CN104478431B - Ion modification titanium dioxide ceramic material and preparation method with high-k - Google Patents
Ion modification titanium dioxide ceramic material and preparation method with high-k Download PDFInfo
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Abstract
The present invention relates to ion modification titanium dioxide ceramic material of a kind of high-k and low-dielectric loss and preparation method thereof, belong to environmentally friendly dielectric ceramic field.Ceramic material of the present invention is expressed as (A with formula0.5Nb0.5)xTi1‑xO2, wherein A is Bi, Al, Ga, Y, Sc, Yb, Dy, Sm, Gd and Pr, the molar content of 0.005≤x≤0.150；The ceramic material uses conventional solid sintering process preparation technology, and different trivalent element As and identical pentavalent Nb elements are added in formula dispensing；Its dielectric constant of gained ceramic material is up to 106, dielectric loss as little as 6%.Ceramics prepared by the present invention have larger practical value in the miniaturization of nowadays electronic component, light-weighted epoch.The device that especially prepared by the ceramics has actual application value in the various electronic devices such as capacitor and dynamic memory.
Description
Technical field
The present invention relates to a class ceramic material, the ion modification titanium dioxide ceramic material of more particularly to a kind of high-k
Material and preparation method thereof, belongs to environmentally friendly dielectric ceramic field.
Background technology
In past more than the 30 years time, the microelectronic industry based on semi-conductor industry has been achieved for considerable
Progressive, microelectronic industry has become various countries' key pillars of the national economy.The miniaturization of device, it is integrated, high density into
To promote the key factor of microelectronic industry development, high dielectric constant material also possesses more and more important in terms of microelectronic component
Status.
So-called high dielectric constant material refers to that dielectric constant (ε) is more than the general of the dielectric material of silica (ε=3.9)
Claim.And most of high-k ε '>1000 belong to ferroelectric, such as BaTiO3、Pb(Zr,Ti)O3And (Ba, Sr)
TiO3Deng.However, the dielectric properties of these materials understand variation with temperature and have and significantly change, therefore device can be influenceed
Stability.BaTiO3Be dielectric material initially 1945 by Japan and the United States, Su Deng states while succeeding in developing.BaTiO3Dielectric
Constant reaches as high as 25000, but pure BaTiO3Dielectric constant at room temperature only has 1600 or so, such as to make its dielectric constant
Increase moves peak agent, it is necessary to add, and the Curie temperature of material is down near room temperature, its dielectric constant can just increase.However, with
The increase of dielectric constant, to reduce its rate of temperature change, will also add broadening agent, though the peak value of the material dielectric constant by
To oppressive and broadening.2000, Subramanian et al. reported a kind of CaCu with high-k first3Ti4O12
(following letter CCTO) material.Dielectric constant of this material under the conditions of room temperature, 1kHz can be up to 12000, and 100~
Its dielectric constant is kept to be basically unchanged within the temperature range of 600K.The material has been widely used in manufacture capacitor and dynamic is deposited
In the various electronic devices such as reservoir (DRAM).But because it has of a relatively high dielectric loss and needs further raising.Cause
This, research has the new dielectric material of high-k and low-dielectric loss concurrently simultaneously, is current main direction of studying, is also
Where the task of the present invention.
The content of the invention
It is an object of the invention to obtained by adding new trivalent and pentavalent doped chemical simultaneously in titanium dioxide
Obtain the ion modification titanium dioxide ceramic material of high-k and low-dielectric loss；And the system of the dielectric ceramic material is provided
Preparation Method.This method uses conventional solid sintering process, the ion modification titanium dioxide ceramic material of preparation, its dielectric constant (εr)
Up to 106, dielectric loss (tan δ) as little as 6%.
To realize the above-mentioned purpose of the present invention, what the present invention was realized using the technical scheme of following technical measures composition.
The present invention basic ideas be：By adding new different triad A simultaneously and identical in titanium dioxide
Pentad Nb, and conventional solid sintering process is used, sintering temperature is controlled in sintering to obtain high-k and low dielectric
The titanium dioxide ceramic of loss.The titania systems can produce high-k and the general principle of low-dielectric loss may
It is：(1) due to Ti4+Ion is plied in the centre position, six O with surrounding2-Formed【TiO6】Octahedron, works as A3+And Nb5+After addition,
Replace Ti4+Formed【AO6】It is octahedra and【NbO6】Octahedron, triad A3+Ion needs Lacking oxygen to carry out electric charge as acceptor
Supplement, and then certain Lacking oxygen is formed in the material, it is theoretical according to Inner barrier layers (IBLC), it is brilliant in the solid solution of formation
Grain and crystal boundary have different conductance mechanism, and the presence of Lacking oxygen can cause Ti4+To Ti3+Conversion；Grain boundaries are due to then
Lacking oxygen migrates and forms high conductivity；Low-dielectric loss is due to the overactivity energy of its grain boundaries.(2) managed according to electronics pinning
By：Zonule in crystal grain forms the disfigurement model of electronics and Lacking oxygen.Electronics is due to Ti4+To Ti3+Conversion is formed
, Lacking oxygen is due to A3+Replace Ti4+Produce.Such multiple dipoles it is integrated so that it has high-k；It is low
Dielectric loss is, because its electronics is captured, to form dipole, its specific mechanism needs further to be probed into.
