CN104478431A - Ion modified titanium dioxide ceramic material with high dielectric constant and preparation method thereof - Google Patents
Ion modified titanium dioxide ceramic material with high dielectric constant and preparation method thereof Download PDFInfo
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- CN104478431A CN104478431A CN201410705357.XA CN201410705357A CN104478431A CN 104478431 A CN104478431 A CN 104478431A CN 201410705357 A CN201410705357 A CN 201410705357A CN 104478431 A CN104478431 A CN 104478431A
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Abstract
The invention relates to an ion modified titanium dioxide ceramic material with a high dielectric constant and a preparation method thereof, and belongs to the field of environment-friendly dielectric ceramics. The ceramic material disclosed by the invention is as shown in a general formula as follows: (A0.5Nb0.5)xTi(1-x)O2, wherein A is Bi, Al, Ga, Y, Sc, Yb, Dy, Sm, Gd and Pr, and x is not smaller than 0.005 mol content and not larger than 0.150 mol content. The ceramic material is prepared by adopting a traditional solid phase sintering process; the raw materials in the general formula are added with different trivalent A elements and the same pentavalent Nb element; the obtained ceramic material is as high as 10<6> in dielectric constant and as low as 6% in dielectric loss. The ceramic prepared by the method disclosed by the invention has a relatively large practical value in the present age when electronic elements are miniaturized and lightened, and especially the elements prepared from the ceramic have practical application values in various electronic elements such as capacitors and dynamic storage.
Description
Technical field
The present invention relates to a class stupalith, particularly a kind of ion modification titanium dioxide ceramic material and preparation method thereof of high-k, belongs to environmentally friendly dielectric ceramic field.
Background technology
In three times more than ten years in the past, the microelectronic industry based on semi-conductor industry achieves significant progress, and microelectronic industry has become various countries' key pillars of the national economy.The miniaturization of device, integrated, high-density becomes the important factor promoting microelectronic industry development, and high dielectric constant material also has more and more consequence in microelectronic device.
So-called high dielectric constant material refers to that specific inductivity (ε) is greater than the general term of the dielectric materials of silicon-dioxide (ε=3.9).And most of high-k ε ' >1000 all belong to ferroelectrics, such as BaTiO
3, Pb (Zr, Ti) O
3and (Ba, Sr) TiO
3deng.But the dielectric properties of these materials can variation with temperature and having significantly change, and therefore can affect the stability of device.BaTiO
3be that dielectric material was succeeded in developing by Japan and the United States, Su Deng state in 1945 at first simultaneously.BaTiO
3specific inductivity reach as high as 25000, but pure BaTiO
3specific inductivity at room temperature only has about 1600, and as its specific inductivity will be made to increase, need interpolation to move peak agent, the Curie temperature of material is down near room temperature, its specific inductivity just can increase.But, along with the increase of specific inductivity, to reduce its rate of temperature change, also to add broadening agent, even if the peak value of this material dielectric constant is subject to constraining and broadening.2000 years, a kind of CaCu with high-k of people's reported first such as Subramanian
3ti
4o
12(following simple CCTO) material.The specific inductivity of this material under room temperature, 1kHz condition can up to 12000, and keep its specific inductivity substantially constant in the temperature range of 100 ~ 600K.This material has been widely used in manufacturing in the various electron device such as electrical condenser and dynamic storage (DRAM).But need because it has relatively high dielectric loss to be improved further.Therefore, research has the novel dielectric materials of high-k and low-dielectric loss concurrently simultaneously, and being current main direction of studying, is also task place of the present invention.
Summary of the invention
The object of the invention is to the ion modification titanium dioxide ceramic material obtaining high-k and low-dielectric loss by adding novel trivalent and pentavalent doped element simultaneously in titanium dioxide; And the preparation method of this dielectric ceramic material is provided.The method adopts conventional solid sintering process, the ion modification titanium dioxide ceramic material of preparation, its specific inductivity (ε
r) can up to 10
6, dielectric loss (tan δ) is low to moderate 6%.
For realizing above-mentioned purpose of the present invention, the technical scheme that the present invention adopts following technical measures to form realizes.
