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CN103193389B - Microwave dielectric glass ceramics material and constituent thereof - Google Patents

Microwave dielectric glass ceramics material and constituent thereof Download PDF

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Publication number
CN103193389B
CN103193389B CN201210003557.1A CN201210003557A CN103193389B CN 103193389 B CN103193389 B CN 103193389B CN 201210003557 A CN201210003557 A CN 201210003557A CN 103193389 B CN103193389 B CN 103193389B
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glass ceramics
phase composition
microwave dielectric
ceramics material
dielectric glass
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CN103193389A (en
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周振嘉
冯奎智
陈书缨
朱立文
庄朝栋
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Dongguan Huake Electronic Co Ltd
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Dongguan Huake Electronic Co Ltd
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Abstract

The invention provides a kind of microwave dielectric glass ceramics material, comprising: a principal phase composition, this principal phase composition comprises at least one glass ceramic material Ca xmg ysi zo (x+y+2z), wherein x, y are respectively 0 to 50mole%, and z is 0 to 50mole%; And second-phase composition, this second-phase composition can be CaTiO 3, Mg 2siO 4, ZrO 2, TiO 2or its combination, it is by this principal phase composition of mixing and at least three kinds or four kinds of dielectric materialss, and common sintering generated at 900 DEG C, and wherein, dielectric materials is selected from CaTiO 3, MgTiO 3, ZrTiO 4and TiO 2the group formed.The present invention also provides a kind of microwave dielectric glass ceramics powder constituent thing for the preparation of microwave dielectric glass ceramics material.Accordingly, microwave dielectric glass ceramics material of the present invention can possess the characteristics such as low-k, high quality factor, low temperature Drift Parameter and low capacitance temperature factor simultaneously, becomes a kind of microwave dielectric glass ceramics material possessing height using value.

