CN108975914B - ZnO-TiO2-Nb2O5Base LTCC material and preparation method thereof - Google Patents
ZnO-TiO2-Nb2O5Base LTCC material and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000005245 sintering Methods 0.000 claims abstract description 18
- 239000000919 ceramic Substances 0.000 claims abstract description 14
- 239000013078 crystal Substances 0.000 claims abstract description 12
- 229910019792 NbO4 Inorganic materials 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000012071 phase Substances 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052681 coesite Inorganic materials 0.000 claims description 12
- 229910052906 cristobalite Inorganic materials 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 229910052682 stishovite Inorganic materials 0.000 claims description 12
- 229910052905 tridymite Inorganic materials 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 9
- 229910052726 zirconium Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000004615 ingredient Substances 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000003825 pressing Methods 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 239000003292 glue Substances 0.000 claims description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000012752 auxiliary agent Substances 0.000 abstract description 2
- 238000004891 communication Methods 0.000 description 4
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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Abstract
The invention belongs to the field of electronic ceramics and manufacture thereof, and relates to ZnO-TiO2‑Nb2O5A base LTCC material and a preparation method thereof. The main crystal phase of the material provided by the invention is Zn0.5Ti0.5NbO4Phase, secondary crystal phase Zn0.15Nb0.3Ti0.55O2Phase, and a secondary crystal phase ZnNb is also present during sintering at 850-875 DEG C2O6The sintering temperature is as low as 850 ℃, the dielectric constant is 40-48, and the loss is as low as 2.9 multiplied by 10‑4Temperature coefficient of frequency τf+ 60-24 ppm/. degree.C. Compared with the prior art, the preparation method reduces the preparation of the auxiliary agent and the secondary batching after the pre-sintering, simplifies the preparation process, and finally prepares the ZnO-TiO2‑Nb2O5The performance of the base system LTCC material is superior to that of the prior art.
Description
Technical Field
The invention belongs to the field of electronic ceramics and manufacture thereof, and relates to ZnO-TiO2-Nb2O5A low temperature co-fired ceramic (LTCC) material and a preparation method thereof.
Background
Modern communication systems are increasingly demanding in microwave dielectric ceramic materials. Microwave dielectric ceramic materials are now widely used in dielectric resonators, microstrip antennas, filters, and the like. With the continuous high-speed development of the domestic communication industry in recent decades, the radio mobile communication equipment is frequently updated, and has the development characteristics of small size, stronger function and pursuit of low cost. The Low Temperature Co-fired Ceramic (LTCC) technology plays a key role in the production of multilayer Ceramic circuits, and the volume of various communication radio frequency devices can be effectively reduced due to the adoption of a laminated three-dimensional layout process design, so that the LTCC technology is widely applied to the fields of medical treatment, automobile manufacturing, communication equipment and the like.
The LTCC material is required to be co-fired with electrodes such as Ag and Cu used in the current production, so that the Ag electrode is prevented from melting due to overhigh temperature (the melting point of Ag is 961 ℃). Therefore, the LTCC material is required to have lower sintering temperature (less than or equal to 950 ℃) and good chemical compatibility with an electrode. Further, the microwave dielectric ceramics to be used are required to have different relative dielectric constants (. epsilon.) depending on the field of user) High quality factor (Qxf) and near-zero temperature coefficient of resonant frequency (τ)f). Wherein it corresponds to a dielectric constant εrPhysical parameters commonly used to characterize dielectric or polarization properties of dielectric materials, whose values are equal to the ratio of the capacitance of a capacitor of the same size made with the predicted material as the medium and with the vacuum as the medium; the quality factor Qxf is used to represent a quality index of the ratio of the energy stored in an energy storage device (such as an inductance coil, a capacitor, etc.) and the resonant circuit to the energy lost per cycle; temperature coefficient of resonance frequency taufExpressed as the sensitivity of the resonance frequency to temperature changes.
At present, on ZnO-TiO2-Nb2O5The research on the sintering temperature reduction of the base ceramics focuses on adding sintering aids, such as CuO and Li, to the pre-sintered material2O-ZnO-B2O3、ZnO、BaO-CuO-B2O3And the like. According to the existing report, the temperature of the ceramic matrix can be reduced to 875-950 ℃, but the dielectric constant epsilon of the final ceramic isrLower (30) and τfThe value is large (-59 ppm/. degree.C.).
Disclosure of Invention
Aiming at solving the problems or the defects, the ZnO-TiO2-Nb2O5Base LTCC Material epsilonrLower and τfThe invention provides a ZnO-TiO with larger value2-Nb2O5The electronic ceramic material can be sintered and compacted at low temperature and simultaneously improve the microwave dielectric property.