Basic ideas of the present invention are: by adding novel different trivalent element A and identical pentad Nb in titanium dioxide simultaneously, and adopt conventional solid sintering process, in sintering, control sintering temperature to obtain the titanium dioxide ceramic of high-k and low-dielectric loss.The ultimate principle that this titania systems can produce high-k and low-dielectric loss may be: (1) is due to Ti
4+ion is plied in the centre position, with six O of surrounding
2-form [TiO
6] octahedra, work as A
3+and Nb
5+after adding, replace Ti
4+form [AO
6] octahedra and [NbO
6] octahedra, trivalent element A
3+ion as acceptor need Lacking oxygen carry out electric charge supplement, and then form certain Lacking oxygen in the material, theoretical according to Inner barrier layer (IBLC), in the sosoloid formed, grain and grain boundary has different electric conductivity mechanism, and the existence of Lacking oxygen can make Ti
4+to Ti
3+transform; Grain boundaries is then form high conductivity due to Lacking oxygen migration; Low-dielectric loss is the overactivity energy due to its grain boundaries.(2) according to electronics pinning theory: the zonule in crystal grain forms the disfigurement model of electronics and Lacking oxygen.Electronics is due to Ti
4+to Ti
3+conversion is formed, and Lacking oxygen is due to A
3+replace Ti
4+produce.The integrated of multiple dipoles like this makes it have high-k; Low-dielectric loss is because its electronics is captured, and form dipole, its concrete mechanism needs to be probed into further.
Because this titania additive material has susceptibility to processing condition used, thus need by regulating sintering temperature to optimize its dielectric properties.Therefore, the present invention is exactly the dielectric ceramic material for obtaining high-k and the low-dielectric loss expected, the titanium dioxide ceramic material of the ion modification namely prepared, its general formula is expressed as (A
0.5nb
0.5)
xti
1-xo
2.
A kind of ion modification titanium dioxide ceramic material with high-k of the present invention, according to the present invention, this titanium dioxide ceramic material is by general formula (A
0.5nb
0.5)
xti
1-xo
2represent, in formula, A is Bi, Al, Ga, Y, Sc, Yb, Dy, Sm, Gd, Pr; The span of its x is 0.005 ~ 0.150 molar content.
In technique scheme of the present invention, described ion modification titanium dioxide ceramic material, its specific inductivity is up to 10
6, meanwhile, dielectric loss is low to moderate 6%.
The preparation method of the ion modification titanium dioxide ceramic material of a kind of high-k of the present invention, is characterized in that comprising following processing step:
(1) conventional solid sintering process preparation technology is adopted, at general formula (A
0.5nb
0.5)
xti
1-xo
2add trivalent element A and pentavalent Nb element in formula simultaneously, with analytically pure titanium dioxide, or bismuth oxide, or aluminum oxide, or gallium oxide, or yttrium oxide, or Scium trioxide, or ytterbium oxide, or dysprosium oxide, or Samarium trioxide, or gadolinium sesquioxide, or Praseodymium trioxide, or Niobium Pentxoxide is raw material; According to the formula (A of corresponding system
0.5nb
0.5)
xti
1-xo
2prepare burden, in formula, A is Bi, Al, Ga, Y, Sc, Yb, Dy, Sm, Gd and Pr, and the span of x is 0.005 ~ 0.150 molar content;
(2) raw material step (1) prepared is that medium carries out rolling ball milling with dehydrated alcohol, is dried by the powder of rolling ball milling after 24 hours, obtains mixed powder;
(3) pre-burning after the mixed powder of step (2) gained being incubated 4 hours at 1050-1100 DEG C of temperature; In mixed powder burned in advance, add the polyvinyl alcohol water solution granulation of 8wt%;
(4) by the powder after step (3) granulation, grinding tool is utilized to be pressed into sequin and binder removal; Sinter after again the sequin after binder removal being incubated 4-5 hour at 1220 ~ 1450 DEG C of temperature, obtain ceramic plate;
(5) by step (4) gained ceramic plate by upper silver electrode, namely obtain the ion modification titanium dioxide ceramic material of high-k; Then its electric property is measured.
In preparation method of the present invention, described by adding trivalent element and the ion modification titanium dioxide ceramic material prepared by pentad, its specific inductivity is up to 10
6, dielectric loss is low to moderate 6%.
The meaning of ion modification of the present invention is to add the stupalith that novel trivalent element A and pentad Nb obtains high-k and low-dielectric loss in titanium dioxide simultaneously.The specific inductivity of usually pure titanium dioxide is 10
4, dielectric loss is 25%, and therefore, in titanium dioxide, make its specific inductivity higher by adding element of the present invention, dielectric loss is lower.
The present invention has the following advantages and useful technique effect:
1, the part doped element of ion modification titanium dioxide dielectric ceramic provided by the invention, as Bi, Al, Ga, Y, Sc, Yb, Dy, Sm, Gd, Pr and all general formulas doping combination, belongs to technological precedence in current Related Research Domain; Novel trivalent element A and the interpolation of pentad Nb optimize the performance of this stupalith system, make it have application space widely in field of electronic devices.
2, ion modification titanium dioxide dielectric ceramic provided by the invention has higher specific inductivity and lower dielectric loss, and its specific inductivity is up to 10
6, and dielectric loss is low to moderate 6%.
