CN1854105A - Nanometer ceramic-material doping agent, ceramic capacitor media material and production thereof - Google Patents

Nanometer ceramic-material doping agent, ceramic capacitor media material and production thereof Download PDF

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CN1854105A
CN1854105A CN 200510048278 CN200510048278A CN1854105A CN 1854105 A CN1854105 A CN 1854105A CN 200510048278 CN200510048278 CN 200510048278 CN 200510048278 A CN200510048278 A CN 200510048278A CN 1854105 A CN1854105 A CN 1854105A
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nano ceramic
earth metal
dopant
dielectric material
ceramic dopant
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周晓华
张树人
李波
朱文奕
钟朝位
杨成韬
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University of Electronic Science and Technology of China
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University of Electronic Science and Technology of China
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Abstract

A nanometer ceramic material dopant, medium material of ceramic capacitor and their production are disclosed. The formula of the dopant consists of aA.bB.cC.dR2 O3.eSiO2; A contains Na2O; B contains one or multiple of MgO and CaO; C contains one or multiple of MnO2 and Co3O4; R contains one of multiple of Y, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu, among them a, b, c, d and e are coefficient, by computing mol%, 0<=a<=10%, 0<=b<=25%, 0<=c<=15%, 20%<=d<=60%, 10%<=e<=50% and b and c can't be zero at same time. Its advantages include large capacity, adjustable material formula, low sintering temperature, less medium loss, high dielectric constant and better reliability.

Description

Nano ceramic dopant, ceramic capacitor dielectric material and the preparation method of the two
Technical field
The invention belongs to technical field of electronic materials, particularly nano ceramic dopant, ceramic capacitor dielectric material and the preparation method of the two.
Background technology
Laminated ceramic capacitor (Multilayer Ceramic Capacitors) is called for short MLCC.It is that electrode materials is replaced in parallel being superimposed together with ceramic idiosome with multilayer, and burns till an integral body simultaneously.(X7R type MLCC is meant between temperature range-55～125 ℃, temperature coefficient of capacitance＜± 15%, dielectric loss (DF)≤2.0% for Electronic Industries Association, EIA) standard according to international Electronic Industries Association.X7R type MLCC is divided into two big classes by composition: a class is made up of plumbiferous relaxation type ferroelectrics, and is another kind of with barium titanate (BaTiO 3) be that basic non-lead is that ferroelectrics is formed.Because latter's environmentally safe, and physical strength and reliability be better than the former, and therefore non-lead is BaTiO 3Base X7R type MLCC has broad application prospects.
Be to reduce the production cost of MLCC, base metal Ni, Cu and alloy thereof are that research and the production of the MLCC of interior electrode has obtained very big development in recent years.The MLCC majority of producing in the world is base-metal inner-electrode MLCC (Base-Metal-Electrode MLCC at present, BME-MLCC), in the production of BME-MLCC, owing to will use base metal Ni, Cu and alloy thereof as interior electrode, and easy oxidation during sintering in air of these two kinds of metals, so BME-MLCC is generally at the atmosphere such as the N of reductibility 2/ H 2Or CO/CO 2In sintering, cause performance to reduce for avoiding dielectric material that semiconductor takes place during sintering in reducing atmosphere, so the general resistance to reduction that adds recipient elements such as Mn, Mg with the increase dielectric material in the BME-MLCC dielectric material.It mainly is with BaTiO that the X7R type MLCC of non-plumbous system forms 3Be base-material, add rare earth oxide R 2O 3(R=Dy, Ho, Er etc.) a kind of or several, alkaline earth metal oxide MgO etc. a kind of or several and MnO 2, Co 3O 4A kind of or several, play doping vario-property as the alms giver that advocated peace, also add SiO 2, Al 2O 3And some vitreums etc. reduce sintering temperature as sintering agent.
