CN105801119A - Microwave dielectric LTCC material and preparation method thereof - Google Patents

Microwave dielectric LTCC material and preparation method thereof Download PDF

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CN105801119A
CN105801119A CN201610310609.8A CN201610310609A CN105801119A CN 105801119 A CN105801119 A CN 105801119A CN 201610310609 A CN201610310609 A CN 201610310609A CN 105801119 A CN105801119 A CN 105801119A
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tio
ltcc
cawo
raw material
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CN105801119B (en
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苏桦
张硕
唐晓莉
张怀武
荆玉兰
李元勋
刘保元
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University of Electronic Science and Technology of China
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Abstract

The invention belongs to the field of electronic ceramic materials and preparation thereof, and in particular relates to a microwave dielectric LTCC material and a preparation method thereof. The CaWO4 system microwave dielectric LTCC material provided by the invention comprises two phases of mixed CaWO4 and Li2TiO3 and 0.5-1wt% of an LBSCA glass fluxing agent, wherein tetragonal-phase scheelite CaWO4 is taken as the main crystal phase; a monoclinic system structure Li2TiO3 is taken as the auxiliary phase; the weight percentage ratio of the mixed material CaWO4 to Li2TiO3 is (84-86%):(14-16%); the total mixed material weight percentage of the LBSCA glass fluxing agent is 0.5-1wt%. The sintering temperature of the material is 900-950 DEG C, the dielectric constant of the material is 11.8-12.4, the Q*f value of the material is 57000-76000GHz, and the temperature coefficient of resonance frequency of the material is minus 2.9-1.1ppm/DEG C. The microwave dielectric LTCC material can be widely applied to LTCC microwave substrates and laminated microwave devices and modules.