3, dielectric ceramic provided by the invention is owing to having good temperature stability, thus has wider use temperature scope by the electron device of this ceramic making.
4, the preparation method of dielectric ceramic provided by the invention is simple to operation, adds the possibility of its suitability for industrialized production.
Accompanying drawing explanation
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 for change value time, when A is Bi fixed element, general formula is (Bi
0.5nb
0.5)
xti
1-xo
2dielectric ceramic relative permittivity variation with temperature curve at 1 khz.
Fig. 2 be the embodiment of the present invention 2 prepare work as x=0.005,0.100,0.150 for change value time, when A is Ga fixed element, general formula is (Ga
0.5nb
0.5)
xti
1-xo
2dielectric ceramic relative permittivity variation with temperature curve at 1 khz.
Fig. 3 be the embodiment of the present invention 3 prepare work as x=0.005,0.100,0.150 for change value time, when A is Al fixed element, general formula is (Al
0.5nb
0.5)
xti
1-xo
2dielectric ceramic relative permittivity variation with temperature curve at 1 khz.
Fig. 4 be the embodiment of the present invention 4 prepare work as x=0.005,0.100,0.150 for change value time, when A is Y fixed element, general formula is (Y
0.5nb
0.5)
xti
1-xo
2dielectric ceramic relative permittivity variation with temperature curve at 1 khz.
Fig. 5 be the embodiment of the present invention 5 prepare work as x=0.005,0.100,0.150 for change value time, when A is Sc fixed element, general formula is (Sc
0.5nb
0.5)
xti
1-xo
2dielectric ceramic relative permittivity variation with temperature curve at 1 khz.
Fig. 6 be the embodiment of the present invention 6 prepare work as x=0.005,0.150 for change value time, when A is Dy fixed element, general formula is (Dy
0.5nb
0.5)
xti
1-xo
2dielectric ceramic relative permittivity at 1 khz
rvariation with temperature curve.
Fig. 7 be the embodiment of the present invention 7 prepare work as x=0.005,0.150 for change value time, when A is Sm fixed element, general formula is (Sm
0.5nb
0.5)
xti
1-xo
2dielectric ceramic relative permittivity variation with temperature curve at 1 khz.
Fig. 8 be the embodiment of the present invention 8 prepare work as x=0.005,0.150 for change value time, when A is Yb fixed element, general formula is (Yb
0.5nb
0.5)
xti
1-xo
2dielectric ceramic relative permittivity ε at 1 khz
rvariation with temperature curve.
Fig. 9 be the embodiment of the present invention 9 prepare work as x=0.005,0.150 for change value time, when A is Pr fixed element, general formula is (Pr
0.5nb
0.5)
xti
1-xo
2dielectric ceramic relative permittivity ε at 1 khz
rvariation with temperature curve.
Figure 10 be the embodiment of the present invention 10 prepare work as x=0.005,0.150 for change value time, when A is Gd fixed element, general formula is (Gd
0.5nb
0.5)
xti
1-xo
2dielectric ceramic relative permittivity ε at 1 khz
rvariation with temperature curve.
Embodiment
Below by embodiment, ion modification titanium dioxide ceramic material of the present invention is further described; what be necessary to herein means out is that described embodiment is just for further illustrating of the present invention; but any restriction that should not be understood as scope, the those of skill in the art in this field can make improvement and the adjustment of some non-intrinsically safes according to the content of the invention described above.
In following examples, the ion modification titanium dioxide ceramic giving various combination obtains ε under concrete preparation process condition
rwith the performance perameter of tan δ etc.:
Embodiment 1
According to general formula (A
0.5nb
0.5)
xti
1-xo
2the ion modification titanium dioxide ceramic component concentration represented is prepared burden;
Work as x=0.005, during A=Bi,
Its formula one is: (Bi
0.5nb
0.5)
0.005ti
0.995o
2,
Work as x=0.010, during A=Bi,
Its formula two is: (Bi
0.5nb
0.5)
0.01ti
0.99o
2,
Work as x=0.025, during A=Bi,
Its formula three is: (Bi
0.5nb
0.5)
0.025ti
0.975o
2,
Work as x=0.035, during A=Bi,
Its formula four is: (Bi
0.5nb
0.5)
0.035ti
0.965o
2,
Work as x=0.050, during A=Bi,
Its formula five is: (Bi
0.5nb
0.5)
0.05ti
0.95o
2,
Work as x=0.100, during A=Bi,
Its formula six is: (Bi
0.5nb
0.5)
0.1ti
0.9o
2,
Work as x=0.150, during A=Bi,
Its formula seven is: (Bi
0.5nb
0.5)
0.15ti
0.85o
2.