Because the titania additive material has sensitiveness to process conditions used, thus need by adjusting sintering temperature
Spend to optimize its dielectric properties.Therefore, the present invention is exactly to be made pottery to obtain the dielectric of desired high-k and low-dielectric loss
Ceramic material, that is, the titanium dioxide ceramic material for the ion modification prepared, its formula is expressed as (A0.5Nb0.5)xTi1-xO2。
A kind of ion modification titanium dioxide ceramic material with high-k of the present invention, it is proposed, according to the invention,
The titanium dioxide ceramic material is by formula (A0.5Nb0.5)xTi1-xO2Represent, A is Bi, Al, Ga, Y, Sc, Yb, Dy, Sm, Gd in formula,
Pr；Its x span is 0.005~0.150 molar content.
In above-mentioned technical proposal of the present invention, the ion modification titanium dioxide ceramic material, its dielectric constant is up to 106,
Meanwhile, dielectric loss as little as 6%.
A kind of preparation method of the ion modification titanium dioxide ceramic material of high-k of the present invention, its feature exists
In comprising the following steps that：
(1) conventional solid sintering process preparation technology is used, in formula (A0.5Nb0.5)xTi1-xO2Trivalent is added in formula simultaneously
Element A and pentavalent Nb elements, with analytically pure titanium dioxide, or bismuth oxide, or aluminum oxide, or gallium oxide, or yittrium oxide, or oxygen
Change scandium, or ytterbium oxide, or dysprosia, or samarium oxide, or gadolinium oxide, or praseodymium oxide, or niobium pentaoxide is raw material；According to corresponding
Formula (the A of system0.5Nb0.5)xTi1-xO2It is Bi, Al, Ga, Y, Sc, Yb, Dy, Sm, Gd and Pr to carry out A in dispensing, formula, and x's takes
Value scope is 0.005~0.150 molar content；
(2) raw material for preparing step (1) carried out rolling ball milling by medium of absolute ethyl alcohol, by rolling ball milling 24 hours
Powder afterwards is dried, and obtains mixed powder；
(3) pre-burning after the mixed powder obtained by step (2) being incubated into 4 hours at a temperature of 1050-1100 DEG C；Pre- burned
Mixed powder in, add 8wt% polyvinyl alcohol water solution granulation；
(4) powder after step (3) is granulated, sequin and dumping are compressed into using grinding tool；Again by after dumping
Sequin is sintered after being incubated 4-5 hours at a temperature of 1220~1450 DEG C, obtains potsherd；
(5) potsherd obtained by step (4) is obtained into the ion modification titanium dioxide pottery of high-k by upper silver electrode
Ceramic material；Then its electric property is measured.
It is described by adding triad and the ion modification prepared by pentad in preparation method of the present invention
Titanium dioxide ceramic material, its dielectric constant is up to 106, dielectric loss as little as 6%.
The meaning of ion modification of the present invention is while adding new triad A and pentad Nb in titanium dioxide
The ceramic material of high-k and low-dielectric loss is obtained in titanium.Generally the dielectric constant of pure titanium dioxide is 104, it is situated between
Electrical loss is 25%, therefore, causes that its dielectric constant is higher in titanium dioxide by adding element of the present invention, dielectric
Loss is lower.
The present invention has advantages below and beneficial technique effect：
1st, the part doped chemical for the ion modification titanium dioxide dielectric ceramic that the present invention is provided, such as Bi, Al, Ga, Y, Sc,
Yb, Dy, Sm, Gd, Pr and all formula doping combinations, belong to technological precedence in presently relevant research field；New three
Valency elements A and pentad Nb addition optimize the performance of the ceramic material system, it is had more in field of electronic devices
It is widely applied space.
2nd, the ion modification titanium dioxide dielectric ceramic that the present invention is provided has higher dielectric constant and relatively low dielectric
Loss, its dielectric constant is up to 106, and dielectric loss as little as 6%.
3rd, the dielectric ceramic that provides of the present invention is due to good temperature stability, thus by the electronics of the ceramic making
Device has wider temperature in use scope.
4th, the preparation method for the dielectric ceramic that the present invention is provided is simple to operation, adds the possibility of its industrialized production
Property.
