CN103183510B - Niobium-magnesium-acid-bismuth based lithium-titanium co-replaced microwave dielectric ceramic material and preparation method thereof - Google Patents
Niobium-magnesium-acid-bismuth based lithium-titanium co-replaced microwave dielectric ceramic material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of microwave dielectric ceramic material manufacturing and particularly relates to a niobium-magnesium-acid-bismuth based microwave dielectric ceramic material and a preparation method thereof. The ceramic material comprises the following components in mole percentage by adjusting the reasonable proportions of dielectric function additives: 59%-60% of Bi2O3, 6.9%-7.0% of MgO, 30%-33.2% of Nb2O5, 0.15%-3.0% of Li3CO3 and 0.15%-3.0% of TiO2, wherein the Bi2O3, the MgO and the Nb2O5 are host materials, and the Li3CO3 and the TiO2 are the dielectric function additives. The dielectric constant of niobium-magnesium-acid-bismuth based ceramic material prepared by a conventional solid-phase synthesis method is 188-213, the dielectric loss is 0.00027-0.00031, and the dielectric temperature coefficient is -683ppm/DEG C-523ppm/DEG C. The niobium-magnesium-acid-bismuth based microwave dielectric ceramic material can be used for medium voltage controlled microwave devices in integrated circuits.
Description
Technical field
The present invention relates to microwave dielectric ceramic material manufacturing technology field, specifically magnoniobate bismuth base microwave dielectric ceramic material and preparation method.
Background technology
For adapting to the fast development of integrated circuit, scientist has done a large amount of research work; In recent years, Bi cubic pyrochlore structure has obtained research widely mutually, the pottery with this phase structure has very high dielectric constant and dielectric tuning rate, under room temperature, within the scope of sizable test frequency, have low dielectric loss, and sintering temperature is also lower, these performances make Bi base cubic pyrochlore structural ceramics in multi-layer capacitor and integrated equipment, have good application prospect.
As far back as the sixties in 20th century, Ba
xsr
1 xtiO
3(BST) the micro-wave dielectric tuning performance of ferroelectric material has just caused people's broad interest.The feature of BST ceramic material is that dielectric tuning rate is high, but dielectric loss is larger, and relevant research is many; In recent years, research finds that some Bi-based pyrochlor structural ceramic material has higher Dielectric tunable properties, and dielectric loss is little, moderate dielectric constant, and temperature coefficient is little, is a kind of micro-wave dielectric material with adjustable that has development prospect.
Consist of Bi
1.5znNb
1.5o
7bismuthino BZN material there is pyrochlore structure, dielectric constant is moderate.But BZN ceramic material tuning rate is low, reach certain tuning rate, tuning electric field requires very high; With respect to BZN ceramic material, another one take bismuth as matrix, there is cubic pyrochlore structure, with the Bi of ternary system
2o
3-MgO-Nb
2o
5for basic dielectric ceramic system (be called for short BMN base pottery) starts to be paid close attention in embedded capacitor application, reason is exactly the high dielectric constant that has of this individual system and low dielectric loss; Research shows, compd B i
2mg
2/3nb
4/3o
7dielectric constant very high, up to 210.And compd B i
2zn
2/3nb
4/3o
7dielectric constant be only 86, the introducing of divalence magnesium ion may have been played the effect that strengthens dielectric response, BMN Bi-based pyrochlor material is a kind of very promising novel microwave dielectric material with adjustable.
The preparation method of microwave dielectric ceramic materials is a lot, there are synthesis by solid state reaction, hydrothermal synthesis method, chemical codeposition method (CVD), sol-gal process (Sol-gel) etc., wherein adopt the maximum of solid-phase synthesis, the advantage of synthesis by solid state reaction is that method is simple to operation, and cost is lower.
Domestic and international many scholars do a lot of work preparing aspect bismuthino dielectric ceramic material, main achievement is as follows: the people such as the W.Ren of Pennsylvania State University have prepared the BZN film of Emission in Cubic on Pt/Si substrate by metal organic deposit (MOD) method, has first found the dielectric adjustable of BZN; The people such as R.L.Thayer are with having found Bi in the process of metal organic deposit (MOD) legal system for BZN film
2o
3-ZnO-Nb
2o
5a kind of low-temperature phase Bi in system
1.5zn
0.5nb
1.5o
6.5, this low-temperature phase is to obtain under lower than the condition of 600 ℃ in annealing temperature, cube pyrochlore constitution, and dielectric constant is 180, adjustable rate is 26%, temperature coefficient TCC Wei – 230ppm/ ℃; The people such as the S.W.Jiang of University of Electronic Science and Technology use pulsed laser deposition (PLD) method at Pt/SiO
2on/Si substrate, prepare BZN film, it is adjustable, and rate is greater than 6%, and loss is lower than 0.004; The Mg such as S.W.Jiang
2+replace the Zn in BZN material
2+ion, adopts PLD legal system for Bi
1.5mgNb
1.5o
7(BMN) Bi-based pyrochlor film, prepared BMN thin-film dielectric loss little (approximately 0.002), dielectric constant moderate (approximately 86), varies with temperature less (the about 500ppm/K of dielectric temperature coefficient T CC); The people such as the neat blast of University of Electronic Science and Technology, Jiang Shuwen adopt the method for magnetron sputtering to prepare Bi
1.5znNb
1.5o
7(BZN) dielectric loss of Bi-based pyrochlor film is 0.002 ~ 0.004, and dielectric tuning rate is about 20%; In addition the people such as AEHOON P, JIWEI W L studies and finds that BMN base ceramic material also exists application in phase shifter; The present invention adopts solid-phase synthesis directly to prepare the micro-wave dielectric magnoniobate bismuthino ceramic material of multi-component doped.
