CN104529430B - Titanium dioxide base composite ceramic dielectric materials and preparation method thereof and application - Google Patents
Titanium dioxide base composite ceramic dielectric materials and preparation method thereof and application Download PDFInfo
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Abstract
The present invention relates to titanium dioxide base composite ceramic dielectric materials and preparation method thereof and application.This materials chemistry formula is as follows: xSrTiO
3-(1 – x) A; Wherein, x=0.03 ~ 0.40; A is through codoping modified titanium dioxide, chemical composition expression formula (B, C)
y(TiO
2)
1 – y; In formula, the element that the element that B is ionic valence condition+5 valency, C are ionic valence condition+3 valency or+divalent; The molar ratio of B, C is determined according to the electric neutrality principle of stupalith; Y=0.005 ~ 0.15.Titanium dioxide base composite ceramic dielectric materials of the present invention has relative permittivity ε
rgreatly, resistance to electric field strength E
bthe feature of high excellent combination dielectric properties, is adapted to the high performance of the electronic products such as electrical condenser, resonator, wave filter and storer and microminiaturized requirement.
Description
Technical field
The present invention relates to titanium dioxide base composite ceramic dielectric materials and preparation method thereof and application, being specifically related to have high-k with strong anti-resistance to breakdown electric field is the titanium dioxide base composite ceramic dielectric materials of feature and the application in electronic product thereof, belongs to composite ceramic material technical field.
Technical background
High dielectric oxide material is the important foundation that capacitive device realizes high capacity and size microminiaturization, therefore receives increasing concern.Traditionally, relative permittivity ε
rthe high dielectric oxide material being greater than 1000 can be divided into two classes substantially.One class is the perovskite oxide of ferroelectricity or ferroelectric relaxation body, such as BaTiO
3, Pb (Mg
1/3nb
2/3) O
3deng.In the high dielectric property of this kind of material and material, the electric field response behavior of electric dipole moment is closely related, usually occurs along with structural phase transition.The relative permittivity ε of such material
rvery large near its transformation temperature, but variation with temperature is also very large, therefore in actual applications usually along with the change of envrionment temperature can cause the job insecurity of electron device.Another kind of is the material that the effective dielectric constant that causes due to internal barriers electric capacity (internalbarrier layer capacitance, IBLC) effect is very large.Such as, (Ba, Sr) TiO
3base oxide semiconductor ceramic, with CaCu
3ti
4o
12for the perovskite-like type oxide compound semiconductor ceramic of representative.Crystal grain in the interior microscopic weave construction of such material has lower resistivity, presents the character of semiconductor, and crystal boundary has higher resistivity, presents the character of isolator, causes macroscopically showing huge relative permittivity ε
r.But, when impressed voltage puts on this kind of material, due to the special electrical properties that its heterogeneous microstructure has, the overwhelming majority of impressed voltage value drops to grain boundary layer, and the thickness of grain boundary layer is usually very thin, thus causes the strength of electric field of local very high, be very easy to puncture.Therefore, the high dielectric oxide material of IBLC effect genesis all also exists the not high serious problems of resistance to strength of electric field usually.