The preparation of formula one: with analytically pure Bi
2o
3, Nb
2o
5and TiO
2for raw material, by each raw material stoichiometrically precise, by load weighted raw material using dehydrated alcohol as ball-milling medium, ball milling 24 hours post-dryings obtain mixed powder; By gained dry powder in 1050 DEG C of insulations pre-burning in 4 hours, in powder burned in advance, then add the polyvinyl alcohol water solution granulation that concentration is 8wt%; Be that the grinding tool of 10mm makes sequin at the pressure of 10MPa with diameter after granulation, its diameter is 10mm, and thickness is 1mm, and binder removal, the sequin after binder removal is sintered under following table 1 differing temps, obtains ceramic plate; By the ceramic plate after sintering by upper silver electrode, then measure the electric property of gained pottery.
The preparation of formula two-seven: with analytically pure Bi
2o
3, Nb
2o
5and TiO
2for raw material, prepare burden by the chemical formula of formula two-seven; By each raw material stoichiometrically precise; Other preparation conditions are identical with formula one with parameter used.
Prepared by the present embodiment works as x=0.005, and 0.001,0.025,0.035,0.050,0.100,0.15 is when changing value, (Bi when A=Bi is fixed element
0.5nb
0.5)
xti
1-xo
2dielectric ceramic relative permittivity ε at 1 khz
rvariation with temperature curve as shown in Figure 1.
The present embodiment formula one-seven sinters in different sintering temperature, and the electric property of test gained dielectric ceramic, is shown in Table 1.
Table 1 at ambient temperature, the preparation parameter of dielectric ceramic of formula one-seven and electric property
Embodiment 2
According to general formula (A
0.5nb
0.5)
xti
1-xo
2the ion modification titanium dioxide ceramic component concentration represented is prepared burden;
Work as x=0.005, during A=Ga,
Its formula one is: (Ga
0.5nb
0.5)
0.005ti
0.995o
2,
Work as x=0.100, during A=Ga,
Its formula two is: (Ga
0.5nb
0.5)
0.1ti
0.9o
2,
Work as x=0.150, during A=Ga,
Its formula three is: (Ga
0.5nb
0.5)
0.15ti
0.85o
2.
The preparation of formula one: with analytically pure Ga
2o
3, Nb
2o
5and TiO
2for raw material, by each raw material stoichiometrically precise, by load weighted raw material using dehydrated alcohol as ball-milling medium, ball milling 24 hours post-dryings obtain mixed powder; By gained dry powder in 1100 DEG C of insulations pre-burning in 4 hours, in powder burned in advance, then add the polyvinyl alcohol water solution granulation that concentration is 8wt%; Be that the grinding tool of 10mm makes sequin at the pressure of 10MPa with diameter after granulation, its diameter is 10mm, and thickness is 1mm, and binder removal, the sequin after binder removal is sintered at following table 2 identical (also can directly be write as 1450 DEG C) temperature, obtains ceramic plate; By the ceramic plate after sintering by upper silver electrode, then measure the electric property of gained pottery.
The preparation of formula two-three: with analytically pure Ga
2o
3, Nb
2o
5and TiO
2for raw material, prepare burden by the chemical formula of formula two-three; By each raw material stoichiometrically precise; Other preparation conditions are identical with formula one with parameter used.
Prepared by the present embodiment works as x=0.005, and 0.100,0.150 is when changing value, (Ga when A=Ga is fixed element
0.5nb
0.5)
xti
1-xo
2dielectric ceramic relative permittivity ε at 1 khz
rvariation with temperature curve as shown in Figure 2.
The present embodiment formula one-three sinters in identical sintering temperature, and the electric property of test gained dielectric ceramic, is shown in Table 2.
Table 2 at ambient temperature, the preparation parameter of dielectric ceramic of formula one-three and electric property
Embodiment 3
According to general formula (A
0.5nb
0.5)
xti
1-xo
2the ion modification titanium dioxide ceramic component concentration represented is prepared burden;
Work as x=0.005, during A=Al,
Its formula one is: (Al
0.5nb
0.5)
0.005ti
0.995o
2,
Work as x=0.100, during A=Al,
Its formula two is: (Al
0.5nb
0.5)
0.1ti
0.9o
2,
Work as x=0.150, during A=Al,
Its formula three is: (Al
0.5nb
0.5)
0.15ti
0.85o
2.