The traditional technology of preparation X7R BME-MLCC dielectric material generally is to pass through synthesis by solid state reaction.This processing step comprises batching-ball milling-dry-sieve-granulation-compressing tablet-binder removal-by electrode-sintering etc.Shortcomings such as there is the component skewness in this technology, particle size is bigger than normal, synthesis temperature is high, be subject to contaminating impurity, reproducibility difference, and sintering temperature height, the energy consumption height is unfavorable for technology controlling and process.Another defective of traditional technology is because the ceramic powder particle diameter that uses is excessive, if the doping agent maximum particle diameter exceeds certain value and can make hotchpotch that spot segregation takes place in medium layer, thereby dielectric loss is risen, and cause initial insulation resistance IR to reduce, may cause the disqualification rate of MLCC to raise.Bigger dielectric material particle diameter can cause number of die in the single medium layer to reduce and the reliability of MLCC is reduced.And because the size distribution of the stupalith of traditional technology preparation is inhomogeneous, often make to have a large amount of pores and cavity in the porcelain body, have a strong impact on the performance of the media coating of MLCC, and with the attenuate of media coating, this influence is with increasing.Therefore, the present invention will use mixed nanometer technology to prepare the uniform submicron order of particle diameter to nano level X7R Ni-MLCC dielectric material, with the needs that adapt to MLCC medium layer attenuate and the lifting of MLCC reliability.
At present, preparing medium material for multilayer ceramic capacitors and method thereof both at home and abroad mainly contains following several:
One, in the Chinese patent application number 02131431.4,03147880.8, people such as Wang Xiaohui disclose a kind of ultra-fine temperature-stable multilayer ceramic capacitor dielectric materials.This material contains main composition BaTiO 3And secondary additive CaO, CaTiO 3, BaO, SiO 2, SrO, MnO 2, MgO, Co 2O 3, Co 3O 4, Fe 2O 3, Y 2O 3And one or more rare earth oxide.United States Patent (USP) U.S Pat.No.6673274, people such as Venigalla invent with BaTiO 3Be base-material, the compound of rare earth compound, alkaline earth metal compound, manganese, sexavalence metallic compound (Y for example 2O 3, MgO, MnO 2, Mo 2O 5) as property-modifying additive, silicon base compound is (as BaSiO 3) be sintering agent, by traditional solid phase synthesis, in reducing atmosphere, burn till and can obtain Gao Jie, low-loss temperature-stable X7R type MLCC dielectric material in 1350 ℃, adopt Ni, Cu and alloy thereof as interior electrode.In addition, similar patent is U.S Pat.No.6645897 for example, U.S.Pat.6620753, and U.S Pat.No.6613706, U.S Pat.No.6185087 etc. are with BaTiO 3Be base-material, CaTiO 3, BaO, CaO, SrO, MnO 2, Y 2O 3, CoO is as property-modifying additive, SiO 2Deng low-melting-point material is sintering agent, by traditional solid phase synthesis, at reducing atmosphere N 2/ H 2/ H 2Burn till in 1250～1400 ℃ among the O and can obtain Gao Jie, high insulation resistance, low-loss X7R type MLCC dielectric material, adopt Ni, Cu and alloy thereof as internal and external electrode.Conventional solid-state method is the glass doping agent that adds all kinds of dopant powder respectively and play cooling and anti-reductive action in base-material, as at BaTiO 3Add doping agent powders such as manganese oxide, yttrium oxide, Neodymium trioxide in the base-material respectively and obtain dielectric material.The size distribution inequality of doping agent.
Its two, among the United States Patent (USP) U.S.Pat.5319517, people such as Takeshi Nomura invent with BaTiO 3, BaZrO 3And CaTiO 3Powder is by the synthetic base-material of liquid phase method, and with solid matter mixing and ball milling such as oxide compound, carbonate, dry preparation doping agent, row joins that mixing and ball milling obtains ultra-fine Y5V type MLCC porcelain in the base-material again.But this method needs high-quality abrasive blast equipment and long abrasive material, average and the maximum particle size of strict controlled doping agent in the mixing and ball milling process of doping agent slurry, particle diameter to doping agent requires the more little then abrasive material time to be doubled and redoubled, and this certainly will increase production cost, extends manufacture cycle.
Its three, Horacio E.Bergna among the United States Patent (USP) U.S.Pat.5082810, Salvatore A.Bruno etc. has invented solution coating method and has been used to prepare Y5V type MLCC dielectric material, at first uses coprecipitation method modification BaTiO 3Prepare ultra-fine base-material, then various metals and nonmetallic compound (as acetate, borate) are dissolved in and prepare metallo-chelate solution in the sequestrant, directly with after base-material mixes, drying, calcining obtain surface coated ultra-fine MLCC dielectric material after with decomposition inner complex and removal volatile residue with this solution.This method greatly improves doping agent distribution consistency degree in dielectric material, becomes room and defective in the porcelain to reduce, and has improved the reliability of MLCC.Through repeatedly reflux, filtration procedure obtains stable chelate solution, can cause solution composition deviation theory value.But its complex process, the equipment requirements height, the cost height, growth cycle is long.