Titanium dioxide (TiO
2) common crystalline structure be divided into rutile-type and Detitanium-ore-type two kinds.Can rutile-type structure be changed under Detitanium-ore-type structured high temperature, therefore usually present rutile-type structure through the titanium dioxide ceramic of high temperature sintering.The relative permittivity ε of the pure titinium dioxide pottery of non-modified
rless, about about 90.Utilize Nb
5+deng high price foreign ion to Ti
4+ion carries out the doping of non-equivalence displacement, and under high temperature sintering condition, high price foreign ion diffuses into TiO
2lattice, exist as alms giver in crystal grain thus provide electronics, crystal grain becomes n-type semiconductor.In order to keep electric neutrality, small part Ti
4+ion is then reduced into Ti
3+ion.In the temperature-fall period of sintering, grain boundary layer is because part Ti
3+ion can be reoxidized and become the higher insulation layer of resistivity.Therefore, Nb
5+deng the internal barriers capacity effect that the electrology characteristic of titanium dioxide ceramic in heterogeneous microstructure of high price foreign ion doping is adjoint, on apparent, present very large relative permittivity ε
rvalue, but dielectric loss tan δ is also very large, and resistance to electric field strength E
bbe worth very low.As the measure reducing dielectric loss tan δ, by In
3+deng low price foreign ion and Nb
5+tiO is mixed together Deng high price foreign ion
2in, the effect of valence compensation can be played, thus dielectric loss tan δ can be reduced to a certain extent.Such as, document 1 (W.B.Hu et al, Nature Mater., 12 (2013) 821.) and document 2 (J.L.Li et al, J.Appl.Phys., the TiO of enforcement (Nb, In) codoped 116 (2014) 074105.) is in recent years reported
2the high dielectric property matter of stupalith.Implement the modification TiO of (Nb, In) codoped
2the relative permittivity ε of stupalith
rcan up to 20000 to 100000, dielectric loss tan δ can be down to about 5%, but resistance to strength of electric field is very low, the level that is only approximately 0.10kV/cm.
On the other hand, strontium titanate (SrTiO
3) be a kind of there is perovskite type crystal structure, typical paraelectrics, and there is good thermostability.The energy gap of this material is about 3.4eV, compares rutile TiO
2energy gap value 3.0eV bigger.In addition, the sintering temperature of strontium titanate ceramics and the sintering temperature of titanium dioxide ceramic very close.What is more important, strontium titanate ceramics has larger relative permittivity ε
r, low-down dielectric loss tan δ and good insulativity feature.Such as, the relative permittivity ε of strontium titanate ceramics that reports of document 1 (Z.J.Wanget al, Ceram.Inter., 40 (2014) 929.)
rbe 295, dielectric loss tan δ is 0.2%, resistance to electric field strength E
bfor 210kV/cm.
As mentioned above, although the modifying titanium dioxide pottery of single-phase can realize very large relative permittivity ε
r, but resistance to electric field strength E
bvery low.In contrast, the resistance to electric field strength E of strontium titanate ceramics
balthough very high, relative permittivity ε
rnot quite.Therefore, the modifying titanium dioxide pottery of single-phase or the comprehensive dielectric properties index of strontium titanate ceramics are unfavorable for practical application.
Summary of the invention
The comprehensive dielectric properties index of the modifying titanium dioxide pottery and strontium titanate ceramics that the present invention is directed to single-phase is unfavorable for the problem of practical application, provides a class to have the titanium dioxide base composite ceramic dielectric materials of good comprehensive dielectric properties.
The present invention also provides the application of described titanium dioxide base composite ceramic dielectric materials.
Technical scheme of the present invention is as follows:
A kind of titanium dioxide base composite ceramic dielectric materials, it is characterized in that, chemical formula is as follows:
xSrTiO
3―(1–x)A；
Wherein, x=0.03 ~ 0.40;
A is through codoping modified titanium dioxide, chemical composition expression formula (B, C)
y(TiO
2)
1 – y; In formula, the element that the element that B is ionic valence condition+5 valency, C are ionic valence condition+3 valency or+divalent; The molar ratio of B, C is determined according to the electric neutrality principle of stupalith; Y=0.005 ~ 0.15.
Preferably, x=0.05 ~ 0.30.
Preferably, B is the combination of one of Nb, Ta or Sb or two or more element.
Preferably, C is the element in In and/or La.
Preferably, y=0.01 ~ 0.05.
The preparation method of above-mentioned titanium dioxide base composite ceramic dielectric materials, comprises the steps:
(1) strontium titanate ceramics powder is prepared;
(2) codoping modified titanium dioxide ceramic powder is prepared;
(3) get the obtained strontium titanate ceramics powder of step (1) and the obtained codoping modified titanium dioxide ceramic powder of step (2) by metered proportions weigh batching, through mixing and ball milling, drying, obtain ceramic powder mixture;
(4) formed body, after granulation and forming processes, is carried out plastic removal by ceramic powder mixture step (3) obtained, and then under 1200 ~ 1500 DEG C of temperature condition, sinters 1 ~ 40h, obtained titanium dioxide base composite ceramic dielectric materials.