Brief description of the drawings
Fig. 1 be the embodiment of the present invention 1 prepare work as x=0.005,0.010,0.025,0.035,0.050,0.100,
0.150 is changes during value, when A is Bi fixed elements, and formula is (Bi0.5Nb0.5)xTi1-xO2The phase of dielectric ceramic at 1 khz
To the change curve of dielectric constant with temperature.
Fig. 2 is the x=0.005 that works as of the preparation of the embodiment of the present invention 2, and 0.100,0.150 is changes during value, and A fixes for Ga
During element, formula is (Ga0.5Nb0.5)xTi1-xO2The relative dielectric constant variation with temperature curve of dielectric ceramic at 1 khz.
Fig. 3 is the x=0.005 that works as of the preparation of the embodiment of the present invention 3, and 0.100,0.150 is changes during value, and A fixes for Al
During element, formula is (Al0.5Nb0.5)xTi1-xO2The relative dielectric constant variation with temperature curve of dielectric ceramic at 1 khz.
Fig. 4 is the x=0.005 that works as of the preparation of the embodiment of the present invention 4, and 0.100,0.150 is changes during value, and A is that Y fixations are first
When plain, formula is (Y0.5Nb0.5)xTi1-xO2The relative dielectric constant variation with temperature curve of dielectric ceramic at 1 khz.
Fig. 5 is the x=0.005 that works as of the preparation of the embodiment of the present invention 5, and 0.100,0.150 is changes during value, and A fixes for Sc
During element, formula is (Sc0.5Nb0.5)xTi1-xO2The relative dielectric constant variation with temperature curve of dielectric ceramic at 1 khz.
Fig. 6 is the x=0.005 that works as of the preparation of the embodiment of the present invention 6, and 0.150 is changes during value, when A is Dy fixed elements,
Formula is (Dy0.5Nb0.5)xTi1-xO2The relative dielectric constant of dielectric ceramic at 1 khzrVariation with temperature curve.
Fig. 7 is the x=0.005 that works as of the preparation of the embodiment of the present invention 7, and 0.150 is changes during value, when A is Sm fixed elements,
Formula is (Sm0.5Nb0.5)xTi1-xO2The relative dielectric constant variation with temperature curve of dielectric ceramic at 1 khz.
Fig. 8 is the x=0.005 that works as of the preparation of the embodiment of the present invention 8, and 0.150 is changes during value, when A is Yb fixed elements,
Formula is (Yb0.5Nb0.5)xTi1-xO2The relative dielectric constant ε of dielectric ceramic at 1 khzrVariation with temperature curve.
Fig. 9 is the x=0.005 that works as of the preparation of the embodiment of the present invention 9, and 0.150 is changes during value, when A is Pr fixed elements,
Formula is (Pr0.5Nb0.5)xTi1-xO2The relative dielectric constant ε of dielectric ceramic at 1 khzrVariation with temperature curve.
Figure 10 is the x=0.005 that works as of the preparation of the embodiment of the present invention 10, and 0.150 is changes during value, and A is Gd fixed elements
When, formula is (Gd0.5Nb0.5)xTi1-xO2The relative dielectric constant ε of dielectric ceramic at 1 khzrVariation with temperature curve.
Embodiment
Ion modification titanium dioxide ceramic material of the present invention is further described below by embodiment, it is necessary to
It is pointed out here that be that the embodiment is only intended to further illustrate the present invention, but should not be understood as to the present invention protection
Any limitation of scope, the those of skill in the art in the field can make some non-intrinsically safes according to the content of the invention described above
Modifications and adaptations.
In following examples, the ion modification titanium dioxide ceramic of various combination is given under specific preparation process condition
Resulting εrWith tan δ etc. performance parameter：
Embodiment 1
According to formula (A0.5Nb0.5)xTi1-xO2The ion modification titanium dioxide ceramic constituent content of expression carries out dispensing；
Work as x=0.005, during A=Bi,
It is formulated one：(Bi0.5Nb0.5)0.005Ti0.995O2,
Work as x=0.010, during A=Bi,
It is formulated two：(Bi0.5Nb0.5)0.01Ti0.99O2,
Work as x=0.025, during A=Bi,
It is formulated three：(Bi0.5Nb0.5)0.025Ti0.975O2,
Work as x=0.035, during A=Bi,
It is formulated four：(Bi0.5Nb0.5)0.035Ti0.965O2,
Work as x=0.050, during A=Bi,
It is formulated five：(Bi0.5Nb0.5)0.05Ti0.95O2,
Work as x=0.100, during A=Bi,
It is formulated six：(Bi0.5Nb0.5)0.1Ti0.9O2,
Work as x=0.150, during A=Bi,
It is formulated seven：(Bi0.5Nb0.5)0.15Ti0.85O2。
The preparation of formula one：With analytically pure Bi2O3, Nb2O5And TiO2It is for raw material, each raw material is stoichiometrically accurate
Weigh, by load weighted raw material using absolute ethyl alcohol as ball-milling medium, ball milling is dried after 24 hours and obtains mixed powder；By gained
Dry powder is incubated pre-burning in 4 hours at 1050 DEG C, and the polyvinyl alcohol water solution that concentration is 8wt% is then added in pre- burned powder
Granulation；Sequin is pressed under 10MPa pressure with a diameter of 10mm grinding tool after granulation, its a diameter of 10mm, thickness is
1mm, and dumping, the sequin after dumping is sintered under table 1 below different temperatures, potsherd is obtained；By the potsherd quilt after sintering
The electric property of upper silver electrode, then measurement gained ceramics.