Description

Microwave dielectric glass ceramics material and constituent thereof
Technical field
The present invention about a kind of microwave dielectric glass ceramics material, espespecially a kind of pyroxene microwave dielectric glass ceramics material possessing low-k and high quality factor.
Background technology
In order to meet the demand of communication part miniaturization in contemporary semiconductor industry, high stability, high capacity and high mobility, microwave dielectric material becomes a kind of communication material possessing excellent frequency selectivity and stabilized frequency needing development at present badly.
In the technology making microwave dielectric material, can pass through obtained by glass, pottery or glass ceramic material.Wherein, stupalith is made up of ceramic, after the high temperature sintering step of 1200 to 1350 DEG C, can obtain the polycrystalline sintered compact with certain physical strength; Glass material is after one is cooled rapidly by molten state, each intermolecular a kind of solid not having enough time to form xln; Glass ceramic material is then a kind of polycrystalline solids material mainly comprising glassy phase, and its manufacturing processed first glass melting is formed glassy phase, then after heat treated crystallization step, makes it be formed to have the polycrystalline solids material of xln.
Existing many people drop into the research of microwave dielectric material at present, and in No. I248429th, TaiWan, China patent announcement, disclose a kind of ZST microwave dielectric ceramic material, it is with (Zr x, Sn y) Ti zo 4-(1-n) MO as body base material, and adds a glass baseplate in body base material, can sinter in the sintering temperature of less than 1000 DEG C, possesses the good microwave dielectric property that Q × f is greater than 5000 simultaneously.
In addition, in TaiWan, China patent announcement I339196 and No. I339197, disclose a kind of microwave dielectric ceramic material, it is with Mg 2siO 4(forsterite) as principal phase composition, and with TiO 2, SrTiO 3, CaTiO 3for secondary phase composition, produce the low temperature being suitable for less than 1000 DEG C and sinter, to produce specific inductivity (K) microwave dielectric ceramic material between 9 to 10.
Summary of the invention
The present invention is different from the microwave dielectric material of prior art, develop a kind of microwave dielectric glass ceramics material, it can in conjunction with the characteristic of pyroxene glass ceramic material and dielectric materials, produce the microwave dielectric ceramic constituent simultaneously possessing low-k, high quality factor and stability, use and promote glass ceramic material in the using value of semiconductor industry.
For reaching above-mentioned purpose, the invention provides a kind of microwave dielectric glass ceramics material, comprising: a principal phase composition, this principal phase composition comprises at least one glass ceramic material, and the structural formula of this glass ceramic material is Ca xmg ysi zo (x+y+2z), wherein x is 0 to 50 molar percentage, and y is 0 to 50 molar percentage, and z is 0 to 50 molar percentage; And a second-phase composition, this second-phase composition is that common sintering generated by this principal phase composition of mixing and at least three kinds of dielectric materialss and under a preset temperature, and this dielectric materials is selected from following formed group: calcium titanate (CaTiO 3), magnesium titanate (MgTiO 3), zirconia titanate (ZrTiO 4) and titanium dioxide (TiO 2).
In microwave dielectric glass ceramics material of the present invention, glass ceramic material in principal phase composition is the glass ceramic material of pyroxene, and it is by mixing at least two kinds of magnesium oxide (MgO), calcium oxide (CaO) or silicon-dioxide (SiO 2) oxide compound, at 1500 DEG C to 1800 DEG C, first form a vitreous state, then this vitreous state is sintered at 700 DEG C to 1000 DEG C generated.In this, be 100 molar percentages with the total amount of magnesium oxide, calcium oxide and silicon-dioxide, the addition of this magnesium oxide and calcium oxide is respectively 0 to 50 molar percentage, and the addition of this silicon-dioxide is 0 to 50 molar percentage.According to different adding proportions, at 1500 DEG C to 1800 DEG C, burn till a vitreous state, and this vitreous state is sintered at 700 DEG C to 1000 DEG C, when the temperature being preferably less than 900 DEG C sinters, can be made into the pyroxene glass ceramic material of various different phase structure, such as: CaSiO 3(wollastonite (wollastonite)), Ca 3mgSi 2o 8(manganolite (merwinite)), Ca 2mgSi 2o 7(akermanite (Akermanite)) or CaMgSi 2o 6(diopside (diopside)).Various pyroxene glass ceramic materials obtained by aforesaid method, its specific inductivity (K), even can lower than less than 9 all lower than less than 10; And the quality factor of glass ceramic material (Q × f) is all greater than more than 7000GHz.Accordingly, when using pyroxene glass ceramic material and other dielectric materials jointly to sinter, the microwave dielectric glass ceramics material possessing excellent characteristic can be obtained.
In microwave dielectric glass ceramics material of the present invention, second-phase composition is mutually mixed by above-mentioned principal phase composition and at least three kinds or four kinds of dielectric materialss and jointly sintered in a preset temperature generated.In this, in this second-phase composition, be 100 weight percents with the total amount of principal phase composition and dielectric materials, the content of dielectric materials is between 0 to 30 weight percent, be preferably between 0 to 20 weight percent, better is between 13 to 15 weight percents.Accordingly, when these dielectric materialss make an addition to above-mentioned at least one principal phase composition, and below 900 DEG C, when jointly sintering under being preferably the preset temperature of 700 DEG C to 900 DEG C, be generate as: comprise calcium titanate (CaTiO 3), Magnesium Silicate q-agent (Mg 2siO 4), titanium dioxide (TiO 2) or zirconium white (ZrO 2) second-phase composition.
On the other hand, the present invention also provides a kind of microwave dielectric glass ceramics powder constituent thing for the preparation of aforementioned microwave dielectric glass ceramics material, and it comprises: at least one glass ceramic material, and the structural formula of this glass ceramic material is Ca xmg ysi zo (x+y+2z), wherein x is 0 to 50 molar percentage, and y is at 0 to 50 molar percentage, and z is at 0 to 50 molar percentage; And a ceramic powder, it comprises and is selected from by calcium titanate (CaTiO 3), magnesium titanate (MgTiO 3), zirconia titanate (ZrTiO 4) and titanium dioxide (TiO 2) at least three kinds of dielectric materialss in the group that forms.
Accordingly, jointly sinter rear obtained microwave dielectric glass ceramics material by aforementioned proportion and can possess following several characteristics: (1), low-k (K): the specific inductivity of this constituent is between 7 to 9; (2), high quality factor (Q × f): the quality factor of this constituent, more than 7000GHz, is preferably and is significantly promoted to more than 15000GHz; (3), stable temperature Drift Parameter (τ f): the temperature Drift Parameter of this constituent can be controlled in ± 20 or ± 25ppm between; (4), stable capacitance temperature factor (temperaturecoefficientofcapacitance, TCC): the capacitance temperature factor of this constituent can be controlled in ± 28 or ± 35ppm between.