The application of above-mentioned titanium dioxide base composite ceramic dielectric materials manufacturing electrically, in electronic component.
The concrete form of titanium dioxide base composite ceramic dielectric materials of the present invention can be varied.Comprise ceramics powder, sintered ceramic body and thick film, also comprise the further doping vario-property material carried out based on titanium dioxide base composite ceramic dielectric materials, comprise with titanium dioxide base composite ceramic dielectric materials is a wherein organic ceramic matrix material prepared mutually simultaneously; And be the wherein slurry prepared of a composition with titanium dioxide base composite ceramic dielectric materials, also comprise various electron devices, the parts prepared based on titanium dioxide base composite ceramic dielectric materials.
When preparing above-mentioned titanium dioxide base composite ceramic dielectric materials, all can adopt oxide compound, carbonate powder is raw material, also partly can adopt oxide compound, carbonate powder and rest part adopts the powder utilizing nitrate, acetate or alkoxide etc. to be obtained by the process of the chemical means such as electroless plating, collosol and gel to be raw material, or all adopt the powder obtained by the process of the chemical means such as electroless plating, collosol and gel to be raw material.
For technique when preparing titanium dioxide base composite ceramic dielectric materials, the mode of common solid state reaction can be utilized to obtain titanium dioxide base composite ceramic preburning powdered material, also can obtain modifying titanium dioxide base composite ceramic powder by utilizing chemosynthesis mode.Sintering processing can adopt ordinary sinter mode, also can adopt hot pressed sintering mode, microwave sintering mode, plasma spark spark sintering mode etc.According to the requirement of the dielectric properties index to material, concrete sintering processing, sintering condition can be determined.
The present invention adopts strontium titanate and the method for carrying out compound through codoping modified titanium dioxide, to the resistance to electric field strength E of codoping modified titanium dioxide
bdo and improve improvement significantly.The apparent upper useful chemical expression formula xSrTiO of titanium dioxide base composite ceramic dielectric materials component of invention
3-(1 – x) A is described.Amount x in front formula can according to relative permittivity ε
rwith resistance to electric field strength E
brequirement and determine.Wherein, A is through codoping modified titanium dioxide, useful chemical composition expressions (B, C)
y(TiO
2)
1 – yrepresent.The element of to be ionic valence condition be+5 valencys of the B in front formula, specifically, can be a kind of element in Nb, Ta and Sb, also can be the combination of more than one elements; The element of C to be ionic valence condition be+3 valencys, specifically, a kind of element in ionic valence condition to be+3 valency elements can be In, Al etc. or periodictable in La rare earth series of elements, ionic valence condition for+divalent element can be Ba element, also can be the combination of more than one elements.In codoping modified titanium dioxide, B ion is as donor doping ion, and C ion enters TiO as acceptor doping ion
2lattice.The molar ratio of B, C can according to B ion as donor doping ion, C ion as the efficiency of acceptor doping ion, the modifying titanium dioxide after codoped reaches electroneutral principle and determines.B ion, C ion can be the Ti ion positions that direct solid solution enters crystalline texture, also can be the Ti that the direct solid solution of part enters crystalline texture
4+ion position and rest part segregates to boundary or grain with the form of oxide compound.Aforesaid strontium titanate comprises pure strontium titanate and utilizes a small amount of Ba
2+ion or Ca
2+ions etc. carry out the displacement doping of Ti ion position or utilize a small amount of Zr
4+ion or Sn
4+ions etc. carry out Ti
4+the strontium titanate of ion position displacement doping vario-property.Aforesaid codoping modified titanium dioxide comprises and utilizes a small amount of Zr
4+ion or Sn
4+ions etc. carry out Ti
4+the codoping modified titanium dioxide of ion position displacement doping.