The preparation of formula two-seven：With analytically pure Bi2O3, Nb2O5And TiO2For raw material, enter by the chemical formula of formula two-seven
Row dispensing；By each raw material stoichiometrically precise；Other preparation conditions and parameter used are identical with formula one.
Manufactured in the present embodiment to work as x=0.005,0.001,0.025,0.035,0.050,0.100,0.15 is change value
When, (Bi when A=Bi is fixed element0.5Nb0.5)xTi1-xO2The relative dielectric constant ε of dielectric ceramic at 1 khzrWith temperature
Change curve it is as shown in Figure 1.
The present embodiment formula one-seven is shown in the electric property of different sintering temperatures sintering, and test gained dielectric ceramic
Shown in table 1.
Table 1 at ambient temperature, is formulated the preparation parameter and electric property of one-seven dielectric ceramic
Embodiment 2
According to formula (A0.5Nb0.5)xTi1-xO2The ion modification titanium dioxide ceramic constituent content of expression carries out dispensing；
Work as x=0.005, during A=Ga,
It is formulated one：(Ga0.5Nb0.5)0.005Ti0.995O2,
Work as x=0.100, during A=Ga,
It is formulated two：(Ga0.5Nb0.5)0.1Ti0.9O2,
Work as x=0.150, during A=Ga,
It is formulated three：(Ga0.5Nb0.5)0.15Ti0.85O2。
The preparation of formula one：With analytically pure Ga2O3, Nb2O5And TiO2It is for raw material, each raw material is stoichiometrically accurate
Weigh, by load weighted raw material using absolute ethyl alcohol as ball-milling medium, ball milling is dried after 24 hours and obtains mixed powder；By gained
Dry powder is incubated pre-burning in 4 hours at 1100 DEG C, and the polyvinyl alcohol water solution that concentration is 8wt% is then added in pre- burned powder
Granulation；Sequin is pressed under 10MPa pressure with a diameter of 10mm grinding tool after granulation, its a diameter of 10mm, thickness is
1mm, and dumping, the sequin after dumping is sintered at a temperature of table 2 below identical (also can directly be write as 1450 DEG C), obtains ceramic
Piece；By the potsherd after sintering by the electric property of upper silver electrode, then measurement gained ceramics.
The preparation of formula two-three：With analytically pure Ga2O3, Nb2O5And TiO2For raw material, enter by the chemical formula of formula two-three
Row dispensing；By each raw material stoichiometrically precise；Other preparation conditions and parameter used are identical with formula one.
Manufactured in the present embodiment to work as x=0.005,0.100,0.150 is changes during value, when A=Ga is fixed element
(Ga0.5Nb0.5)xTi1-xO2The relative dielectric constant ε of dielectric ceramic at 1 khzrVariation with temperature curve is as shown in Figure 2.
The present embodiment formula one-three is shown in the electric property of identical sintering temperature sintering, and test gained dielectric ceramic
Shown in table 2.
Table 2 at ambient temperature, is formulated the preparation parameter and electric property of one-three dielectric ceramic
Embodiment 3
According to formula (A0.5Nb0.5)xTi1-xO2The ion modification titanium dioxide ceramic constituent content of expression carries out dispensing；
Work as x=0.005, during A=Al,
It is formulated one：(Al0.5Nb0.5)0.005Ti0.995O2,
Work as x=0.100, during A=Al,
It is formulated two：(Al0.5Nb0.5)0.1Ti0.9O2,
Work as x=0.150, during A=Al,
It is formulated three：(Al0.5Nb0.5)0.15Ti0.85O2。
The preparation of formula one：With analytically pure Al2O3, Nb2O5And TiO2It is for raw material, each raw material is stoichiometrically accurate
Weigh, by load weighted raw material using absolute ethyl alcohol as ball-milling medium, ball milling is dried after 24 hours and obtains mixed powder；By gained
Dry powder is incubated pre-burning in 4 hours at 1100 DEG C, and the polyvinyl alcohol water solution that concentration is 8wt% is then added in pre- burned powder
Granulation；Sequin is pressed under 10MPa pressure with a diameter of 10mm grinding tool after granulation, its a diameter of 10mm, thickness is
1mm, and dumping, the sequin after dumping is sintered at the identical temperature of table 3 below, potsherd is obtained；By the potsherd quilt after sintering
The electric property of upper silver electrode, then measurement gained ceramics.