Its four, United States Patent (USP) U.S.Pat.6072688, people such as Detlev Hennings have invented the technology that directly prepares Y5V type BME-MLCC dielectric material with sol-gel method.With anhydrous metal alkoxide is metatitanic acid fourth fat TBT-Ti (CH 4H 9) 4With zirconic acid fourth fat TBZ-Ti (CH 4H 9O) 4, and anhydrous calcium acetate, barium acetate, manganese acetate etc. are main raw material, by the dielectric material of sol-gel method one-step synthesis.Wherein in the process of preparation acetic acid-collosol intermixture, need repeatedly reflow step for a long time, and guarantee anhydrous.Yet this technology exists the production cycle long equally, equipment requirements height, complex process, the shortcoming that cost is high.
Its five, in the Chinese patent application number 0117624.8, the people such as didactics literary composition grade that records adopts the coprecipitation method in the wet-chemical to prepare a kind of nano level Y5V type medium material for multilayer ceramic capacitors.But this method preparation is plumbous series ceramic material, and its main component is PMN-PT (PMN-PT), contains harmful element lead and is unfavorable for environmental protection.In this patent various raw materials such as base-material and doping agent are passed through coprecipitation method one-step synthesis dielectric material.
Summary of the invention
Technical problem to be solved by this invention is, for solving or improving the problem that exists in the traditional technology, nano ceramic dopant, ultra-fine temperature-stable reduction-resistant multilayer ceramic capacitor dielectric material and the preparation method of the two are proposed, can realize the difference mass production of base-material and doping agent, thereby production process is simplified, the simple and control easily of equipment.Make the additive granules size and reach nano level, meet the trend of MLCC large vol, high reliability and miniaturization; Little and the good dispersity of doping agent granularity, can be in base-material homodisperse and the base-material powder granule realized evenly parcel; And the mixed nanometer agent of preparation can reduce the sintering temperature of MLCC porcelain effectively, cuts down the consumption of energy the little and narrow diameter distribution of dielectric material mean particle size that obtains, it is simply adjustable to fill a prescription, firing temperature is low, the specific inductivity height, and dielectric loss is little, the preparation technology's method that proposes is easy, sintering process is easily controlled, and the material homogeneity of making is good, the performance good reproducibility, help improving the reliability of electrical condenser, can be used for preparing large vol and miniaturization MLCC.
The present invention solve the technical problem the technical scheme that is adopted, and a kind of nano ceramic dopant is provided, and it is characterized in that, its formula table is shown:
aA·bB·cC·dR 2O 3·eSiO 2
Wherein, A represents alkalimetal oxide, comprises Na 2O;
B represents alkaline earth metal oxide, comprises one or more of MgO, CaO;
C represents transition metal oxide, comprises MnO 2, Co 3O 4One or more;
R represents rare earth metal, comprises one or more of Y, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu;
Wherein, a, b, c, d, e are coefficients, calculate with mol%, and 0≤a≤10%, 0≤b≤25%, 0≤c≤15%, 20%≤d≤60%, 10%≤e≤50%, b and c are not 0 simultaneously.
Further, the alkalimetal oxide of A representative also comprises Li 2O, K 2One or both of O; The alkaline earth metal oxide of B representative also comprises one or more of SrO, BaO; The transition metal oxide of C representative also comprises one or more in the oxide compound of V, Fe, Ni, Cu, Zn, Nb, Mo, W; The rare earth metal of R representative also comprises one or more of Sc, La, Ce, Pr, Nd.Median size is 10～100 nanometers.