The present invention adopt make strontium titanate together modified titanium dioxide doped method of carrying out compound prepare titanium dioxide base composite ceramic dielectric materials, for raising resistance to electric field strength E
bthere is following effect.Because strontium titanate crystal grain has very large resistivity and very high resistance to electric field strength E
bvalue, by strontium titanate grain dispersion between codoping modified titania, thus increases the distance between codoping modified titania, can increase substantially resistance value and insulativity, reaches and strengthens resistance to electric field strength E
beffect.Because strontium titanate and titanium dioxide have close sintering temperature, thus easily can form the composite dielectric pottery of high-compactness, reach and strengthen resistance to electric field strength E
beffect.During sintering, strontium titanate also can form non-crystalline coating layer on the crystal boundary face of codoping modified titania, and strontium titanate amorphism coating layer is compared with the codoping modified titania layer of single-phase, for the resistance to electric field strength E of raising
balso there is very good effect.In addition, the misgrowth of crystal grain when the modified titanium dioxide doped together compound of strontium titanate can also suppress to sinter, promote the uniform crystal particles of heterogeneous microstructure, can make each uniform crystal particles of codoping modified titanium dioxide when there being DC Electric Field share electric field, thus improve overall resistance to electric field strength E
b.
In the present invention, the chemical composition expression formula of the titanium dioxide base composite ceramic dielectric materials of invention is xSrTiO
3the value of-(1 – x) A, x generally should be less than 0.5.Ideal situation, x=0.05 ~ 0.40.Ideal situation more, x=0.10 ~ 0.30.X value is too small, does not reach and improves resistance to electric field strength E
bmodification object; And x value is excessive, the relative permittivity ε of material can be caused
rbe worth very low.
Beneficial effect
1. titanium dioxide base composite ceramic dielectric materials of the present invention fundamentally solves the resistance to electric field strength E of the titania-doped pottery of single-phase in prior art
blow problem, has relative permittivity ε
rgreatly, resistance to electric field strength E
bthe feature of high excellent combination dielectric properties;
2. titanium dioxide base composite ceramic dielectric materials of the present invention is adapted to the high performance of the electronic products such as electrical condenser, resonator, wave filter and storer and microminiaturized requirement.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is further elaborated, but institute of the present invention protection domain is not limited to the embodiment that these are specifically recorded.
Embodiment 1
A kind of titanium dioxide base composite ceramic dielectric materials, chemical formula is as follows:
0.15SrTiO
3―0.85(In
0.50,Nb
0.50)
0.01(TiO
2)
0.99。
The preparation method of above-mentioned titanium dioxide base composite ceramic dielectric materials, have employed the carbonate SrCO of purity assay respectively
3(99.0%), oxide compound TiO
2(99.8%), In
2o
3and Nb (99.0%)
2o
5(99.8%) be raw material, utilize traditional solid phase reaction process to prepare titanium dioxide base composite ceramic sample, step is as follows:
(1) by component chemical expression formula SrTiO
3metering than weighing SrCO
3and TiO
2, through ball milling, drying after mixing, then pre-burning 3h at 1250 DEG C of temperature, makes raw material fully chemical reaction occur; And then through ball milling, drying, obtained SrTiO
3ceramics powder;
(2) by component chemical expression formula (In
0.50, Nb
0.50)
0.01(TiO
2)
0.99metering than weighing TiO
2, In
2o
3and Nb
2o
5, through ball milling, drying after mixing, then pre-burning 3h at 1250 DEG C of temperature, makes raw material fully solid solution occur; And then through ball milling, drying, obtained (In
0.50, Nb
0.50)
0.01(TiO
2)
0.99ceramics powder;
(3) by SrTiO obtained for step (1)
3(the In that ceramics powder and step (2) obtain
0.50, Nb
0.50)
0.01(TiO
2)
0.99ceramics powder is 0.15SrTiO by component chemical expression formula
3-0.85 (In
0.50, Nb
0.50)
0.01(TiO
2)
0.99metering than weighing, mixing, through ball milling, dry obtained ceramic powder mixture;
(4) add polyvinyl alcohol (PVA) organic binder bond in 5wt% ratio and carry out granulation, under the pressure condition of 300MPa, then make the thin discs of diameter 15mm, thickness 1.0mm; Be incubated 3h under 650 DEG C of temperature condition in atmosphere and carry out plastic removal, tackiness agent is volatilized, then, in atmosphere with 1350 DEG C of sintering 3h, obtain composite ceramics sample.