In sum, the present invention is in conjunction with pyroxene glass ceramic material and different dielectric properties of materials, be suitable for LTCC (LowTemperatureCo-firedCeramics, LTCC) sinter under sintering temperature, obtain and possess the microwave dielectric glass ceramics material of excellent electrical quality and stability, to use in lifting prior art glass ceramic material in the using value of semiconductor industry.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction chart of microwave dielectric ceramic material of the present invention.
Embodiment
Below, will be further described content of the present invention through the following example, but it is to be understood that, this embodiment only in order to the use of explanation, and should not be regarded as implementing restriction of the present invention.
Embodiment
The characteristic that the present invention possesses in conjunction with glass ceramic material and dielectric materials, under certain blending ratio, common sintering produces the microwave dielectric glass ceramics material possessing excellent electrical quality and stability.
1, the glass ceramic material as principal phase composition is prepared
Mixed oxidization magnesium (MgO), calcium oxide (CaO) and silicon-dioxide (SiO 2) three kinds of oxide powders, and at the temperature of 900 DEG C, after sintering, form the pyroxene glass ceramic material of various different phase structure, be respectively CaSiO 3" wollastonite (wollastonite) ", Ca 3mgSi 2o 8" manganolite ", Ca 2mgSi 2o 7" akermanite (Akermanite) " or CaMgSi 2o 6" diopside (diopside) ".Wherein, the addition of various oxide compound and the specific inductivity of glass ceramic material thereof and quality factor test result as shown in table 1.
Table 1: various oxide compound addition and the specific inductivity of glass ceramic material made thereof and quality factor.
CaSiO 3 Ca 3MgSi 2O 8 Ca 2MgSi 2O 7 CaMgSi 2O 6
CaO addition 50mol% 50mol% 40mol% 25mol%
MgO addition 0mol% 16.7mol% 20mol% 25mol%
SiO 2Addition 50mol% 33.3mol% 40mol% 50mol%
Specific inductivity 6.6-7.4 6.1-7.8 7.3-7.9 7.1-8.2
Quality factor (GHz) 13000 7300 8800 8000
2, preparation is containing the microwave dielectric glass ceramics material of second-phase composition
Using above-mentioned a kind of glass ceramic material powder as principal phase composition, it is made to mix with ceramic powder, wherein this ceramic powder comprises at least four kinds of dielectric materials mixing and jointly sinters, and to generate second-phase composition, uses the obtained microwave dielectric glass ceramics material comprising second-phase composition.
Mixed C aMgSi 2o 6glass ceramic material and CaTiO 3, MgTiO 3, ZrTiO 4and TiO 2deng dielectric materials, at 1500 DEG C to 1800 DEG C, melting forms a vitreous state, and to be placed in the sintering environment of 900 DEG C common sintering 2 hours, generates and comprises CaTiO 3, TiO 2, Mg 2siO 4or ZrO 2second-phase composition.
Accordingly, can complete the preparation of microwave dielectric glass ceramics material through above-mentioned making method, this constituent can comprise principal phase composition and second-phase composition simultaneously, to form the microwave dielectric glass ceramics material possessing excellent characteristic.Analyze the structure of microwave dielectric glass ceramics material of the present invention with X-ray powder diffraction instrument, its result as shown in Figure 1.Wherein, 2 θ are 29.8 °, 35.5 °, 30.8 °, 30.3 °, 34.8 ° and represent CaMgSi 2o 6the X-ray diffraction peak of (diopside); 2 θ are 33.14 ° and represent CaTiO 3x-ray diffraction peak; 2 θ are 36.4 ° and 32.3 ° and represent Mg 2siO 4x-ray diffraction peak; 2 θ are 31.4 ° and then represent ZrO 2x-ray diffraction peak.
Wherein, be 100 weight percents with the total amount of principal phase composition and dielectric materials, the test result of the content of this dielectric materials and the electrical quality of microwave dielectric glass ceramics material and stability is as shown in table 2.
Table 2: the electrical quality of microwave dielectric glass ceramics material and stable test result.
Shown by the test result of upper table, when the content of dielectric materials is between 0 to 30 weight percent, its specific inductivity is all lower than less than 9, and quality factor is paramount reaches 15100GHz.Especially, when the content of dielectric materials is between 10 to 21 weight percent, more can the temperature Drift Parameter of stability microwave dielectric glass ceramic material and capacitance temperature factor effectively, make temperature Drift Parameter maintain ± 30ppm between, and its capacitance temperature factor also can maintain ± 40ppm between.Be more preferred from, when the content of dielectric materials is between 13 to 15 weight percent, the specific inductivity of this microwave dielectric glass ceramics material, quality factor, temperature Drift Parameter and capacitance temperature factor all possess excellent characteristic.
3, the another kind of microwave dielectric glass ceramics material containing second-phase composition of preparation
Using above-mentioned at least two kinds of glass ceramic material powder as principal phase composition, it is made to mix with ceramic powder, wherein this ceramic powder comprises three kinds of dielectric materialss, mixes and jointly sinters to produce second-phase composition, using the microwave dielectric glass ceramics material that obtained another kind comprises second-phase composition.
Mixed C aSiO 3, CaMgSi 2o 6the glass ceramic material of (diopside) and CaTiO 3, MgTiO 3and ZrTiO 4deng dielectric materials, at 1500 DEG C to 1800 DEG C, melting forms a vitreous state, and to be placed in the sintering environment of 900 DEG C common sintering 2 hours, comprises CaTiO to generate 3, Mg 2siO 4or ZrO 2second-phase composition.
Accordingly, can be completed the preparation of microwave dielectric glass ceramics material by above-mentioned making method, this constituent can comprise principal phase composition and second-phase composition simultaneously, to form the microwave dielectric glass ceramics material possessing excellent characteristic.
Wherein, be 100 weight percents with the total amount of principal phase composition and dielectric materials, the test result of the content of this dielectric materials and the electrical quality of microwave dielectric glass ceramics material and stability is as shown in table 3.
Table 3: the electrical quality of microwave dielectric glass ceramics material and stable test result.
Shown by the test result of upper table, when the content of dielectric materials is between 0 to 30 weight percent, its specific inductivity is all lower than less than 10, and quality factor is paramount reaches 15000GHz.Especially, when the content of dielectric materials is between 13 to 21 weight percent, more can the temperature Drift Parameter of stability microwave dielectric glass ceramic material and capacitance temperature factor effectively, make temperature Drift Parameter maintain ± 25ppm between, and its capacitance temperature factor also can maintain ± 35ppm between.Be more preferred from, when the content of dielectric materials is between 19 to 21 weight percent, the specific inductivity of this microwave dielectric glass ceramics material, quality factor, temperature Drift Parameter and capacitance temperature factor all possess excellent characteristic.
Accordingly, two kinds of microwave dielectric glass ceramics materials of the present invention in conjunction with the characteristic of glass ceramic material and dielectric materials, can produce the microwave dielectric glass ceramics material having electrical quality and stability concurrently.