The present invention also provides a kind of preparation method of nano ceramic dopant, may further comprise the steps:
1. the mineral compound with basic metal, alkaline-earth metal, transition metal and rare earth metal is a raw material, forms inorganic solution by being dissolved in nitric acid behind each raw material of stoichiometric ratio weighing and mixing;
Described basic metal comprises Na, and alkaline-earth metal comprises one or both of Mg, Ca, and transition metal comprises one or more of Mn, Co, and rare earth metal comprises one or more of Y, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu;
2. with tetraethoxy, ethanol, polyoxyethylene glycol by volume 1: X: Y mixes and is organic solution, wherein, and X=1～5, Y=0～2;
3. with the inorganic solution heating evaporation, count by volume, when inorganic solution: organic solution=1～4: in the time of 1, under 50～90 ℃ of temperature, two kinds of solution are mixed to stir and it is fully reacted obtain colloidal sol, and control pH≤3, ageing, drying obtain clear gel, form xerogel behind the oven dry a few days desolventizing;
4. xerogel is heat-treated,, after grinding, sieving, obtain nano ceramic dopant promptly 300～1000 ℃ of following roastings.
Basic metal also comprises one or more of Li, K in its raw material; Alkaline-earth metal also comprises one or more of Sr, Ba; Transition metal also comprises one or more of V, Fe, Ni, Cu, Zn, Nb, Mo, W; Rare earth metal also comprises one or more of Sc, La, Ce, Pr, Nd.Mineral compound described in its raw material comprises oxide compound, carbonate, nitrate, acetate, ammonium meta-vanadate.
The present invention also provides a kind of ceramic capacitor dielectric material, it is characterized in that, formula table is shown:
The BaTiO3+ nano ceramic dopant
Wherein, BaTiO 3The shared quality percentage composition of base-material is 95%～99%, and the quality percentage composition of nano ceramic dopant is 1.0%～5.0%.
Described ceramic capacitor dielectric material median size is 0.05～1.5 micron.
The present invention also provides a kind of preparation method of ceramic capacitor dielectric material, it is characterized in that, may further comprise the steps:
A1, BaTiO 3Mixing nano ceramic dopant in the base-material, is the medium mixing and ball milling with the deionized water; Wherein, BaTiO 3The shared quality percentage composition of base-material is 95%～99%, and the quality percentage composition of nano ceramic dopant is 1.0%～5.0%;
A2, drying, sieve, binder removal after the granulation, compression molding;
A3, at N 2/ H 2Sintering in the reducing atmosphere.
Nano ceramic dopant that the present invention proposes and preparation method thereof has following advantage:
The particle size of this ceramic dopant reaches nano level, helps the further attenuate of MLCC medium layer, satisfies the needs of the further miniaturization of MLCC, high capacity; Specific surface area is big, active high, can reduce doping; Cost is low, and used organic and inorganic raw material is simple and easy to; Can realize the height homogenizing, chemical uniformity is good, the good uniformity of material purity, performance good reproducibility; A synthetic additive is beneficial to large-scale industrialization production, the complicacy that effectively reduces production costs and reduce the preparation link, and technology is simple, and control is easy, the suitable for mass production manufacturing; Reduce sintering temperature greatly, improve specific inductivity and stability, trace element is controlled well, and the Nanosurface effect is with smooth realization " shell-core " structure; Make the various chemical ingredientss in the doping agent reach uniform distribution and the mixing that arrives molecular level.
The anti-reducing medium preparation methods of ultra-fine temperature-stable multilayer ceramic capacitor that the present invention proposes, the dielectric material primary particles that this method obtains is ultra-fine, the trend that meets MLCC large vol, miniaturization can be used for preparing the interior electrode MLCC of Ni of large vol and miniaturization; Material prescription is adjustable, and sintering temperature is low; The specific inductivity height, dielectric loss is little, and the material homogeneity of making is good, and the performance good reproducibility helps improving the reliability of electrical condenser.
The anti-reducing medium Material formula makeup of ultra-fine temperature-stable multilayer ceramic capacitor that the present invention proposes can go out the X7R type Ni-MLCC dielectric material of excellent performance at the temperature range sintering under 1180 ℃～1300 ℃, its room temperature dielectric constant is greater than 2500, temperature coefficient of capacitance＜± 15% in-55 ℃～125 ℃ temperature range, and has a high insulation resistivity, high-breakdown-voltage, stable performance, physical strength is big, the reliability advantages of higher.