Embodiment 2
A kind of titanium dioxide base composite ceramic dielectric materials, chemical formula is as follows:
0.15SrTiO
3―0.85(In
0.50,Nb
0.50)
0.01(TiO
2)
0.99。
As described in Example 1, difference is preparation method, and in step (4), sintering time is 10h.
Embodiment 3
A kind of titanium dioxide base composite ceramic dielectric materials, chemical formula is as follows:
0.05SrTiO
3―0.95(In
0.50,Nb
0.50)
0.01(TiO
2)
0.99。
As described in Example 1, difference is preparation method, and material rate is not identical.
Embodiment 4
A kind of titanium dioxide base composite ceramic dielectric materials, chemical formula is as follows:
0.10SrTiO
3―0.90(In
0.50,Nb
0.50)
0.01(TiO
2)
0.95。
As described in Example 1, difference is preparation method, and material rate is not identical.
Embodiment 5
A kind of titanium dioxide base composite ceramic dielectric materials, chemical formula is as follows:
0.20SrTiO
3―0.80(In
0.50,Nb
0.50)
0.01(TiO
2)
0.99。
As described in Example 1, difference is preparation method, and material rate is not identical.
Embodiment 6
A kind of titanium dioxide base composite ceramic dielectric materials, chemical formula is as follows:
0.25SrTiO
3―0.75(In
0.50,Nb
0.50)
0.01(TiO
2)
0.99。
As described in Example 1, difference is preparation method, and material rate is not identical.
Embodiment 7
A kind of titanium dioxide base composite ceramic dielectric materials, chemical formula is as follows:
0.30SrTiO
3―0.70(In
0.50,Nb
0.50)
0.01(TiO
2)
0.99。
As described in Example 1, difference is preparation method, and material rate is not identical.
Embodiment 8
A kind of titanium dioxide base composite ceramic dielectric materials, chemical formula is as follows:
0.15SrTiO
3―0.85(In
0.50,Nb
0.50)
0.05(TiO
2)
0.95。
As described in Example 1, difference is preparation method, and material rate is not identical.
Embodiment 9
A kind of titanium dioxide base composite ceramic dielectric materials, chemical formula is as follows:
0.15SrTiO
3―0.85(In
0.50,Nb
0.50)
0.10(TiO
2)
0.90。
As described in Example 1, difference is preparation method, and material rate is not identical.
Embodiment 10
A kind of titanium dioxide base composite ceramic dielectric materials, chemical formula is as follows:
0.15SrTiO
3―0.85(In
0.50,Ta
0.50)
0.01(TiO
2)
0.99。
As described in Example 1, difference is preparation method, and raw material and ratio are not identical.
Embodiment 11
A kind of titanium dioxide base composite ceramic dielectric materials, chemical formula is as follows:
0.15SrTiO
3―0.85(In
0.50,Sb
0.50)
0.01(TiO
2)
0.99。
As described in Example 1, difference is preparation method, and raw material and ratio are not identical.
Embodiment 12
A kind of titanium dioxide base composite ceramic dielectric materials, chemical formula is as follows:
0.15SrTiO
3―0.85(La
0.50,Nb
0.50)
0.01(TiO
2)
0.99。
As described in Example 1, difference is preparation method, and raw material and ratio are not identical.
Embodiment 13
A kind of titanium dioxide base composite ceramic dielectric materials, chemical formula is as follows:
0.15SrTiO
3―0.85(Ba
1.50,Nb
0.50)
0.01(TiO
2)
0.99。
As described in Example 1, difference is preparation method, and raw material and ratio are not identical.