Claims (10)

1. a microwave dielectric glass ceramics material, comprising:
One principal phase composition, this principal phase composition comprises at least one glass ceramic material, and the structural formula of this glass ceramic material is Ca xmg ysi zo (x+y+2z), wherein x is 0 to 50 molar percentage, and y is 0 to 50 molar percentage, and z is 0 to 50 molar percentage; And,
One second-phase composition, this second-phase composition is by after the described principal phase composition of mixing and dielectric materials, after at 1500 DEG C to 1800 DEG C, melting forms a vitreous state and at a predetermined temperature common sintering generated, and described dielectric materials is calcium titanate, magnesium titanate and zirconia titanate.
2. microwave dielectric glass ceramics material as claimed in claim 1, wherein, the glass ceramic material of described principal phase composition is by mixing at least two oxides, at 1500 DEG C to 1800 DEG C, melting forms a vitreous state, again this vitreous state is sintered at 700 DEG C to 1000 DEG C and generated, described oxide compound is selected from following formed group: magnesium oxide, calcium oxide and silicon-dioxide, wherein, with magnesium oxide, the total amount of calcium oxide and silicon-dioxide is 100 molar percentages, the addition of described magnesium oxide and calcium oxide is respectively 0 to 50 molar percentage, and the addition of described silicon-dioxide is 0 to 50 molar percentage.
3. microwave dielectric glass ceramics material as claimed in claim 1, wherein, described glass ceramic material is CaSiO 3, Ca 3mgSi 2o 8, CaMgSi 2o 6or Ca 2mgSi 2o 7.
4. microwave dielectric glass ceramics material as claimed in claim 1, wherein, described second-phase composition is calcium titanate, Magnesium Silicate q-agent, titanium dioxide or zirconium dioxide.
5. microwave dielectric glass ceramics material as claimed in claim 1, in described second-phase composition, be 100 weight percents with the total amount of described principal phase composition and described dielectric materials, the content of described dielectric materials is 0 to 30 weight percent.
6. microwave dielectric glass ceramics material as claimed in claim 1, wherein, described preset temperature is 700 DEG C to 900 DEG C.
7. the microwave dielectric glass ceramics material as described in any one of claim 1-6, its specific inductivity is lower than 10.
8. the microwave dielectric glass ceramics material as described in any one of claim 1-6, its quality factor is greater than 7000GHz.
9. microwave dielectric glass ceramics material as claimed in claim 4, wherein, be 100 weight percents with the total amount of described principal phase composition and described dielectric materials, when the content of described dielectric materials is 13 to 15 weight percent, the temperature Drift Parameter of described microwave dielectric glass ceramics material is between ± 20ppm.
10. microwave dielectric glass ceramics material as claimed in claim 4, wherein, be 100 weight percents with the total amount of described principal phase composition and described dielectric materials, when the content of described dielectric materials is 13 to 15 weight percent, the capacitance temperature factor of described microwave dielectric glass ceramics material is between ± 28ppm.
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CN107176834B (en) * 2016-03-11 2020-02-14 上海卡翱投资管理合伙企业(有限合伙) LTCC (Low temperature Co-fired ceramic) ceramic material with medium and high dielectric constant and preparation method thereof
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