The preparation of formula one: with analytically pure Al
2o
3, Nb
2o
5and TiO
2for raw material, by each raw material stoichiometrically precise, by load weighted raw material using dehydrated alcohol as ball-milling medium, ball milling 24 hours post-dryings obtain mixed powder; By gained dry powder in 1100 DEG C of insulations pre-burning in 4 hours, in powder burned in advance, then add the polyvinyl alcohol water solution granulation that concentration is 8wt%; Be that the grinding tool of 10mm makes sequin at the pressure of 10MPa with diameter after granulation, its diameter is 10mm, and thickness is 1mm, and binder removal, the sequin after binder removal is sintered under following table 3 uniform temp, obtains ceramic plate; By the ceramic plate after sintering by upper silver electrode, then measure the electric property of gained pottery.
The preparation of formula two-three: with analytically pure Al
2o
3, Nb
2o
5and TiO
2for raw material, prepare burden by the chemical formula of formula two-three; By each raw material stoichiometrically precise; Other preparation conditions are identical with formula one with parameter used.
Prepared by the present embodiment works as x=0.005, and 0.100,0.150 is when changing value, (Al when A=Al is fixed element
0.5nb
0.5)
xti
1-xo
2dielectric ceramic relative permittivity ε at 1 khz
rvariation with temperature curve as shown in Figure 3.
The present embodiment formula one-three sinters in identical sintering temperature, and the electric property of test gained dielectric ceramic, is shown in Table 3.
Table 3 at ambient temperature, the preparation parameter of dielectric ceramic of formula one-three and electric property
Embodiment 4
According to general formula (A
0.5nb
0.5)
xti
1-xo
2the ion modification titanium dioxide ceramic component concentration represented is prepared burden;
Work as x=0.005, during A=Y,
Its formula one is: (Y
0.5nb
0.5)
0.005ti
0.995o
2,
Work as x=0.100, during A=Y,
Its formula two is: (Y
0.5nb
0.5)
0.1ti
0.9o
2,
Work as x=0.150, during A=Y,
Its formula three is: (Y
0.5nb
0.5)
0.15ti
0.85o
2.
The preparation of formula one: with analytically pure Y
2o
3, Nb
2o
5and TiO
2for raw material, by each raw material stoichiometrically precise, by load weighted raw material using dehydrated alcohol as ball-milling medium, ball milling 24 hours post-dryings obtain mixed powder; By gained dry powder in 1100 DEG C of insulations pre-burning in 4 hours, in powder burned in advance, then add the polyvinyl alcohol water solution granulation that concentration is 8wt%; Be that the grinding tool of 10mm makes sequin at the pressure of 10MPa with diameter after granulation, its diameter is 10mm, and thickness is 1mm, and binder removal, (is sintered at temperature, obtains ceramic plate following table 4 is identical by the sequin after binder removal; By the ceramic plate after sintering by upper silver electrode, then measure the electric property of gained pottery.
The preparation of formula two-three: with analytically pure Y
2o
3, Nb
2o
5and TiO
2for raw material, prepare burden by the chemical formula of formula two-three; By each raw material stoichiometrically precise; Other preparation conditions are identical with formula one with parameter used.
Prepared by the present embodiment works as x=0.005, and 0.100,0.150 is when changing value, (Y when A=Y is fixed element
0.5nb
0.5)
xti
1-xo
2dielectric ceramic relative permittivity ε at 1 khz
rvariation with temperature curve as shown in Figure 4.
The present embodiment formula one-three sinters in identical sintering temperature, and the electric property of test gained dielectric ceramic, is shown in Table 4.
Table 4 at ambient temperature, the preparation parameter of dielectric ceramic of formula one-three and electric property
Embodiment 5
According to general formula (A
0.5nb
0.5)
xti
1-xo
2the ion modification titanium dioxide ceramic component concentration represented is prepared burden;
Work as x=0.005, during A=Sc,
Its formula one is: (Sc
0.5nb
0.5)
0.005ti
0.995o
2,
Work as x=0.100, during A=Sc,
Its formula two is: (Sc
0.5nb
0.5)
0.1ti
0.9o
2,
Work as x=0.150, during A=Sc,
Its formula three is: (Sc
0.5nb
0.5)
0.15ti
0.85o
2.
The preparation of formula one: with analytically pure Sc
2o
3, Nb
2o
5and TiO
2for raw material, by each raw material stoichiometrically precise, by load weighted raw material using dehydrated alcohol as ball-milling medium, ball milling 24 hours post-dryings obtain mixed powder; By gained dry powder in 1100 DEG C of insulations pre-burning in 4 hours, in powder burned in advance, then add the polyvinyl alcohol water solution granulation that concentration is 8wt%; Be that the grinding tool of 10mm makes sequin at the pressure of 10MPa with diameter after granulation, its diameter is 10mm, and thickness is 1mm, and binder removal, the sequin after binder removal is sintered under following table 5 uniform temp, obtains ceramic plate; By the ceramic plate after sintering by upper silver electrode, then measure the electric property of gained pottery.