The preparation of formula two-three：With analytically pure Al2O3, Nb2O5And TiO2For raw material, enter by the chemical formula of formula two-three
Row dispensing；By each raw material stoichiometrically precise；Other preparation conditions and parameter used are identical with formula one.
Manufactured in the present embodiment to work as x=0.005,0.100,0.150 is changes during value, when A=Al is fixed element
(Al0.5Nb0.5)xTi1-xO2The relative dielectric constant ε of dielectric ceramic at 1 khzrVariation with temperature curve is as shown in Figure 3.
The present embodiment formula one-three is shown in the electric property of identical sintering temperature sintering, and test gained dielectric ceramic
Shown in table 3.
Table 3 at ambient temperature, is formulated the preparation parameter and electric property of one-three dielectric ceramic
Embodiment 4
According to formula (A0.5Nb0.5)xTi1-xO2The ion modification titanium dioxide ceramic constituent content of expression carries out dispensing；
Work as x=0.005, during A=Y,
It is formulated one：(Y0.5Nb0.5)0.005Ti0.995O2,
Work as x=0.100, during A=Y,
It is formulated two：(Y0.5Nb0.5)0.1Ti0.9O2,
Work as x=0.150, during A=Y,
It is formulated three：(Y0.5Nb0.5)0.15Ti0.85O2。
The preparation of formula one：With analytically pure Y2O3, Nb2O5And TiO2It is for raw material, each raw material is stoichiometrically accurate
Weigh, by load weighted raw material using absolute ethyl alcohol as ball-milling medium, ball milling is dried after 24 hours and obtains mixed powder；By gained
Dry powder is incubated pre-burning in 4 hours at 1100 DEG C, and the polyvinyl alcohol water solution that concentration is 8wt% is then added in pre- burned powder
Granulation；Sequin is pressed under 10MPa pressure with a diameter of 10mm grinding tool after granulation, its a diameter of 10mm, thickness is
1mm, and dumping, by the sequin after dumping table 4 below it is identical (at a temperature of sinter, obtain potsherd；By the potsherd quilt after sintering
The electric property of upper silver electrode, then measurement gained ceramics.
The preparation of formula two-three：With analytically pure Y2O3, Nb2O5And TiO2For raw material, enter by the chemical formula of formula two-three
Row dispensing；By each raw material stoichiometrically precise；Other preparation conditions and parameter used are identical with formula one.
Manufactured in the present embodiment to work as x=0.005,0.100,0.150 is changes during value, when A=Y is fixed element
(Y0.5Nb0.5)xTi1-xO2The relative dielectric constant ε of dielectric ceramic at 1 khzrVariation with temperature curve is as shown in Figure 4.
The present embodiment formula one-three is shown in the electric property of identical sintering temperature sintering, and test gained dielectric ceramic
Shown in table 4.
Table 4 at ambient temperature, is formulated the preparation parameter and electric property of one-three dielectric ceramic
Embodiment 5
According to formula (A0.5Nb0.5)xTi1-xO2The ion modification titanium dioxide ceramic constituent content of expression carries out dispensing；
Work as x=0.005, during A=Sc,
It is formulated one：(Sc0.5Nb0.5)0.005Ti0.995O2,
Work as x=0.100, during A=Sc,
It is formulated two：(Sc0.5Nb0.5)0.1Ti0.9O2,
Work as x=0.150, during A=Sc,
It is formulated three：(Sc0.5Nb0.5)0.15Ti0.85O2。
The preparation of formula one：With analytically pure Sc2O3, Nb2O5And TiO2It is for raw material, each raw material is stoichiometrically accurate
Weigh, by load weighted raw material using absolute ethyl alcohol as ball-milling medium, ball milling is dried after 24 hours and obtains mixed powder；By gained
Dry powder is incubated pre-burning in 4 hours at 1100 DEG C, and the polyvinyl alcohol water solution that concentration is 8wt% is then added in pre- burned powder
Granulation；Sequin is pressed under 10MPa pressure with a diameter of 10mm grinding tool after granulation, its a diameter of 10mm, thickness is
1mm, and dumping, the sequin after dumping is sintered at the identical temperature of table 5 below, potsherd is obtained；By the potsherd quilt after sintering
The electric property of upper silver electrode, then measurement gained ceramics.
The preparation of formula two-three：With analytically pure Sc2O3, Nb2O5And TiO2For raw material, enter by the chemical formula of formula two-three
Row dispensing；By each raw material stoichiometrically precise；Other preparation conditions and parameter used are identical with formula one.