Comparative example 1
A kind of ceramic dielectric material, chemical formula is as follows:
(In
0.50,Nb
0.50)
0.01(TiO
2)
0.99。
Preparation process is as follows:
(1) by component chemical expression formula (In
0.50, Nb
0.50)
0.01(TiO
2)
0.99metering than weighing TiO
2, In
2o
3and Nb
2o
5, through ball milling, drying after mixing, then pre-burning 3h at 1250 DEG C of temperature, makes raw material fully solid solution occur; And then through ball milling, drying, obtained (In
0.50, Nb
0.50)
0.01(TiO
2)
0.99ceramic;
(2) add polyvinyl alcohol (PVA) organic binder bond in 5wt% ratio and carry out granulation, under the pressure condition of 300MPa, then make the thin discs of diameter 15mm, thickness 1.0mm; Be incubated 3h under 650 DEG C of temperature condition in atmosphere and carry out plastic removal, tackiness agent is volatilized, then, in atmosphere with 1350 DEG C of sintering 10h, obtain sample.
Comparative example 2
A kind of ceramic dielectric material, chemical formula is as follows:
(In
0.50,Nb
0.50)
0.05(TiO
2)
0.95。
Preparation method is as described in comparative example 1, and difference is, material rate is not identical.
Comparative example 3
A kind of ceramic dielectric material, chemical formula is as follows:
(In
0.50,Nb
0.50)
0.10(TiO
2)
0.90。
Preparation method is as described in comparative example 1, and difference is, material rate is not identical.
Comparative example 4
A kind of ceramic dielectric material, chemical formula is as follows:
(In
0.50,Ta
0.50)
0.01(TiO
2)
0.99。
Preparation method is as described in comparative example 1, and difference is, raw material and ratio are not identical.
Comparative example 5
A kind of ceramic dielectric material, chemical formula is as follows:
(In
0.50,Sb
0.50)
0.01(TiO
2)
0.99。
Preparation method is as described in comparative example 1, and difference is, raw material and ratio are not identical.
Comparative example 6
A kind of ceramic dielectric material, chemical formula is as follows:
(La
0.50,Nb
.50)
0.01(TiO
2)
0.99。
Preparation method is as described in comparative example 1, and difference is, raw material and ratio are not identical.
Comparative example 7
A kind of ceramic dielectric material, chemical formula is as follows:
(Ba
1.50,Nb
0.50)
0.01(TiO
2)
0.99。
Preparation method is as described in comparative example 1, and difference is, raw material and ratio are not identical.
Be handled as follows sample prepared by embodiment and comparative example and detect: for the ceramics sample of electrical properties test, its surface utilizes burning infiltration method to be covered silver electrode, makes tested ceramics sample have the function being similar to parallel plate capacitor.Example use Agilent4294A electric impedance analyzer, with the capacitance of the ceramics sample having measured under 1kHz, 100kHz two representative frequency and the effective amplitude ac voltage signal condition that is 500mV silver electrode surface-coated under chambers temp.Then, according to the size of ceramics sample thickness and electrode, relative permittivity ε is calculated
rvalue.For resistance to electric field strength E
bvalue, tests ceramics sample applying high-voltage dc voltage in silicone oil at room temperature and obtains.
About the various embodiment of titanium dioxide base composite ceramic and the codoping modified TiO of single-phase
2it is as shown in table 1 that the dielectric properties of the various comparative examples of pottery and resistance to sparking can carry out evaluating obtained result.