The preparation of formula two-three: with analytically pure Sc
2o
3, Nb
2o
5and TiO
2for raw material, prepare burden by the chemical formula of formula two-three; By each raw material stoichiometrically precise; Other preparation conditions are identical with formula one with parameter used.
Prepared by the present embodiment works as x=0.005, and 0.100,0.150 is when changing value, (Sc when A=Sc is fixed element
0.5nb
0.5)
xti
1-xo
2dielectric ceramic relative permittivity ε at 1 khz
rvariation with temperature curve as shown in Figure 5.
The present embodiment formula one-three sinters in identical sintering temperature, and the electric property of test gained dielectric ceramic, is shown in Table 5.
Table 5 at ambient temperature, the preparation parameter of dielectric ceramic of formula one-three and electric property
Embodiment 6
According to general formula (A
0.5nb
0.5)
xti
1-xo
2the ion modification titanium dioxide ceramic component concentration represented is prepared burden;
Work as x=0.005, during A=Dy,
Its formula one is: (Dy
0.5nb
0.5)
0.005ti
0.995o
2,
Work as x=0.150, during A=Dy,
Its formula two is: (Dy
0.5nb
0.5)
0.15ti
0.85o
2.
The preparation of formula one: with analytically pure Dy
2o
3, Nb
2o
5and TiO
2for raw material, by each raw material stoichiometrically precise, by load weighted raw material using dehydrated alcohol as ball-milling medium, ball milling 24 hours post-dryings obtain mixed powder; By gained dry powder in 1100 DEG C of insulations pre-burning in 4 hours, in powder burned in advance, then add the polyvinyl alcohol water solution granulation that concentration is 8wt%; Be that the grinding tool of 10mm makes sequin at the pressure of 10MPa with diameter after granulation, its diameter is 10mm, and thickness is 1mm, and binder removal, the sequin after binder removal is sintered under following table 6 uniform temp, obtains ceramic plate; By the ceramic plate after sintering by upper silver electrode, then measure the electric property of gained pottery.
The preparation of formula two: with analytically pure Dy
2o
3, Nb
2o
5and TiO
2for raw material, prepare burden by the chemical formula of formula two; By each raw material stoichiometrically precise; Other preparation conditions are identical with formula one with parameter used.
Prepared by the present embodiment works as x=0.005, and 0.150 is when changing value, (Dy when A=Dy is fixed element
0.5nb
0.5)
xti
1-xo
2dielectric ceramic relative permittivity ε at 1 khz
rvariation with temperature curve as shown in Figure 6.
The present embodiment formula one-two sinters in identical sintering temperature, and the electric property of test gained dielectric ceramic, is shown in Table 6.
Table 6 at ambient temperature, the preparation parameter of dielectric ceramic of formula one-two and electric property
Embodiment 7
According to general formula (A
0.5nb
0.5)
xti
1-xo
2the ion modification titanium dioxide ceramic component concentration represented is prepared burden;
Work as x=0.005, during A=Sm,
Its formula one is: (Sm
0.5nb
0.5)
0.005ti
0.995o
2,
Work as x=0.150, during A=Sm,
Its formula two is: (Sm
0.5nb
0.5)
0.15ti
0.85o
2.
The preparation of formula one: with analytically pure Sm
2o
3, Nb
2o
5and TiO
2for raw material, by each raw material stoichiometrically precise, by load weighted raw material using dehydrated alcohol as ball-milling medium, ball milling 24 hours post-dryings obtain mixed powder; By gained dry powder in 1100 DEG C of insulations pre-burning in 4 hours, in powder burned in advance, then add the polyvinyl alcohol water solution granulation that concentration is 8wt%; Be that the grinding tool of 10mm makes sequin at the pressure of 10MPa with diameter after granulation, its diameter is 10mm, and thickness is 1mm, and binder removal, the sequin after binder removal is sintered under following table 7 uniform temp, obtains ceramic plate; By the ceramic plate after sintering by upper silver electrode, then measure the electric property of gained pottery.
The preparation of formula two: with analytically pure Sm
2o
3, Nb
2o
5and TiO
2for raw material, prepare burden by the chemical formula of formula two; By each raw material stoichiometrically precise; Other preparation conditions are identical with formula one with parameter used.
Prepared by the present embodiment works as x=0.005, and 0.150 is when changing value, (Sm when A=Sm is fixed element
0.5nb
0.5)
xti
1-xo
2dielectric ceramic relative permittivity ε at 1 khz
rvariation with temperature curve as shown in Figure 7.
The present embodiment formula one-two sinters in identical sintering temperature, and the electric property of test gained dielectric ceramic, is shown in Table 7.