The ZnO-TiO2-Nb2O5Based LTCC material with Zn as main crystal phase0.5Ti0.5NbO4Phase, secondary crystal phase Zn0.15Nb0.3Ti0.55O2Phase, and a secondary crystal phase ZnNb is also present during sintering at 850-875 DEG C2O6The sintering temperature is as low as 850 ℃, the dielectric constant is 40-48, and the loss is as low as 2.9 multiplied by 10-4Temperature coefficient of frequency τf+60~-24ppm/℃。
The raw materials are as follows: ZnO, TiO2、Nb2O5、Li2CO3、B2O3And SiO2Mixing (0.15+0.35x) ZnO- (0.55-0.05x) TiO according to a chemical formula2-(0.15+0.35x)Nb2O5-(0.3y+xy)Li2CO3-(0.5y+xy)B2O3 -(0.2y+xy)SiO2(x is 0.4 to 0.6mol, and y is 0.01 to 0.04mol) by a solid phase method.
The preparation method comprises the following steps:
Step 2, filling the ingredients obtained in the step 1 into a ball milling tank, taking zirconium balls and deionized water as grinding media, and mixing the following ingredients: zirconium ball: carrying out planetary ball milling for 5-7 hours at a deionized water mass ratio of 1: 5-7: 2-4, then drying at 80-100 ℃, sieving by using a 40-60 mesh screen, and finally presintering for 2-4 hours at 900-1000 ℃ in an atmosphere;
step 3, mixing the powder subjected to the pre-sintering in the step 2 into powder: zirconium ball: performing secondary ball milling on the deionized water in a mass ratio of 1: 5-7: 1-3 for 3-6 hours, taking out and drying, and adding an acrylic acid solution into the obtained powder for granulation;
and 4, pressing and forming the powder granulated in the step 3, removing the glue, raising the temperature to 850-950 ℃, and preserving the heat for 4-6 hours to obtain the low-temperature sintered microwave dielectric ceramic.
In conclusion, the invention uses ZnO and TiO as raw materials2、Nb2O5、Li2CO3、B2O3And SiO2The preparation method reduces the preparation of the auxiliary agent and the secondary batching after the pre-sintering (simplifies the preparation process) compared with the prior art, and finally the prepared ZnO-TiO is2-Nb2O5The performance of the base system LTCC material is superior to that of the prior art.
Drawings
Fig. 1 shows the shrinkage curve when x is 0.43mol and y is 0.01 mol.
Fig. 2 is an XRD pattern of examples 1-4 where x is 0.43mol and y is 0.01 mol.
Fig. 3 is an SEM image of example 5 with x being 0.43mol and y being 0.01 mol.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
step 2, filling the ingredients obtained in the step 1 into a ball milling tank, taking zirconium balls and deionized water as grinding media, and mixing the following ingredients: zirconium ball: carrying out planetary ball milling for 6 hours at the mass ratio of deionized water of 1:6:4, then drying at 100 ℃, sieving by using a 60-mesh sieve, and finally presintering for 3 hours at 950 ℃ in atmosphere;
and 3, putting the pre-sintered powder into a ball milling tank for secondary ball milling, and mixing the powder: zirconium ball: carrying out planetary ball milling for 4 hours according to the mass ratio of the deionized water to the deionized water of 1:6:3, taking out and drying, and adding an acrylic acid solution into the obtained powder for granulation;
and 4, putting the granulated powder into a phi 15 die, performing dry pressing under the pressure of 20MPa to form a cylindrical block body (the size of the cylindrical block body is 15mm multiplied by 10 mm), then performing heat preservation on the cylindrical block body for 2 hours at 450 ℃ to remove the binder, then raising the temperature to 850-975 ℃, performing heat preservation for 4 hours, and finally preparing the low-temperature sintered microwave dielectric ceramic.
Fig. 1 shows the shrinkage curve when x is 0.43mol and y is 0.01 mol. It can be seen that the temperature at which the sample begins to shrink is around 600 c, and the sample reaches a maximum shrinkage of around 17% when the temperature is increased to around 950 c.
FIG. 2 is the XRD diffraction patterns of examples 1-4, from which it can be seen that the main crystal phase of the ceramic is Zn0.5Ti0.5NbO4Matched with JCPDS card number 48-0323, the secondary crystal phase is Zn0.15Nb0.3Ti0.55O2(JCPDS # 79-1186). In examples 1 and 2, a small amount of ZnNb is present2O6Phase, card number (JCPDS # 37-1371). In examples 3 to 4, ZnNb was observed as the sintering temperature was increased2O6The phases disappeared.