Manufactured in the present embodiment to work as x=0.005,0.100,0.150 is changes during value, when A=Sc is fixed element
(Sc0.5Nb0.5)xTi1-xO2The relative dielectric constant ε of dielectric ceramic at 1 khzrVariation with temperature curve is as shown in Figure 5.
The present embodiment formula one-three is shown in the electric property of identical sintering temperature sintering, and test gained dielectric ceramic
Shown in table 5.
Table 5 at ambient temperature, is formulated the preparation parameter and electric property of one-three dielectric ceramic
Embodiment 6
According to formula (A0.5Nb0.5)xTi1-xO2The ion modification titanium dioxide ceramic constituent content of expression carries out dispensing；
Work as x=0.005, during A=Dy,
It is formulated one：(Dy0.5Nb0.5)0.005Ti0.995O2,
Work as x=0.150, during A=Dy,
It is formulated two：(Dy0.5Nb0.5)0.15Ti0.85O2。
The preparation of formula one：With analytically pure Dy2O3, Nb2O5And TiO2It is for raw material, each raw material is stoichiometrically accurate
Weigh, by load weighted raw material using absolute ethyl alcohol as ball-milling medium, ball milling is dried after 24 hours and obtains mixed powder；By gained
Dry powder is incubated pre-burning in 4 hours at 1100 DEG C, and the polyvinyl alcohol water solution that concentration is 8wt% is then added in pre- burned powder
Granulation；Sequin is pressed under 10MPa pressure with a diameter of 10mm grinding tool after granulation, its a diameter of 10mm, thickness is
1mm, and dumping, the sequin after dumping is sintered at the identical temperature of table 6 below, potsherd is obtained；By the potsherd quilt after sintering
The electric property of upper silver electrode, then measurement gained ceramics.
The preparation of formula two：With analytically pure Dy2O3, Nb2O5And TiO2For raw material, matched somebody with somebody by the chemical formula of formula two
Material；By each raw material stoichiometrically precise；Other preparation conditions and parameter used are identical with formula one.
Manufactured in the present embodiment to work as x=0.005,0.150 is changes during value, when A=Dy is fixed element
(Dy0.5Nb0.5)xTi1-xO2The relative dielectric constant ε of dielectric ceramic at 1 khzrVariation with temperature curve is as shown in Figure 6.
The present embodiment formula one-two is shown in the electric property of identical sintering temperature sintering, and test gained dielectric ceramic
Shown in table 6.
Table 6 at ambient temperature, is formulated the preparation parameter and electric property of one-two dielectric ceramic
Embodiment 7
According to formula (A0.5Nb0.5)xTi1-xO2The ion modification titanium dioxide ceramic constituent content of expression carries out dispensing；
Work as x=0.005, during A=Sm,
It is formulated one：(Sm0.5Nb0.5)0.005Ti0.995O2,
Work as x=0.150, during A=Sm,
It is formulated two：(Sm0.5Nb0.5)0.15Ti0.85O2。
The preparation of formula one：With analytically pure Sm2O3, Nb2O5And TiO2It is for raw material, each raw material is stoichiometrically accurate
Weigh, by load weighted raw material using absolute ethyl alcohol as ball-milling medium, ball milling is dried after 24 hours and obtains mixed powder；By gained
Dry powder is incubated pre-burning in 4 hours at 1100 DEG C, and the polyvinyl alcohol water solution that concentration is 8wt% is then added in pre- burned powder
Granulation；Sequin is pressed under 10MPa pressure with a diameter of 10mm grinding tool after granulation, its a diameter of 10mm, thickness is
1mm, and dumping, the sequin after dumping is sintered at the identical temperature of table 7 below, potsherd is obtained；By the potsherd quilt after sintering
The electric property of upper silver electrode, then measurement gained ceramics.
The preparation of formula two：With analytically pure Sm2O3, Nb2O5And TiO2For raw material, matched somebody with somebody by the chemical formula of formula two
Material；By each raw material stoichiometrically precise；Other preparation conditions and parameter used are identical with formula one.
Manufactured in the present embodiment to work as x=0.005,0.150 is changes during value, when A=Sm is fixed element
(Sm0.5Nb0.5)xTi1-xO2The relative dielectric constant ε of dielectric ceramic at 1 khzrVariation with temperature curve is as shown in Figure 7.
The present embodiment formula one-two is shown in the electric property of identical sintering temperature sintering, and test gained dielectric ceramic
Shown in table 7.
