 3% Comparative Rough surface Less than 2.01 4.02 0.29% Not accepted Example 1-3 3% Comparative Rough surface 5% 0.5 2.11 4.36 0.29% Not accepted Example 2-1 Comparative Rough surface 5% 0.5 2.12 4.40 0.29% Not accepted Example 2-2 Comparative Rough surface 5% 0.5 2.16 5.11 0.28% Not accepted Example 2-3 Comparative Rough surface 5% 0.5 2.14 4.55 0.26% Not accepted Example 3-1 Comparative Rough surface 5% 0.5 2.16 4.56 0.28% Not accepted Example 3-2 Comparative Rough surface 5% 0.5 2.18 5.20 0.27% Not accepted Example 3-3 Comparative Rough surface 6% 0.5 2.13 4.65 0.29% Not accepted Example 4-1 Comparative Rough surface 6% 0.5 2.24 4.81 0.25% Not accepted Example 4-2 Comparative Rough surface 6% 0.5 2.26 5.25 0.24% Not accepted Example 4-3

[0074] FIG. 1 is a curve showing the change of the dielectric constant with the dopant content and the sintering temperature in Examples 1-3 and Comparative Examples 1-4. FIGS. 2A to 2D are respectively the micrographs at the cross section of the samples of CBS-based LTCC materials prepared in Comparative Example 3-2, Comparative Example 4-2, Example 2-2, and Example 3-2 after being sintered at 875 C. for 2 hrs. FIG. 3 shows the dielectric constant and dielectric loss of Example 2-2 within 100 GHz.

[0075] Densification into a ceramic by sintering at 850-900 C. is achieved in all the examples above, and the prepared CBS-based LTCC material has the properties of .sub.r=5.8-6.5 and tan <0.2%. Example 3-2 is the most preferred example where the loss is the lowest and tan =0.12%.

[0076] As an initial dopant, P.sub.2O.sub.5 and nanometer CuO can facilitate the full formation of a main crystal phase during the pre-sintering of CBS and improve the sintering activity of the powder, and have no adverse effect on CBS when added in an amount of 2 wt % or less. V.sub.2O.sub.5 has a melting point of 690 C. and an even higher activity at a nano-scale, facilitates the formation of a liquid phase and the accomplishment of low-temperature sintering as a final sintering aid for the powdered CBS base, and produces no impure phase in CBS when added in an amount of 2 wt % or less. The dielectric constant of the dielectric ceramic mainly depends on the phase type, content and relative density (compactness). Because the dopant content is small, the material in the examples is sintered and shrunk properly at 850-900 C. to form a dense ceramic, and the dielectric constant and loss are stable. Moreover, the logarithmic mixture rule of the dielectric material shows that the more the pore number is (that is, the poor the density is), the lower the dielectric constant is, and the higher the loss is. The data in both the examples and comparative example follows this rule. Therefore, in a CBS system having a certain composition, densification into a ceramic by sintering at 850 C.-900 C., stable dielectric constant, low loss, and good overall performance can be achieved by using (either or both of) P.sub.2O.sub.5 and nanometer CuO, and nanometer V.sub.2O.sub.5 in combination.

[0077] Although the present invention is described above in further detail through specific embodiments, the present invention is not limited to the specific embodiments. It should be understood by persons of ordinary skill in the art that any simple deduction or replacement made without departing from the spirit of the present invention shall fall within the protection scope of the present invention.