FIG. 3 is a SEM surface topography of example 5. It is seen from the figure that the sample surface is porous, and has crystal grains with different sizes and states, and the crystal grain size is smaller.
The compositions and microwave dielectric properties of the examples are shown in the table below
As can be seen from the above table data, the samples all achieved excellent performance between 850 ℃ and 975 ℃, and for examples 1 to 6, the dielectric constant of the samples increased and then decreased with increasing sintering temperature, and the best dielectric was 42.22 at 925 ℃ sintering (example 4), at which time the Q f value of the samples reached 18904 GHz. Taking into account τfThe sample achieved excellent performance at example 2, where the sintering temperature was 875 ℃. For examples 7-12, the dielectric constant of the samples increased with temperature from 41.73 to 47.53, and the Q x f value of the samples increased from 11413 to 13263 GHz. The overall optimum performance was also achieved at a sintering temperature of 875 ℃ (example 8).
In summary, the invention adjusts the raw materials of ZnO and TiO2、Nb2O5、Li2CO3、B2O3And SiO2The molar ratio of the components is high, and finally ZnO-TiO with excellent performance is obtained at low temperature2-Nb2O5A microwave dielectric ceramic system.
Claims (2)
1. ZnO-TiO2-Nb2O5The LTCC material is characterized in that:
the main crystal phase being Zn0.5Ti0.5NbO4Phase, secondary crystal phase Zn0.15Nb0.3Ti0.55O2Phase, the sintering temperature is 875-950 ℃, and a paracrystalline phase ZnNb is also existed during sintering at 875 DEG C2O6Phase, dielectric constant 40 to 48, loss as low as 2.9X 10-4Temperature coefficient of frequency τf -23.47~-15.78ppm/℃;
The raw materials are as follows: ZnO, TiO2、Nb2O5、Li2CO3、B2O3And SiO2Mixing (0.15+0.35x) ZnO- (0.55-0.05x) TiO according to a chemical formula2-(0.15+0.35x)Nb2O5-(0.3y+xy)Li2CO3-(0.5y+xy)B2O3 -(0.2y+xy)SiO2X =0.4-0.6, y =0.01-0.04, prepared by a solid phase method.
2. The ZnO-TiO of claim 12-Nb2O5The preparation method of the base LTCC material comprises the following specific steps:
step 1, adding ZnO and TiO2、Nb2O5、Li2CO3、B2O3And SiO2The original powder is prepared into (0.15+0.35x) ZnO- (0.55-0.05x) TiO according to a chemical general formula2-(0.15+0.35x)Nb2O5-(0.3y+xy)Li2CO3-(0.5y+xy)B2O3 -(0.2y+xy)SiO2 ,x=0.4-0.6, y=0.01-0.04;
Step 2, filling the ingredients obtained in the step 1 into a ball milling tank, taking zirconium balls and deionized water as grinding media, and mixing the following ingredients: zirconium ball: carrying out planetary ball milling for 5-7 hours at a deionized water mass ratio of 1: 5-7: 2-4, then drying at 80-100 ℃, sieving by using a 40-60 mesh screen, and finally presintering for 2-4 hours at 900-1000 ℃ in an atmosphere;
step 3, mixing the powder subjected to the pre-sintering in the step 2 into powder: zirconium ball: performing secondary ball milling on the deionized water in a mass ratio of 1: 5-7: 1-3 for 3-6 hours, taking out and drying, and adding an acrylic acid solution into the obtained powder for granulation;
and 4, pressing and molding the powder granulated in the step 3, removing the glue, raising the temperature to 875-950 ℃, and preserving the heat for 4-6 hours to obtain the low-temperature sintered microwave dielectric ceramic.
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Effects of B2O3 addition on sintering behavior and microwave dielectric properties of ixiolite-structure ZnTiNb2O8 ceramics;Haitao Wu等;《Journal of alloys and compounds》;20160407;第679卷;第26页摘要部分,第27页第2节第1段 * |
Effects of Li2O-B2O3-SiO2 glass on the low-temperature sintering of Zn0.15Nb0.3Ti0.55O2 ceramics;Li,Enzhu等;《Ceramics International》;20180131;第44卷;第8072页第2.1节,第8077页第3.4.节第1段及图9,第8073页第3.1.节第1段及图1,第8080页第4节 * |
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