Table 7 at ambient temperature, the preparation parameter of dielectric ceramic of formula one-two and electric property
Embodiment 8
According to general formula (A
0.5nb
0.5)
xti
1-xo
2the ion modification titanium dioxide ceramic component concentration represented is prepared burden;
Work as x=0.005, during A=Yb,
Its formula one is: (Yb
0.5nb
0.5)
0.005ti
0.995o
2,
Work as x=0.150, during A=Yb,
Its formula two is: (Yb
0.5nb
0.5)
0.15ti
0.85o
2.
The preparation of formula one: with analytically pure Yb
2o
3, Nb
2o
5and TiO
2for raw material, by each raw material stoichiometrically precise, by load weighted raw material using dehydrated alcohol as ball-milling medium, ball milling 24 hours post-dryings obtain mixed powder; By gained dry powder in 1100 DEG C of insulations pre-burning in 4 hours, in powder burned in advance, then add the polyvinyl alcohol water solution granulation that concentration is 8wt%; Be that the grinding tool of 10mm makes sequin at the pressure of 10MPa with diameter after granulation, its diameter is 10mm, and thickness is 1mm, and binder removal, the sequin after binder removal is sintered under following table 8 uniform temp, obtains ceramic plate; By the ceramic plate after sintering by upper silver electrode, then measure the electric property of gained pottery.
The preparation of formula two: with analytically pure Yb
2o
3, Nb
2o
5and TiO
2for raw material, prepare burden by the chemical formula of formula two; By each raw material stoichiometrically precise; Other preparation conditions are identical with formula one with parameter used.
Prepared by the present embodiment works as x=0.005, and 0.150 is when changing value, (Yb when A=Yb is fixed element
0.5nb
0.5)
xti
1-xo
2dielectric ceramic relative permittivity ε at 1 khz
rvariation with temperature curve as shown in Figure 8.
The present embodiment formula one-two sinters in identical sintering temperature, and the electric property of test gained dielectric ceramic, is shown in Table 8.
Table 8 at ambient temperature, the preparation parameter of dielectric ceramic of formula one-two and electric property
Embodiment 9
According to general formula (A
0.5nb
0.5)
xti
1-xo
2the ion modification titanium dioxide ceramic content represented is prepared burden;
Work as x=0.005, during A=Pr,
Its formula one is: (Pr
0.5nb
0.5)
0.005ti
0.995o
2,
Work as x=0.150, during A=Pr,
Its formula two is: (Pr
0.5nb
0.5)
0.15ti
0.85o
2.
The preparation of formula one: with analytically pure Pr
2o
3, Nb
2o
5and TiO
2for raw material, by each raw material stoichiometrically precise, by load weighted raw material using dehydrated alcohol as ball-milling medium, ball milling 24 hours post-dryings obtain mixed powder; By gained dry powder in 1100 DEG C of insulations pre-burning in 4 hours, in powder burned in advance, then add the polyvinyl alcohol water solution granulation that concentration is 8wt%; Be that the grinding tool of 10mm makes sequin at the pressure of 10MPa with diameter after granulation, its diameter is 10mm, and thickness is 1mm, and binder removal, the sequin after binder removal is sintered under following table 9 uniform temp, obtains ceramic plate; By the ceramic plate after sintering by upper silver electrode, then measure the electric property of gained pottery.
The preparation of formula two: with analytically pure Pr
2o
3, Nb
2o
5and TiO
2for raw material, prepare burden by the chemical formula of formula two; By each raw material stoichiometrically precise; Other preparation conditions are identical with formula one with parameter used.
Prepared by the present embodiment works as x=0.005, and 0.150 is when changing value, (Pr when A=Pr is fixed element
0.5nb
0.5)
xti
1-xo
2dielectric ceramic relative permittivity ε at 1 khz
rvariation with temperature curve as shown in Figure 9.
The present embodiment formula one-two sinters in identical sintering temperature, and the electric property of test gained dielectric ceramic, is shown in Table 9.
Table 9 at ambient temperature, the preparation parameter of dielectric ceramic of formula one-two and electric property
Embodiment 10
According to general formula (A
0.5nb
0.5)
xti
1-xo
2the ion modification titanium dioxide ceramic component concentration represented is prepared burden;
Work as x=0.005, during A=Gd,
Its formula one is: (Gd
0.5nb
0.5)
0.005ti
0.995o
2,
Work as x=0.150, during A=Gd,
Its formula two is: (Gd
0.5nb
0.5)
0.15ti
0.85o
2.