Description

A kind of micro-wave dielectric LTCC material and preparation method thereof
Technical field
The invention belongs to electron ceramic material and manufacture field thereof, be specifically related to one and there is low-loss and low resonance Micro-wave dielectric LTCC material of frequency-temperature coefficient characteristic and preparation method thereof.
Background technology
In recent years, the appearance of LTCC (LTCC) technology, for passive device and passive/active The development of device hybrid integrated creates condition, and obtains widely in lamination sheet type passive device rapidly Application.A lot of electronically materials and component manufacturing enterprises and colleges and universities all to various LTCC planar passive devices and Assembly expands research and development and produces, and in order to obtain high performance LTCC passive integrated devices and assembly, first First need high performance LTCC material.
But the high-performance LTCC material of at present commercialization is mainly abroad monopolized, domestic in this field the most not Key breakthrough can be obtained, cause LTCC integrated device that China researches and develops and assembly cost the highest, be unfavorable for The application of corresponding product and popularization, on the other hand due under one's control in core key technology, seriously hinder The development of China's LTCC industry.Therefore, exploitation has the high-performance LTCC material of independent intellectual property right Extremely urgent.
Micro-wave dielectric LTCC material is the branch being most widely used in LTCC material.General is micro- Ripple dielectric ceramic material sintering temperature is all more than 1100 DEG C, but in order to (sintering temperature is with LTCC technique 800 DEG C～950 DEG C) compatible, its sintering temperature need to be reduced to less than 950 DEG C.Frequently with method mainly wrap Include interpolation eutectic oxide or glass helps burning, introduces chemical synthesis process and use superfine powder to do raw material etc.； Latter two is with high costs and has certain process limitation, thus interpolation eutectic oxide or glass are current Realize the main method of LTCC microwave dielectric ceramic material.Even if but take this method, the most many micro- The sintering temperature of ripple dielectric ceramic material is the highest, it is also difficult to realize low-temperature sintering, and secondly, too much eutectic aoxidizes Thing or the incorporation of glass, also can constitute the biggest impact to the drain performance of material, cause Q × f to decline the biggest. And conventional eutectic oxide B2O3And V2O5, can be easily caused in LTCC technique later stage casting processes Slurry viscosity is excessive and unstable, limits its actual application.Additionally, in order to make LTCC material energy more preferably Apply in LTCC integrated device and assembly, the requirement to its temperature coefficient of resonance frequency is more and more higher, I.e. require that its dielectric properties variation with temperature should be the least, so could preferably ensure LTCC collection Become device and the stability of assembly property.
CaWO4Material, conventional research report is concentrated mainly on photo cathode, scintillator detector and optical fiber The aspects such as application.Discovered in recent years CaWO4System material also has the microwave dielectric property that comparison is excellent, because of This also has been reported that has carried out some research work as microwave dielectric material.CaWO4For scheelite-type structure, Belong to tetragonal crystal system.CaWO4Sintering temperature be about 1200 DEG C, its dielectric properties are as follows: DIELECTRIC CONSTANT εr Being about 9～10, Q × f is about 50000～60000GHz, temperature coefficient of resonance frequency τf=(-50～-40) ppm/℃。CaWO4One prominent shortcoming of ceramic material is exactly difficult one-tenth porcelain, and sintered sample hollow air-gap is relatively Many.
Sung HunYoon et al. have studied employing hot pressing sintering method to improve CaWO4The one-tenth porcelain density of sample, And under 1150 DEG C of sintering temperatures, obtained the ceramic ε that microwave property is followingr=10.4, Q × f=63000GHz, τf=-53ppm/ DEG C of (" Investigation of the relations between structure and microwave Dielectric properties of divalent metal tungstate compounds ", J.Eur.Ceram.Soc., 2006, 26,2051-2054).I1-Hwan Park reports CaWO4With Mg2SiO4Mix, improve material The one-tenth porcelain density of system also obtains good microwave property: 0.9CaWO4-0.1Mg2SiO41200 DEG C of burnings Forge, εr=10.0, Q × f=129858GHz, τf=-49.6ppm/ DEG C of (" Microwave dielectric properties and mixture behavior of CaWO4-Mg2SiO4Ceramics ", Jpn.J.Appl.Phys.Vol.40 (2001) pp.4956-4960), this mixing material system has the lowest dielectric to be damaged Consumption, but high temperature sintering can only be realized.
Summary of the invention
For above-mentioned existing problems or deficiency, the invention provides a kind of micro-wave dielectric LTCC material and system thereof Preparation Method, with CaWO4And Li2TiO3It is mixed with, and comprises 0.5～1wt%LBSCA glass and flux reality Existing CaWO4The micro-wave dielectric LTCC material of system.While achieving low-temperature sintering, it is lost low, and And temperature coefficient of resonance frequency is little, and its good application prospect in LTCC integrated device and assembly.
This micro-wave dielectric LTCC material, comprises CaWO4And Li2TiO3Mix is biphase, also comprises 0.5～1wt%LBSCA glass flux, wherein principal crystalline phase is Tetragonal scheelite CaWO4, auxiliary phase is Monoclinic structure Li2TiO3；CaWO4And Li2TiO3The percentage by weight of compound is 84～86%: 14～16%, and the LBSCA glass cosolvent that total compound percentage by weight is 0.5～1wt%.
Described principal crystalline phase CaWO4Its raw material composition is CaCO according to mol ratio3: WO3=1:1.
Described auxiliary phase Li2TiO3Its raw material composition is Li according to mol ratio2CO3: TiO2=1:1.
Described LBSCA glass flux, its raw material composition is Li in molar ratio2CO3:B2O3:SiO2: CaO: Al2O3=52.35～52.55:30.96～31.16:11.89～12.09:2.15～2.35:2.15～2.35.
The CaWO that the present invention provides4System micro-wave dielectric LTCC material, its sintering temperature is 900～950 DEG C, Dielectric constant 11.8～12.4, Q × f value 57000～76000GHz, temperature coefficient of resonance frequency-2.9～1.1 ppm/℃.Can be widely applied in LTCC microwave base plate, laminated microwave device and module.