The ultra-fine temperature-stable reduction-resistant multilayer ceramic capacitor material that the present invention proposes is used to prepare Ni-MLCC has four advantage: a. can reduce sintering temperature, reduce energy consumption, b. the dielectric material initial particle is little, narrow diameter distribution, the further attenuate that helps the MLCC thickness of dielectric layers meets the needs of the further miniaturization of MLCC.C. chemical uniformity is good, and the performance good reproducibility has improved the physical strength and the reliability of material greatly, has improved the insulativity and the voltage endurance of material, and d. technology is simple, control easily, the suitable for mass production manufacturing.Doping agent is at base-material surface uniform distribution; Make various compositions in the doping agent reach the mixing of molecular level, so the part of its composition of dielectric material of the method for this patent preparation is departed from littler.
The present invention earlier is mixed in proportion all kinds of doping agents the back to prepare nano ceramic dopant with sol-gel method, is solid powder, obtains dielectric material after again this nano ceramic dopant and base-material being mixed in proportion ball milling, drying.The difference that the present invention is compared with the prior art is tangible.Especially the preparation of doping agent and granularity and introducing mode thereof.
The present invention is further illustrated below in conjunction with embodiment and accompanying drawing.
Description of drawings
Fig. 1 is the TEM photo of sample among the embodiment 1.
Fig. 2 is the XRD figure spectrum of sample among the embodiment 1.
Fig. 3 is the dielectric temperature characteristic curve and the temperature coefficient of capacitance curve of sample among the embodiment 2.
Fig. 4 is the dielectric temperature characteristic curve and the temperature coefficient of capacitance curve of sample among the embodiment 3.
Fig. 5 is the dielectric temperature characteristic curve and the temperature coefficient of capacitance curve of sample among the embodiment 4.
Fig. 6 is the dielectric temperature characteristic curve and the temperature coefficient of capacitance curve of sample among the embodiment 5.
Fig. 3～Fig. 6 is corresponding to the dielectric temperature characteristic curve of each sample among the embodiment 1～5 and temperature coefficient of capacitance curve.Probe temperature is-55 ℃～130 ℃.
The meaning of each parameter representative is as follows in table 1～table 5:
K 25 ℃: the specific inductivity of dielectric material during 25 ℃ of room temperatures;
Tg δ 25 ℃: the dielectric loss of dielectric material during 25 ℃ of room temperatures;
IR: the insulation resistance of dielectric material during 25 ℃ of room temperatures;
TCC -55 ℃: the percentage of capacitance variation with temperature of dielectric material in the time of-55 ℃;
TCC 125 ℃: the percentage of capacitance variation with temperature of dielectric material in the time of 125 ℃.
Percentage of capacitance variation with temperature TCC T%=100 * (K T-K 25 ℃)/K 25 ℃
Embodiment
In conjunction with test chart, enumerate following examples and respectively the present invention illustrated:
Embodiment 1: adopting process method 1 preparation nano ceramic dopant N1～N4, and as shown in table 1.It is as follows to be with preparation N3 that example specifies: with 12.5mol% magnesiumcarbonate (MgCO in the mineral compound 3), 12mol% lime carbonate (CaCO 3), 11.5mol% manganese oxide (MnO 2), 1mol% tricobalt tetroxide (Co 3O 4), 33mol% yttrium oxide (Y 2O 3) be dissolved in nitric acid; To be equivalent to the tetraethoxysilance of 30mol% and methyl ethyl diketone, dehydrated alcohol, polyoxyethylene glycol 3: 1: 3 by volume: 1 is mixed into organic solvent.Adopting process method 1 prepares sol-gel, obtains xerogel through 50～100 ℃ of oven dry and grinds to form powder 750 ℃ of following thermal treatments after 1 hour.The gained nano ceramic dopant is observed its microscopic appearance and size distribution with transmission electron microscope (TEM).Fig. 1 has provided the TEM photo of this sample that amplifies 100,000 times.According to XRD analysis, compare with standard card (JCPDS 20-1410) by retrieval, find that this product principal crystalline phase is composition silicate Y 4MgSi 3O 13The hexagonal crystal phase.Fig. 2 has provided the XRD figure spectrum of this sample.