Table 1 embodiment and the dielectric properties of comparative example and comparing of resistance to sparking energy
As shown in Table 1, the relative permittivity ε of all titanium dioxide base composite ceramics of embodiment 1 to embodiment 13
rvalue is all greater than 2000, and resistance to electric field strength E
bvalue is then all higher than 3.6kV/cm.Compare with the titania-doped ceramic phase of single-phase, although titanium dioxide based composite ceramic material presents low relative permittivity ε
rvalue, but its relative permittivity ε being greater than 2000
rvalue itself still belongs to than very high value.The relative permittivity ε of the titanium dioxide base composite ceramic of obtained embodiment 1 to embodiment 13 is tested under the condition of test frequency for 1kHz
rvalue is between 2470 to 16550.On the other hand, with the codoping modified TiO of the single-phase of comparative example 1 to comparative example 7
2the resistance to electric field strength E of pottery
bvalue is compared, the resistance to electric field strength E of the titanium dioxide base composite ceramic of embodiment 1 to embodiment 13
bvalue has significant raising.The codoping modified TiO of the single-phase of comparative example 1 to comparative example 7
2the resistance to electric field strength E of pottery
bvalue is all lower than 0.2kV/cm, and the resistance to electric field strength E of the titanium dioxide base composite ceramic of embodiment 1 to embodiment 13
bvalue is then between 3.6kV/cm to 19.4kV/cm, and increase rate reaches more than decades of times.The larger relative permittivity ε of titanium dioxide base composite ceramic
rvalue and higher resistance to electric field strength E
bvalue is a kind of good characteristic for material when practical application.
Below to resistance to electric field strength E
bother embodiment of the two-stage that value varies in size and comparative example, be described in detail respectively and analyze:
(In, Nb) codoping modified TiO
2with SrTiO
3compound and the resistance to electric field strength E of the titanium dioxide base composite ceramic of embodiment 1 to the embodiment 7 obtained
bvalue has brought up to 3.6kV/cm to 19.4kV/cm, relative permittivity ε
rstill the high level being greater than 2470 is presented.Corresponding comparative example 1 for chemical composition expression formula be (In
0.50, Nb
0.50)
0.01(TiO
2)
0.99pottery, its relative permittivity ε
ralthough value is up to 42580, resistance to electric field strength E
bvalue is only 0.13kV/cm.
(In, Nb) codoping modified TiO
2with SrTiO
3compound and the resistance to electric field strength E of the titanium dioxide base composite ceramic of the embodiment 8 obtained
bvalue has brought up to 12.4kV/cm, relative permittivity ε
rstill there is the high level of 8310.Corresponding comparative example 2 for chemical composition expression formula be (In
0.50, Nb
0.50)
0.05(TiO
2)
0.95pottery, its relative permittivity ε
ralthough value is up to 55840, resistance to electric field strength E
bvalue is only 0.09kV/cm.
(In, Nb) codoping modified TiO
2with SrTiO
3compound and the resistance to electric field strength E of the titanium dioxide base composite ceramic of the embodiment 9 obtained
bvalue has brought up to 10.3kV/cm, relative permittivity ε
rstill there is the high level of 9670.Corresponding comparative example 3 for chemical composition expression formula be (In
0.50, Nb
0.50)
0.10(TiO
2)
0.10pottery, its relative permittivity ε
ralthough value is up to 87350, resistance to electric field strength E
bvalue is only 0.07kV/cm.
(In, Ta) codoping modified TiO
2with SrTiO
3compound and the resistance to electric field strength E of the titanium dioxide base composite ceramic of the embodiment 10 obtained
bvalue has brought up to 16.4kV/cm, relative permittivity ε
rstill there is the high level of 6930.Corresponding comparative example 4 for chemical composition expression formula be (In
0.50, Ta
0.50)
0.01(TiO
2)
0.99pottery, its relative permittivity ε
ralthough value is up to 36260, resistance to electric field strength E
bvalue is only 0.14kV/cm.
(In, Sb) codoping modified TiO
2with SrTiO
3compound and the resistance to electric field strength E of the titanium dioxide base composite ceramic of the embodiment 11 obtained
bvalue has brought up to 13.7kV/cm, relative permittivity ε
rstill there is the high level of 6110.Corresponding comparative example 5 for chemical composition expression formula be (In
0.50, Sb
0.50)
0.01(TiO
2)
0.99pottery, its relative permittivity ε
ralthough value is up to 25690, resistance to electric field strength E
bvalue is only 0.12kV/cm.