Summary of the invention
One of object of the present invention is to provide that a kind of properties of product are good, production cost is low, method is simple, can be suitable for the microwave dielectric ceramic material of suitability for industrialized production.
Two of object of the present invention is to provide a kind of preparation method of magnoniobate bismuth base microwave dielectric ceramic material.
To achieve these goals, the present invention is by the following technical solutions:
A kind of Bi
1.5mgNb
1.5o
7based microwave dielectric ceramics material, is characterized in that: the component of described material is by mole% being calculated as: Bi
2o
359%～60%, MgO6.9%～7.0%, Nb
2o
530%～33.2% is material of main part, Li
2cO
3, TiO
2being respectively 0.15%～3%, is dielectric function additive.
Described a kind of Bi
1.5mgNb
1.5o
7the preparation method of based microwave dielectric ceramics material, is characterized in that: utilize traditional solid-phase synthesis to prepare Bi
1.5mgNb
1.5o
7based microwave dielectric ceramics material: according to following molar percentage component, prepare burden, Bi
2o
359%～60%, MgO6.9%～7.0%, Nb
2o
530%～33.2% is material of main part, Li
2cO
3, TiO
2be respectively 0.15%～3% for dielectric function additive; Adopt agate ball and stainless cylinder of steel, absolute ethyl alcohol is ball-milling medium, agate ball: batching powder: the mass ratio of absolute ethyl alcohol is 2:1:1, and wet-milling 10h in planetary high-energy ball mill, rotating speed is 150rpm; The slurry that ball milling is good becomes dry powder at 70 ℃ of insulation 24 h; The PVA aqueous solution that employing mass fraction is 2% is as binding agent, and powder and PVA solution quality, than being 9:1, are then crossed the accurate sub-sieve of 150 target, and with the pressurize of 20MPa pressure, 5min suppresses, and makes powder become base; Base substrate is put into Si-Mo rod high-temperature electric resistance furnace, with the speed of 3 ℃/min, from room temperature, rise to 950 ℃, in air atmosphere, be incubated 150min, cool to room temperature with the furnace, complete the pre-burning to idiosome; After pre-burning, idiosome is smashed and carried out secondary ball milling, secondary ball milling parameter is identical with a ball milling, and the slurry that ball milling is good becomes dry powder at 70 ℃ of insulation 24 h; The PVA aqueous solution that employing mass fraction is 2% is as binding agent, and powder and PVA solution quality, than being 10:1, are then crossed the accurate sub-sieve of 100 target, and with the pressurize of 45MPa pressure, 5min suppresses, and makes powder become base; Base substrate is put into Si-Mo rod high-temperature electric resistance furnace, with the speed of 1 ℃/min, from room temperature, rises to 550 ℃, in air atmosphere, be incubated 300min, after with the speed of 2 ℃/min, rise to 1130 ℃ of sintering temperatures, in air atmosphere, be incubated 90min, cool to room temperature with the furnace.
After sintering completes, to billet surface fine sandpaper sanding and polishing, guarantee that base substrate two sides is smooth, zero defect, then by ceramic body coated on both sides silver slurry, in drying baker in 70 ℃ of oven dry; Sample after drying is put in resistance furnace, by room temperature, rises to 600 ℃, insulation 30min, forms silver electrode, obtains magnoniobate bismuthino ceramic material.