Its preparation method is as follows:
Step 1: according to mol ratio CaCO3: WO3=1:1 weighing configuration CaWO4Raw material；According to mole Compare Li2CO3: TiO2=1:1 weighing configuration Li2TiO3Raw material；The CaWO that will prepare4And Li2TiO3Raw material Carry out a ball milling respectively uniform with batch mixing, then be respectively dried standby；
Step 2: be respectively put into crucible and compacting, by 2～3 DEG C after being sieved by two kinds of drying material of step 1 gained / minute heating rate rise to 850 DEG C and carry out pre-burning, be incubated 2～3 hours, furnace cooling obtains respective pre- Imitation frosted glass, and it is respectively put in mortar levigate standby；
Step 3: by raw material Li in molar ratio2CO3:B2O3:SiO2: CaO:Al2O3=52.35～52.55: 30.96～31.16:11.89～12.09:2.15～2.35:2.15～2.35 dispensings, wet mixing loads after drying Crucible, is warmed up to 1000 DEG C by 3 DEG C/minute in sintering furnace, directly takes out from stove and pour into after being incubated 2 hours Quenching in cold water, then dries and levigate obtains LBSCA glass cosolvent；
Step 4: the CaWO that step 2 is prepared4And Li2TiO3Preburning material is according to percentage by weight CaWO4: Li2TiO3=84～86%:14～16% carry out dispensing mixing, are subsequently adding compound and cosolvent gross weight 0.5～1wt% step 3 gained LBSCA glass cosolvent, three one arises from and carries out secondary ball milling in ball mill, And dry；
Step 5: product step 4 prepared adds the PVA solution that mass percent is 10%～20% and makees For binding agent, carry out pelletize dry-pressing formed；
Step 6: put in sintering furnace by step 5 products therefrom, is risen to by the heating rate of 2～3 DEG C/min 300 DEG C and be incubated 2～3 hours, it is further continued for being warming up to 500～550 DEG C and being incubated 2～4 hours；The most again by 2～4 DEG C / minute heating rate rise to 900 DEG C～950 DEG C and be sintered, and be incubated 2～3 hours, then by 2～4 DEG C/minute The rate of temperature fall of clock is down to 500～550 DEG C, and last furnace cooling obtains LTCC microwave dielectric ceramic material.
In described step 5, the concentration of PVA solution is 8～10%.
By based on scheelite-type structure CaWO in the present invention4With monoclinic structure Li2TiO3Compound, then Further by appropriate LBSCA glass flux formed micro-wave dielectric LTCC material system.Due to Li2TiO3There is the sintering temperature less than 900 DEG C and there is positive temperature coefficient of resonance frequency, thus by its with There is the CaWO of negative temperature coefficient of resonance frequency4It is combined according to a certain percentage, on the one hand can by material just The counteracting of negative temperature performance, it is thus achieved that close to the temperature coefficient of resonance frequency characteristic of zero point, the most all right Suitably reduce the sintering temperature of whole material system, less amount of glass cosolvent thus can be used to adulterate Realizing material system low-temperature sintering, therefore the loss to reducing material system is the most very good.At LTCC Technical field has the highest using value.
In sum, the CaWO that the present invention provides4System micro-wave dielectric LTCC ceramic material: it sinters temperature Degree is 900～950 DEG C, dielectric constant 11.8～12.4, Q × f value 57000～76000GHz, resonant frequency temperature Degree coefficient-2.9～1.1ppm/ DEG C.Can be widely applied in LTCC microwave base plate, laminated microwave device and module.
Accompanying drawing explanation
Low-loss that Fig. 1 provides for the present invention, the preparation of low-temperature coefficient LTCC microwave dielectric ceramic material Process flow diagram；
Fig. 2 is the XRD figure spectrum of the sample of sintering doping LBSCA at a temperature of 900 DEG C.
Detailed description of the invention
A kind of specific embodiments of the described LTCC microwave dielectric ceramic material being the present invention below.Such as figure Shown in 1, the concrete preparation method of this material is as follows:
Step 1: according to mol ratio CaCO3: WO3=1:1 weighing configuration CaWO4Raw material, according to rubbing You compare Li2CO3: TiO2=1:1 weighing configuration Li2TiO3Raw material；The CaWO that will prepare4And Li2TiO3 Raw material carries out a ball milling respectively, and the uniform post-drying of batch mixing is standby；
Step 2: be respectively put into crucible and compacting after being sieved by two kinds of drying material of step 1 gained, 3 DEG C/minute The heating rate of clock rises to 850 DEG C and carries out pre-burning, is incubated 3 hours, and furnace cooling obtains respective Preburning material；
Step 3: raw material Li in molar ratio2CO3:B2O3:SiO2: CaO:Al2O3=52.45:31.06: 11.99:2.25:2.25 dispensing, wet mixing loads crucible after drying, heats up by 3 DEG C/minute in sintering furnace To 1000 DEG C, directly take out from stove after being incubated 2 hours and pour quenching in cold water into, then dry levigate obtaining LBSCA glass flux；
Step 4: by CaWO4 and Li of step 2 gained2TiO3Preburning material takes out from crucible, puts respectively Enter in mortar levigate, then according to percentage by weight CaWO4: Li2TiO3=86%:14% carries out weighing to be mixed Close, press the 0.5wt% addition LBSCA glass flux of compound and flux gross weight the most again, then Secondary ball milling is carried out together in ball mill；
Step 5: after secondary ball abrasive material step 4 prepared is dried, adding mass percent is the PVA of 20% Solution carries out pelletize and dry-pressing formed for cylinder；
Step 6: put in sintering furnace by step 5 products therefrom, rises to 300 DEG C by the heating rate of 2 DEG C/min And it is incubated 2 hours, it is further continued for being warming up to 500 DEG C and being incubated 4 hours；The most again by the intensification of 4 DEG C/min Speed rises to 900 DEG C respectively, 925 DEG C, and 950 DEG C are sintered, and is incubated 3 hours, then by 4 DEG C/min Rate of temperature fall be down to 500 DEG C, last furnace cooling obtains LTCC microwave dielectric ceramic material.
Table 1
Table 1 is that different sintering temperature and different LBSCA glass doping are to material system microwave dielectric property Impact.
XRD figure spectrum time (a) represents doping 0.5wt%LBSCA in Fig. 2；B () represents doping XRD figure spectrum when 1wt%LBSCA.Can there is two kinds of characteristic peak as seen from the figure, be respectively Principal crystalline phase CaWO4 (◆) and auxiliary phase Li2TiO3(●).Other are not had after doping LBSCA glass Generate mutually.