Table 1
Doping agent Composition (mol%) Thermal treatment
N1 24％Mg+54％Y+22％Si 400℃
N2
25％Mg+10％Mn+35％Y+30％Si 600℃
N3 12.5％Mg+12％Ca+11.5％Mn+1％Co+33％Y+30％Si 600℃
N4 1％Na+12％Mg+12％Ca+11％Mn+1％Co+33％Y+30％Si 800℃
Embodiment 2: the ultra-fine temperature-stable reduction-resistant multilayer ceramic capacitor dielectric material of adopting process method 2 preparations.Be the BaTiO of 0.3 μ m with hydrothermal method synthetic median size in the prescription 3Be base-material, account for 97% of dielectric material total mass; Doping agent is the nano ceramic dopant N1～N4 of preparation in the embodiment of the invention 1, accounts for 3% of dielectric material total mass respectively.After the dielectric material drying that mixing, ball milling obtain, add the PVA mixing granulation of 10wt%, compression moulding under 10Mpa pressure, diameter is that 10mm, thickness are the disk of 1mm, in air, behind 600 ℃ of binder removals,, place N then at disk dual coating nickel inner electrode slurry 2/ H 2Reducing atmosphere (oxygen partial pressure P (O 2)=10 -12Pa) sintering in, sintering temperature are 1200 ℃ of insulations 4 hours, at weak oxygen atmosphere (oxygen partial pressure P (O 2)=10 -7Pa) in 1000 ℃ of annealing 1.5 hours, temperature rise rate and rate of temperature fall were 5 ℃/min in.The dielectric properties parameter of gained ceramics sample sees Table 2, and Fig. 3 has provided the dielectric temperature characteristic curve and the temperature coefficient of capacitance curve of present embodiment sample.
Table 2
Sample The mixed nanometer agent K 25℃ tgδ 25℃ IR Ω·cm TCC -55℃ TCC 125℃
2-1 N1 3021 0.37％ 4×10 11 -6.82％ 5.56％
2-2 N2 2740 0.49％ 2×10 11 -8.03％ 5.47％
2-3 N3 2666 0.35％ 7×10 11 -6.45％ 4.95％
2-4 N4 2894 0.54％ 5×10 11 -14.03％ 7.50％
Embodiment 3: the ultra-fine temperature-stable reduction-resistant multilayer ceramic capacitor dielectric material of adopting process method 2 preparations.Be the BaTiO of 0.5 μ m with hydrothermal method synthetic median size in the prescription 3Be base-material, account for 92～99.5% of dielectric material total mass; Doping agent is the nano ceramic dopant N1 of preparation in the embodiment of the invention 1, accounts for 0.5%～8.0% of dielectric material total mass respectively.After the dielectric material drying that mixing, ball milling obtain, add the PVA mixing granulation of 10wt%, compression moulding under 10Mpa pressure, diameter is that 10mm, thickness are the disk of 1mm, in air, behind 600 ℃ of binder removals,, place N then at disk dual coating nickel inner electrode slurry 2/ H 2Reducing atmosphere (oxygen partial pressure P (O 2)=10 -12Pa) sintering in, sintering temperature are 1220 ℃ of insulations 3 hours, at weak oxygen atmosphere (oxygen partial pressure P (O 2)=10 -7Pa) in 1000 ℃ of annealing 2 hours, temperature rise rate and rate of temperature fall were 5 ℃/min in.The dielectric properties parameter of gained ceramics sample sees Table 3, and Fig. 4 has provided the dielectric temperature characteristic curve and the temperature coefficient of capacitance curve of this enforcement sample.
Table 3
Sample Wt K 25℃ tgδ 25℃ IR Ω·cm TCC -55℃ TCC 125℃
3-1 0.5％ 2887 1.24％ 1.3×10 11 -14.06％ 47.21％
3-2 1.0％ 3048 0.89％ 3.5×10 11 -10.10％ 21.06％
3-3 2.0％ 3230 0.32％ 8.6×10 11 -7.59％ 6.81％
3-4 4.0％ 2840 0.47％ 7.2×10 11 -5.88％ 3.52％
3-5 8.0％ 2781 1.12％ 5.2×10 11 -8.38％ -7.30％
Embodiment 4: the ultra-fine temperature-stable reduction-resistant multilayer ceramic capacitor dielectric material of adopting process method 2 preparations.Be the BaTiO of 0.7 μ m with hydrothermal method, coprecipitation method, solid phase method synthetic median size respectively in the prescription 3Be base-material, account for 97.5% of dielectric material total mass; Doping agent is the nano ceramic dopant N3 of preparation in the embodiment of the invention 1, accounts for 2.5% of dielectric material total mass.After the dielectric material drying that mixing, ball milling obtain, add the PVA mixing granulation of 10wt%, compression moulding under 10Mpa pressure, diameter is that 10mm, thickness are the disk of 1mm, in air, behind 600 ℃ of binder removals,, place N then at disk dual coating nickel inner electrode slurry 2/ H 2Reducing atmosphere (oxygen partial pressure P (O 2)=10 -12Pa) sintering in, sintering temperature are 1260 ℃ of insulations 2 hours, at weak oxygen atmosphere (oxygen partial pressure P (O 2)=10 -7Pa) in 1000 ℃ of annealing 1 hour, temperature rise rate and rate of temperature fall were 5 ℃/min in.The dielectric properties parameter of gained ceramics sample sees Table 4, and Fig. 5 has provided the dielectric temperature characteristic curve and the temperature coefficient of capacitance curve of this enforcement sample.