Table 7 at ambient temperature, is formulated the preparation parameter and electric property of one-two dielectric ceramic
Embodiment 8
According to formula (A0.5Nb0.5)xTi1-xO2The ion modification titanium dioxide ceramic constituent content of expression carries out dispensing；
Work as x=0.005, during A=Yb,
It is formulated one：(Yb0.5Nb0.5)0.005Ti0.995O2,
Work as x=0.150, during A=Yb,
It is formulated two：(Yb0.5Nb0.5)0.15Ti0.85O2。
The preparation of formula one：With analytically pure Yb2O3, Nb2O5And TiO2It is for raw material, each raw material is stoichiometrically accurate
Weigh, by load weighted raw material using absolute ethyl alcohol as ball-milling medium, ball milling is dried after 24 hours and obtains mixed powder；By gained
Dry powder is incubated pre-burning in 4 hours at 1100 DEG C, and the polyvinyl alcohol water solution that concentration is 8wt% is then added in pre- burned powder
Granulation；Sequin is pressed under 10MPa pressure with a diameter of 10mm grinding tool after granulation, its a diameter of 10mm, thickness is
1mm, and dumping, the sequin after dumping is sintered at the identical temperature of table 8 below, potsherd is obtained；By the potsherd quilt after sintering
The electric property of upper silver electrode, then measurement gained ceramics.
The preparation of formula two：With analytically pure Yb2O3, Nb2O5And TiO2For raw material, matched somebody with somebody by the chemical formula of formula two
Material；By each raw material stoichiometrically precise；Other preparation conditions and parameter used are identical with formula one.
Manufactured in the present embodiment to work as x=0.005,0.150 is changes during value, when A=Yb is fixed element
(Yb0.5Nb0.5)xTi1-xO2The relative dielectric constant ε of dielectric ceramic at 1 khzrVariation with temperature curve is as shown in Figure 8.
The present embodiment formula one-two is shown in the electric property of identical sintering temperature sintering, and test gained dielectric ceramic
Shown in table 8.
Table 8 at ambient temperature, is formulated the preparation parameter and electric property of one-two dielectric ceramic
Embodiment 9
According to formula (A0.5Nb0.5)xTi1-xO2The ion modification titanium dioxide ceramic content of expression carries out dispensing；
Work as x=0.005, during A=Pr,
It is formulated one：(Pr0.5Nb0.5)0.005Ti0.995O2,
Work as x=0.150, during A=Pr,
It is formulated two：(Pr0.5Nb0.5)0.15Ti0.85O2。
The preparation of formula one：With analytically pure Pr2O3, Nb2O5And TiO2It is for raw material, each raw material is stoichiometrically accurate
Weigh, by load weighted raw material using absolute ethyl alcohol as ball-milling medium, ball milling is dried after 24 hours and obtains mixed powder；By gained
Dry powder is incubated pre-burning in 4 hours at 1100 DEG C, and the polyvinyl alcohol water solution that concentration is 8wt% is then added in pre- burned powder
Granulation；Sequin is pressed under 10MPa pressure with a diameter of 10mm grinding tool after granulation, its a diameter of 10mm, thickness is
1mm, and dumping, the sequin after dumping is sintered at the identical temperature of table 9 below, potsherd is obtained；By the potsherd quilt after sintering
The electric property of upper silver electrode, then measurement gained ceramics.
The preparation of formula two：With analytically pure Pr2O3, Nb2O5And TiO2For raw material, matched somebody with somebody by the chemical formula of formula two
Material；By each raw material stoichiometrically precise；Other preparation conditions and parameter used are identical with formula one.
Manufactured in the present embodiment to work as x=0.005,0.150 is changes during value, when A=Pr is fixed element
(Pr0.5Nb0.5)xTi1-xO2The relative dielectric constant ε of dielectric ceramic at 1 khzrVariation with temperature curve is as shown in Figure 9.
The present embodiment formula one-two is shown in the electric property of identical sintering temperature sintering, and test gained dielectric ceramic
Shown in table 9.
Table 9 at ambient temperature, is formulated the preparation parameter and electric property of one-two dielectric ceramic
Embodiment 10
According to formula (A0.5Nb0.5)xTi1-xO2The ion modification titanium dioxide ceramic constituent content of expression carries out dispensing；
Work as x=0.005, during A=Gd,
It is formulated one：(Gd0.5Nb0.5)0.005Ti0.995O2,
Work as x=0.150, during A=Gd,
It is formulated two：(Gd0.5Nb0.5)0.15Ti0.85O2。
The preparation of formula one：With analytically pure Gd2O3, Nb2O5And TiO2It is for raw material, each raw material is stoichiometrically accurate
Weigh, by load weighted raw material using absolute ethyl alcohol as ball-milling medium, ball milling is dried after 24 hours and obtains mixed powder；By gained
Dry powder is incubated pre-burning in 4 hours at 1100 DEG C, and the polyvinyl alcohol water solution that concentration is 8wt% is then added in pre- burned powder
Granulation；Sequin is pressed under 10MPa pressure with a diameter of 10mm grinding tool after granulation, its a diameter of 10mm, thickness is
1mm, and dumping, the sequin after dumping is sintered at the identical temperature of table 10 below, potsherd is obtained；By the potsherd quilt after sintering
The electric property of upper silver electrode, then measurement gained ceramics.