The preparation of formula one: with analytically pure Gd
2o
3, Nb
2o
5and TiO
2for raw material, by each raw material stoichiometrically precise, by load weighted raw material using dehydrated alcohol as ball-milling medium, ball milling 24 hours post-dryings obtain mixed powder; By gained dry powder in 1100 DEG C of insulations pre-burning in 4 hours, in powder burned in advance, then add the polyvinyl alcohol water solution granulation that concentration is 8wt%; Be that the grinding tool of 10mm makes sequin at the pressure of 10MPa with diameter after granulation, its diameter is 10mm, and thickness is 1mm, and binder removal, the sequin after binder removal is sintered under following table 10 uniform temp, obtains ceramic plate; By the ceramic plate after sintering by upper silver electrode, then measure the electric property of gained pottery.
The preparation of formula two: with analytically pure Gd
2o
3, Nb
2o
5and TiO
2for raw material, prepare burden by the chemical formula of formula two; By each raw material stoichiometrically precise; Other preparation conditions are identical with formula one with parameter used.
Prepared by the present embodiment works as x=0.005, and 0.150 is when changing value, (Gd when A=Gd is fixed element
0.5nb
0.5)
xti
1-xo
2dielectric ceramic relative permittivity ε at 1 khz
rvariation with temperature curve as shown in Figure 10.
The present embodiment formula one-two sinters in identical sintering temperature, and the electric property of test gained dielectric ceramic, is shown in Table 10.
Table 10 at ambient temperature, the preparation parameter of dielectric ceramic of formula one-two and electric property
Through ion modification titanium dioxide ceramic material prepared by the above embodiment of the present invention, its dielectric properties listed result from table can be seen, its specific inductivity and dielectric loss have clear superiority in similar high-k dielectric materials.Chemical constitution formula (the A of this material
0.5nb
0.5)
xti
1-xo
2, when A is Bi element, during x=0.010, the DIELECTRIC CONSTANT ε of described titanium dioxide ceramic
rcan up to 275768, when A is Bi element, during x=0.005, its dielectric loss tan δ is 0.06737, is low to moderate 6%.Thus the device prepared by titanium dioxide ceramic of the present invention has actual using value in the various electron devices such as electrical condenser and dynamic storage (DRAM).
Claims (4)
1. there is an ion modification titanium dioxide ceramic material for high-k, it is characterized in that it is by general formula (A
0.5nb
0.5)
xti
1-xo
2represent, in formula, A is Bi, Al, Ga, Y, Sc, Yb, Dy, Sm, Gd and Pr, and the span of x is 0.005 ~ 0.150 molar content.
2. ion modification titanium dioxide ceramic material according to claim 1, is characterized in that its specific inductivity of this stupalith is high to 10
6, dielectric loss is low to moderate 6%.
3. a preparation method for the ion modification titanium dioxide ceramic material of high-k according to any one of claim 1-2, is characterized in that comprising following processing step successively:
(1) conventional solid sintering process preparation technology is adopted, at general formula (A
0.5nb
0.5)
xti
1-xo
2add trivalent element A and pentavalent Nb element in formula simultaneously, with analytically pure titanium dioxide, or bismuth oxide, or aluminum oxide, or gallium oxide, or yttrium oxide, or Scium trioxide, or ytterbium oxide, or dysprosium oxide, or Samarium trioxide, or gadolinium sesquioxide, or Praseodymium trioxide, or Niobium Pentxoxide is raw material; According to the formula (A of corresponding system
0.5nb
0.5)
xti
1-xo
2prepare burden, in formula, A is Bi, Al, Ga, Y, Sc, Yb, Dy, Sm, Gd and Pr, and the span of x is 0.005 ~ 0.150 molar content;
(2) raw material step (1) prepared is that medium carries out rolling ball milling with dehydrated alcohol, is dried by the powder of rolling ball milling after 24 hours and obtains mixed powder;
(3) mixed powder of step (2) gained is incubated pre-burning in 4 hours at 1050-1100 DEG C of temperature; Mixed powder burned is in advance added the polyvinyl alcohol water solution granulation of 8wt%, obtain even-grained powder;
(4) by the powder after step (3) granulation, grinding tool is utilized to be pressed into sequin and binder removal; Sequin after binder removal is incubated at 1220 ~ 1450 DEG C of temperature 4-5 hour sintering, obtains ceramic plate;
(5) ceramic plate after step (4) being sintered, by upper silver electrode, namely obtains the ion modification titanium dioxide ceramic material of high-k, then measures specific inductivity and the dielectric loss of gained stupalith.
4. the ion modification titanium dioxide ceramic material prepared by method according to claim 3, is characterized in that making the specific inductivity of the stupalith prepared up to 10 by adding described trivalent element A and pentavalent Nb element
6, its dielectric loss is low to moderate 6%.
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