Table 4
Sample BT is synthetic K 25℃ tgδ 25℃ IR Ω·cm TCC -55℃ TCC 125℃
4-1 Hydrothermal method 2688 0.35％ 6.7×10 11 -6.09％ -7.27％
4-2 Coprecipitation method 2778 0.52％ 4.3×10 11 -5.64％ -9.70％
4-3 Solid phase method 2883 0.74％ 3.9×10 11 -6.97％ -11.37％
Embodiment 5: the ultra-fine temperature-stable reduction-resistant multilayer ceramic capacitor dielectric material of adopting process method 2 preparations.Be the BaTiO of 0.4 μ m with hydrothermal method synthetic median size respectively in the prescription 3Be base-material, account for 96.5% of dielectric material total mass; Doping agent is the nano ceramic dopant N2 of preparation in the embodiment of the invention 1, accounts for 3.5% of dielectric material total mass.After the dielectric material drying that mixing, ball milling obtain, add the PVA mixing granulation of 10wt%, compression moulding under 10Mpa pressure, diameter is that 10mm, thickness are the disk of 1mm, in air, behind 600 ℃ of binder removals,, place N then at disk dual coating nickel inner electrode slurry 2/ H 2Reducing atmosphere (oxygen partial pressure P (O 2)=10 -12Pa) sintering in is respectively 1180,1240,1300 ℃ of insulations 2.5 hours, at weak oxygen atmosphere (oxygen partial pressure P (O 2)=10 -7Pa) in 1000 ℃ of annealing 1 hour, temperature rise rate and rate of temperature fall were 5 ℃/min in.The dielectric properties parameter of gained ceramics sample sees Table 5, and Fig. 6 has provided the dielectric temperature characteristic curve and the temperature coefficient of capacitance curve of this enforcement sample.
Table 5
Sample Sintering temperature K 25℃ tgδ 25℃ IR Ω·cm TCC -55℃ TCC 125℃
5-1 1180℃ 3031 0.73％ 7.3×10 11 -5.44％ 0.03％
5-2 1240℃ 3104 0.41％ 9.4×10 11 -11.46％ -10.85％
5-3 1300℃ 2820 0.68％ 3.6×10 11 -9.17％ 7.40％
The various embodiments described above explanation by optimizing and revising of prescription and technology, can obtain high performance BaTiO 3Base X7R Ni-MLCC dielectric material.This dielectric material possesses good resistance to reduction, can be at N 2+ H 2(N 2: H 2=100: burn altogether with the Ni electrode in the reducing atmosphere 5).Wafer sample burnt till in 1180～1300 ℃ through 2～3 hours in reducing atmosphere, and its dielectric properties satisfy the requirement of EIA-X7R performance index.The room temperature dielectric constant of wafer sample 〉=2500, dielectric loss≤1.0%, resistivity 〉=10 11Ω cm, voltage breakdown 〉=10kV/mm, average crystal grain diameter≤1 μ m, temperature coefficient of capacitance between-55 ℃～125 ℃≤± 15%.Utilize prescription of the present invention and technology, particularly owing to adopt the submicron order BaTiO of solid phase method, coprecipitation method, Hydrothermal Preparation 3The nano ceramic dopant of base-material and the preparation of sol-gel method, it is low to obtain firing temperature, and sintering range is wide 1180～1300 ℃, the BaTiO that performance is adjustable and stable 3Base X7R Ni-MLCC dielectric material.And the uniform crystal particles of dielectric material, median size is less than 1 micron, and physical strength height, reliability height, anti-breakdown characteristics are strong.This method equipment is simple, with low cost, can satisfy the trend of MLCC high performance miniization, is the anti-reducing medium material of high-performance multilayer ceramic condenser with wide application prospect.