The preparation of formula two：With analytically pure Gd2O3, Nb2O5And TiO2For raw material, matched somebody with somebody by the chemical formula of formula two
Material；By each raw material stoichiometrically precise；Other preparation conditions and parameter used are identical with formula one.
Manufactured in the present embodiment to work as x=0.005,0.150 is changes during value, when A=Gd is fixed element
(Gd0.5Nb0.5)xTi1-xO2The relative dielectric constant ε of dielectric ceramic at 1 khzrVariation with temperature curve is as shown in Figure 10.
The present embodiment formula one-two is shown in the electric property of identical sintering temperature sintering, and test gained dielectric ceramic
Shown in table 10.
Table 10 at ambient temperature, is formulated the preparation parameter and electric property of one-two dielectric ceramic
The ion modification titanium dioxide ceramic material prepared through the above embodiment of the present invention, its dielectric properties are listed from table
As a result it can be seen that, its dielectric constant and dielectric loss have a clear superiority in similar high-k dielectric materials.The material
Chemical constitution formula (the A of material0.5Nb0.5)xTi1-xO2, when A is Bi elements, during x=0.010, the dielectric of the titanium dioxide ceramic is normal
Number εrUp to 275768, when A is Bi elements, during x=0.005, its dielectric loss tan δ are 0.06737, as little as 6%.Thus
The device prepared by the titanium dioxide ceramic of the present invention has in the various electronic devices such as capacitor and dynamic memory (DRAM)
There is actual application value.
Claims (1)
1. a kind of preparation method of the ion modification titanium dioxide ceramic material with high-k, it is characterised in that including with
Lower processing step：
(1) conventional solid sintering process preparation technology is used, in formula (A0.5Nb0.5)xTi1-xO2Trivalent A members are added in formula simultaneously
Element and pentavalent Nb elements, with analytically pure titanium dioxide, or bismuth oxide, or aluminum oxide, or gallium oxide, or yittrium oxide, or oxidation
Scandium, or ytterbium oxide, or dysprosia, or samarium oxide, or gadolinium oxide, or praseodymium oxide, or niobium pentaoxide are raw material；According to corresponding body
Formula (the A of system0.5Nb0.5)xTi1-xO2Dispensing is carried out, A is Bi in formula, or Al, or Ga, or Y, or Sc, or Yb, or Dy, or Sm,
Or Gd, or Pr；X span is 0.005~0.150 molar content；
(2) raw material for preparing step (1) carries out rolling ball milling by medium of absolute ethyl alcohol, after rolling ball milling 24 hours
Powder drying obtains mixed powder；
(3) mixed powder obtained by step (2) is incubated pre-burning in 4 hours at a temperature of 1050-1100 DEG C；By pre- burned mixing
Dry powder adds 8wt% polyvinyl alcohol water solution granulation, obtains even-grained powder；
(4) powder after step (3) is granulated, sequin and dumping are compressed into using grinding tool；By the sequin after dumping
4-5 hours are incubated at a temperature of 1220~1450 DEG C to sinter, and obtain potsherd；
(5) the potsherd after step (4) is sintered obtains the ion modification titanium dioxide of tool high-k by upper silver electrode
Ceramic material, the dielectric constant and dielectric loss of measurement gained ceramic material；
By adding the trivalent element A and pentavalent Nb elements so that the dielectric constant of the titanium dioxide ceramic material prepared is up to
106, its dielectric loss as little as 6%.
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| CN106006726B (en) * | 2016-05-03 | 2018-11-27 | 广东风华高新科技股份有限公司 | Doped anatase titanic oxide material, preparation method and its application |
| CN107640970B (en) * | 2017-10-26 | 2019-12-03 | 陕西师范大学 | The AgNb of low frequency low-dielectric loss is co-doped with titania-based dielectric ceramic material and preparation method thereof |
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| CN108530069A (en) * | 2018-04-10 | 2018-09-14 | 四川大学 | A kind of preparation method for the ion modification titanium dioxide ceramic material that high-k has both with low-dielectric loss |
| CN108546112B (en) * | 2018-04-11 | 2021-02-09 | 广东风华高新科技股份有限公司 | Annular piezoresistor material, preparation method and application thereof |
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| CN111205085B (en) * | 2020-02-03 | 2021-07-27 | 河南理工大学 | Preparation method of titanium dioxide-based ceramic with ultrahigh dielectric constant and low dielectric loss |
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