The present invention is by adjusting the rational proportion of dielectric function additive, the magnoniobate bismuthino ceramic material of preparing in conjunction with preparation method, and dielectric constant is 188～213, and dielectric loss is 0.00027～0.00031, and dielectric temperature coefficient is-683ppm/ ℃ ~-523ppm/ ℃; Magnoniobate bismuth base microwave dielectric ceramic material of the present invention can be used for the voltage-controlled microwave device of integrated circuit medium.
technical advantage
1, preparation process is simple, and repeatability is higher, and cost is lower, is convenient to realize large-scale production
2, by adjusting the ratio of dielectric function additive, BMN base ceramic material dielectric property are greatly improved; The Bi before reporting
1.5mgNb
1.5o
7dielectric ceramic material dielectric constant is 86 left and right, and dielectric loss is less than 0.005, and dielectric temperature coefficient is-550ppm/ ℃; Contrast therewith, prepared ceramic dielectric loss is less, and dielectric constant is improved, and dielectric temperature coefficient is less, and relaxation temperature, well below room temperature, can serve in integrated circuit BMN base ceramic material better.
Embodiment
After now embodiments of the invention being described in.
eXAMPLE l
1) utilize traditional solid-phase synthesis to prepare magnoniobate bismuth base microwave dielectric ceramic target: according to following molar percentage component, prepare burden, Bi
2o
3: 59.0866%, MgO:6.931%, Nb
2o
5: 33.137%, Li
2cO
3: 0.1588%, TiO
2: 0.6866%.
2) adopt agate ball, stainless cylinder of steel, absolute ethyl alcohol is ball-milling medium, agate ball: batching powder: nothing
The mass ratio of water-ethanol is 2:1:1, wet-milling 10h in planetary high-energy ball mill, and rotating speed is 150rpm; The slurry that ball milling is good becomes dry powder at 70 ℃ of insulation 24 h; The PVA aqueous solution that employing mass fraction is 2% is as binding agent, and powder and PVA solution quality, than being 9:1, are then crossed after the accurate sub-sieve of 150 target, and with the pressurize of 20MPa pressure, 5min suppresses, and makes powder become base; Base substrate is put into Si-Mo rod high-temperature electric resistance furnace, with the speed of 3 ℃/min, from room temperature, rise to 950 ℃, in air atmosphere, be incubated 150min, cool to room temperature with the furnace, complete the pre-burning to idiosome.
3) after pre-burning, idiosome is smashed and carried out secondary ball milling, secondary ball milling parameter is identical with a ball milling; Ball
The slurry of milled becomes dry powder at 70 ℃ of insulation 24 h; The PVA aqueous solution that employing mass fraction is 2% is as binding agent, and powder and PVA solution quality, than being 10:1, are then crossed the accurate sub-sieve of 100 target, and with the pressurize of 45MPa pressure, 5min suppresses, and makes powder become base.
4) base substrate is put into Si-Mo rod high-temperature electric resistance furnace, with the speed of 1 ℃/min, from room temperature, is risen to 550 ℃,
In air atmosphere, be incubated 300min, after with the speed of 2 ℃/min, rise to 1130 ℃ of sintering temperatures, in air atmosphere, be incubated 90min, cool to room temperature with the furnace.
5), to billet surface fine sandpaper sanding and polishing, guarantee that base substrate two sides is smooth, zero defect.?
After by ceramic body coated on both sides silver slurry, in drying baker in 70 ℃ of oven dry; Sample after drying is put in resistance furnace, by room temperature, rises to 600 ℃, insulation 30min, forms silver electrode, obtains magnoniobate bismuthino ceramic material.
The magnoniobate bismuth base microwave dielectric ceramic material of the present embodiment made is through performance test, and dielectric constant is 188.4959, and dielectric loss is 0.00030, and dielectric temperature coefficient is-523ppm/ ℃.
embodiment 2
In this example, according to following molar percentage component, prepare burden, Bi
2o
3: 59.358%, MgO:
6.9627%, Nb
2o
5: 32.1403%, Li
2cO
3: 0.1595%, TiO
2: 1.3795%, adopt the processing step identical with embodiment 1 to be made into magnoniobate bismuthino ceramic material.
The magnoniobate bismuth base microwave dielectric ceramic film material of the present embodiment made is through performance test, and dielectric constant is 198.6450, and dielectric loss is 0.00029, and dielectric temperature coefficient is-621ppm/ ℃.
embodiment 3
In this example, according to following molar percentage component, prepare burden, Bi
2o
3: 59.906%, MgO:
7.027%, Nb
2o
5: 30.121%, Li
2cO
3: 0.161%, TiO
2: 2.785%, adopt the processing step identical with embodiment 1 to be made into magnoniobate bismuthino ceramic material.
The magnoniobate bismuth base microwave dielectric ceramic film material of the present embodiment made is through performance test, and dielectric constant is 188.4959, and dielectric loss is 0.00027, and dielectric temperature coefficient is-683ppm/ ℃.