(La, Nb) codoping modified TiO
2with SrTiO
3compound and the resistance to electric field strength E of the titanium dioxide base composite ceramic of the embodiment 12 obtained
bvalue has brought up to 11.6kV/cm, relative permittivity ε
rstill there is the high level of 7820.Corresponding comparative example 6 for chemical composition expression formula be (La
0.50, Nb
0.50)
0.01(TiO
2)
0.99pottery, its relative permittivity ε
ralthough value is up to 43450, resistance to electric field strength E
bvalue is only 0.10kV/cm.
(Ba, Nb) codoping modified TiO
2with SrTiO
3compound and the resistance to electric field strength E of the titanium dioxide base composite ceramic of the embodiment 13 obtained
bvalue has brought up to 12.5kV/cm, relative permittivity ε
rstill there is the high level of 5190.Corresponding comparative example 7 for chemical composition expression formula be (Ba
1.50, Nb
0.50)
0.01(TiO
2)
0.99pottery, its relative permittivity ε
ralthough value is up to 13510, resistance to electric field strength E
bvalue is only 0.18kV/cm.
In sum, with the codoping modified TiO of single-phase
2stupalith is compared, with SrTiO
3the titanium dioxide based composite ceramic material that compound obtains still has larger relative permittivity ε
rvalue, and resistance to electric field strength E
bvalue is significantly improved improvement.
Claims (2)
1. a titanium dioxide base composite ceramic dielectric materials, is characterized in that, chemical formula is as follows:
xSrTiO
3―(1–x)A；
Wherein, x=0.03 ~ 0.40;
A is through codoping modified titanium dioxide, chemical composition expression formula (B, C)
y(TiO
2)
1 – y; In formula, the element that the element that B is ionic valence condition+5 valency, C are ionic valence condition+3 valency or+divalent; The molar ratio of B, C is determined according to the electric neutrality principle of stupalith; Y=0.005 ~ 0.15;
Described B is the combination of one of Nb, Ta or Sb or two or more element;
Described C is a kind of element in In or La rare earth series of elements.
2. titanium dioxide base composite ceramic dielectric materials as claimed in claim 1, is characterized in that, x=0.05 ~ 0.30.
3
.titanium dioxide base composite ceramic dielectric materials as claimed in claim 1, is characterized in that, y=0.01 ~ 0.05.
4
.described in claim 1, the preparation method of titanium dioxide base composite ceramic dielectric materials, is characterized in that, comprise the steps:
(1) strontium titanate ceramics powder is prepared;
(2) codoping modified titanium dioxide ceramic powder is prepared;
(3) get the obtained strontium titanate ceramics powder of step (1) and the obtained codoping modified titanium dioxide ceramic powder of step (2) by metered proportions weigh batching, through mixing and ball milling, drying, obtain ceramic powder mixture;
(4) formed body, after granulation and forming processes, is carried out plastic removal by ceramic powder mixture step (3) obtained, and then under 1200 ~ 1500 DEG C of temperature condition, sinters 1 ~ 40h, obtained titanium dioxide base composite ceramic dielectric materials.
5
.the application of titanium dioxide base composite ceramic dielectric materials described in claim 1 manufacturing electrically, in electronic component.
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| CN105948743B (en) * | 2016-04-29 | 2019-04-09 | 山东大学 | A kind of modified codope titanium dioxide high dielectric ceramic material and its preparation method and application |
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| CN114380590B (en) * | 2022-01-25 | 2022-10-28 | 山东国瓷功能材料股份有限公司 | Titanium oxide-based ceramic filler with high dielectric property and preparation method thereof |
| CN115073164B (en) * | 2022-06-13 | 2023-06-06 | 安徽工程大学 | Ca+Sb co-doped TiO 2 Giant dielectric ceramic, preparation method and application thereof |
| CN115093215B (en) * | 2022-06-17 | 2023-06-23 | 安徽工程大学 | Sr+Sb co-doped TiO 2 Basic giant dielectric ceramic, preparation method and application thereof |
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