Claims (9)

1, nano ceramic dopant is characterized in that, its formula table is shown:
aA·bB·cC·d R 2O 3·e SiO 2
Wherein, A represents alkalimetal oxide, comprises Na 2O;
B represents alkaline earth metal oxide, comprises one or more of MgO, CaO;
C represents transition metal oxide, comprises MnO 2, Co 3O 4One or more;
R represents rare earth metal, comprises one or more of Y, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu;
Wherein, a, b, c, d, e are coefficients, calculate with mol%, and 0≤a≤10%, 0≤b≤25%, 0≤c≤15%, 20%≤d≤60%, 10%≤e≤50%, b and c are not 0 simultaneously.
2, nano ceramic dopant as claimed in claim 1 is characterized in that,
The alkalimetal oxide of A representative also comprises Li 2O, K 2One or both of O;
The alkaline earth metal oxide of B representative also comprises one or more of SrO, BaO;
The transition metal oxide of C representative also comprises one or more in the oxide compound of V, Fe, Ni, Cu, Zn, Nb, Mo, W;
The rare earth metal of R representative also comprises one or more of Sc, LaI, Ce, Pr, Nd.
3, nano ceramic dopant as claimed in claim 1 or 2 is characterized in that, median size is 10～100 nanometers.
4, the preparation method of nano ceramic dopant may further comprise the steps:
1. the mineral compound with basic metal, alkaline-earth metal, transition metal and rare earth metal is a raw material, forms inorganic solution by being dissolved in nitric acid behind each raw material of stoichiometric ratio weighing and mixing;
Described basic metal comprises Na, and alkaline-earth metal comprises one or both of Mg, Ca, and transition metal comprises one or more of Mn, Co, and rare earth metal comprises one or more of Y, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu;
2. with tetraethoxy, ethanol, polyoxyethylene glycol by volume 1: X: Y mixes and is organic solution, wherein, and X=1～5, Y=0～2;
3. with the inorganic solution heating evaporation, count by volume, when inorganic solution: organic solution=1～4: in the time of 1, under 50～90 ℃ of temperature, two kinds of solution are mixed to stir and it is fully reacted obtain colloidal sol, and control pH≤3, ageing, drying obtain clear gel, form xerogel behind the oven dry a few days desolventizing;
4. xerogel is heat-treated,, after grinding, sieving, obtain nano ceramic dopant promptly 300～1000 ℃ of following roastings.
5, the preparation method of nano ceramic dopant as claimed in claim 4 is characterized in that, basic metal also comprises one or more of Li, K in its raw material; Alkaline-earth metal also comprises one or more of Sr, Ba; Transition metal also comprises one or more of V, Fe, Ni, Cu, Zn, Nb, Mo, W; Rare earth metal also comprises one or more of Sc, La, Ce, Pr, Nd.
6, the preparation method of nano ceramic dopant as claimed in claim 4 is characterized in that, the mineral compound described in its raw material comprises oxide compound, carbonate, nitrate, acetate, ammonium meta-vanadate.
7, adopt the ceramic capacitor dielectric material of the described nano ceramic dopant of claim 1, it is characterized in that formula table is shown:
The BaTiO3+ nano ceramic dopant
Wherein, BaTiO 3The shared quality percentage composition of base-material is 95%～99%, and the quality percentage composition of nano ceramic dopant is 1.0%～5.0%.
8, ceramic capacitor dielectric material as claimed in claim 7 is characterized in that, median size is 0.05～1.5 micron.
9, the preparation method of the described ceramic capacitor dielectric material of claim 7 is characterized in that, may further comprise the steps:
A1, BaTiO 3Mixing nano ceramic dopant in the base-material, is the medium mixing and ball milling with the deionized water; Wherein, BaTiO 3The shared quality percentage composition of base-material is 95%～99%, and the quality percentage composition of nano ceramic dopant is 1.0%～5.0%;
A2, drying, sieve, binder removal after the granulation, compression molding;
A3, at N 2/ H 2Sintering in the reducing atmosphere.
CN 200510048278 2004-12-31 2005-12-30 Nanometer ceramic-material doping agent, ceramic capacitor media material and production thereof Pending CN1854105A (en)

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