Claims (1)
1. a magnoniobate bismuthino lithium titanium is replaced the preparation method of microwave dielectric ceramic material altogether, the dielectric constant that described magnoniobate bismuthino lithium titanium is replaced microwave dielectric ceramic material is altogether 188～213, dielectric loss is 0.00027～0.00031, dielectric temperature coefficient is-and 683ppm/ ℃ ~-523ppm/ ℃; Can be used in the voltage-controlled microwave device of integrated circuit medium, it is characterized in that: utilize traditional solid-phase synthesis to prepare Bi
1.5mgNb
1.5o
7based microwave dielectric ceramics material: according to following molar percentage component, prepare burden, Bi
2o
359%～60%, MgO6.9%～7.0%, Nb
2o
530%～33.2% is material of main part, Li
2cO
3, TiO
2being respectively 0.15%～3%, is dielectric function additive; Adopt agate ball and stainless cylinder of steel, absolute ethyl alcohol is ball-milling medium, agate ball: batching powder: the mass ratio of absolute ethyl alcohol is 2:1:1, and wet-milling 10h in planetary high-energy ball mill, rotating speed is 150rpm; The slurry that ball milling is good becomes dry powder at 70 ℃ of insulation 24 h; The PVA aqueous solution that employing mass fraction is 2% is as binding agent, and powder and PVA solution quality, than being 9:1, are then crossed the accurate sub-sieve of 150 target, and with the pressurize of 20MPa pressure, 5min suppresses, and makes powder become base; Base substrate is put into Si-Mo rod high-temperature electric resistance furnace, with the speed of 3 ℃/min, from room temperature, rise to 950 ℃, in air atmosphere, be incubated 150min, cool to room temperature with the furnace, complete the pre-burning to base substrate; After pre-burning, base substrate is smashed and carried out secondary ball milling, secondary ball milling parameter is identical with a ball milling, and the slurry that ball milling is good becomes dry powder at 70 ℃ of insulation 24 h; The PVA aqueous solution that employing mass fraction is 2% is as binding agent, and powder and PVA solution quality, than being 10:1, are then crossed the accurate sub-sieve of 100 target, and with the pressurize of 45MPa pressure, 5min suppresses, and makes powder become base; Base substrate is put into Si-Mo rod high-temperature electric resistance furnace, with the speed of 1 ℃/min, from room temperature, rises to 550 ℃, in air atmosphere, be incubated 300min, after with the speed of 2 ℃/min, rise to 1130 ℃ of sintering temperatures, in air atmosphere, be incubated 90min, cool to room temperature with the furnace.
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| CN103232239A (en) * | 2013-04-22 | 2013-08-07 | 江苏大学 | Microwave dielectric ceramic material and preparation method thereof |
| CN108929110A (en) * | 2018-08-13 | 2018-12-04 | 安徽长容电子有限公司 | A kind of high pressure resistant temperature-stable ceramic capacitor dielectric material and preparation method thereof |
| CN109111225A (en) * | 2018-08-16 | 2019-01-01 | 天津大学 | Regulate and control the lithium titanate base microwave dielectric material of microwave dielectric property by magnesium niobium component |
| CN117153562A (en) * | 2023-09-19 | 2023-12-01 | 江苏飞特尔通信有限公司 | Bismuth-based adjustable MLCC capacitor for LTCC and preparation method |
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|---|---|---|---|---|
| CN101439970A (en) * | 2008-12-17 | 2009-05-27 | 电子科技大学 | Bismuth-based dielectric material for microwave tuning and preparation thereof |
| CN102093046A (en) * | 2010-12-10 | 2011-06-15 | 厦门松元电子有限公司 | BaO-Ln2O3-TiO2-series microwave capacitor medium material and preparation method thereof |
| CN102249307A (en) * | 2011-05-06 | 2011-11-23 | 天津大学 | Preparation method of Bi1.5MgNb1.5O7 (BMN) dielectric film |
| CN102826847A (en) * | 2012-09-19 | 2012-12-19 | 天津大学 | Composite high dielectric constant microwave dielectric ceramic material and preparation method thereof |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101439970A (en) * | 2008-12-17 | 2009-05-27 | 电子科技大学 | Bismuth-based dielectric material for microwave tuning and preparation thereof |
| CN102093046A (en) * | 2010-12-10 | 2011-06-15 | 厦门松元电子有限公司 | BaO-Ln2O3-TiO2-series microwave capacitor medium material and preparation method thereof |
| CN102249307A (en) * | 2011-05-06 | 2011-11-23 | 天津大学 | Preparation method of Bi1.5MgNb1.5O7 (BMN) dielectric film |
| CN102826847A (en) * | 2012-09-19 | 2012-12-19 | 天津大学 | Composite high dielectric constant microwave dielectric ceramic material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 姚国光等.V2O5和Li2CO3共掺杂对Mg4Nb2O9陶瓷烧结行为及微波介电性能的影响.《陕西师范大学学报（自然科学版）》.2006,第34卷(第2期), * |
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