Claims (5)

1. a micro-wave dielectric LTCC material, it is characterised in that: comprise CaWO4And Li2TiO3Mixing Biphase, also comprise 0.5～1wt%LBSCA glass flux, wherein principal crystalline phase is Tetragonal scheelite CaWO4, auxiliary phase is monoclinic structure Li2TiO3；CaWO4And Li2TiO3The weight percent of compound Ratio is 84～86%:14～16%, and the LBSCA glass that total compound percentage by weight is 0.5～1wt% Cosolvent；
Described principal crystalline phase CaWO4Its raw material composition is CaCO according to mol ratio3: WO3=1:1；
Described auxiliary phase Li2TiO3Its raw material composition is Li according to mol ratio2CO3: TiO2=1:1；
Described LBSCA glass flux, its raw material composition is Li in molar ratio2CO3:B2O3:SiO2: CaO: Al2O3=52.35～52.55:30.96～31.16:11.89～12.09:2.15～2.35:2.15～2.35.
2. micro-wave dielectric LTCC material as claimed in claim 1, it is characterised in that: sintering temperature is 900～950 DEG C, dielectric constant 11.8～12.4, Q × f value 57000～76000GHz, temperature coefficient of resonance frequency -2.9～1.1ppm/ DEG C.
3. micro-wave dielectric LTCC material as claimed in claim 1, it is characterised in that: it is applied to LTCC micro- In ripple substrate, laminated microwave device and module.
4. the preparation method of micro-wave dielectric LTCC material as claimed in claim 1, comprises the following steps:
Step 1: according to mol ratio CaCO3: WO3=1:1 weighing configuration CaWO4Raw material；According to rubbing You compare Li2CO3: TiO2=1:1 weighing configuration Li2TiO3Raw material；The CaWO that will prepare4And Li2TiO3 It is uniform with batch mixing that raw material carries out a ball milling respectively, then is respectively dried standby；
Step 2: be respectively put into crucible and compacting, by 2～3 DEG C after being sieved by two kinds of drying material of step 1 gained / minute heating rate rise to 850 DEG C and carry out pre-burning, be incubated 2～3 hours, furnace cooling obtains respective pre- Imitation frosted glass, and it is respectively put in mortar levigate standby；
Step 3: by raw material Li in molar ratio2CO3:B2O3:SiO2: CaO:Al2O3=52.35～52.55: 30.96～31.16:11.89～12.09:2.15～2.35:2.15～2.35 dispensings, wet mixing loads after drying Crucible, is warmed up to 1000 DEG C by 3 DEG C/minute in sintering furnace, directly takes out from stove and pour into after being incubated 2 hours Quenching in cold water, then dries and levigate obtains LBSCA glass cosolvent；
Step 4: the CaWO that step 2 is prepared4And Li2TiO3Preburning material is according to percentage by weight CaWO4: Li2TiO3=84～86%:14～16% carry out dispensing mixing, are subsequently adding compound and cosolvent gross weight 0.5～1wt% step 3 gained LBSCA glass cosolvent, three one arises from and carries out secondary ball milling in ball mill, And dry；
Step 5: product step 4 prepared adds the PVA solution that mass percent is 10%～20% and makees For binding agent, carry out pelletize dry-pressing formed；
Step 6: put in sintering furnace by step 5 products therefrom, is risen to by the heating rate of 2～3 DEG C/min 300 DEG C and be incubated 2～3 hours, it is further continued for being warming up to 500～550 DEG C and being incubated 2～4 hours；The most again by 2～4 DEG C / minute heating rate rise to 900 DEG C～950 DEG C and be sintered, and be incubated 2～3 hours, then by 2～4 DEG C/minute The rate of temperature fall of clock is down to 500～550 DEG C, and last furnace cooling obtains LTCC microwave dielectric ceramic material.
5. the preparation method of micro-wave dielectric LTCC material as claimed in claim 4, it is characterised in that: described In step 5, the concentration of PVA solution is 8～10%.
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CN106904960A (en) * 2017-03-14 2017-06-30 电子科技大学 A kind of Mg2SiO4‑Li2TiO3Compound system LTCC materials and preparation method thereof
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