Be used for microwave-tuned bismuth-based dielectric material and preparation method thereof
Technical field
The present invention relates to microelectronic material, particularly a kind of bismuth-based dielectric material that is used for microwave-tuned components and parts.
Background technology
Microwave technology is since appearance half a century, and development is widely used rapidly.Along with the progress of integrated technology, microwave device has developed into VLSIC (super large-scale integration) stage, and live width reaches sub-micrometer scale.In order to adapt to the demand for development of following high frequency, wideband communication, the MMIC of micron waveband began one's study from the nineties in last century.The development of new high frequency integrated micro chip, microwave device is had higher requirement, as: fast response speed, wide frequency-selecting ability, highly sensitive and good temperature stability etc., with the functions such as transmission, phase shift, filtering and resonant selecting frequency of finishing microwave signal.
Microwave-tuned relative permittivity or the magnetic permeability of electromagnetic medium (the present invention abbreviates medium as) under microwave frequency that be meant can be by the character that certain mode (as extra electric field or magnetic field etc.) changes or quilt is regulated and control.The microwave-tuned device that utilizes this characteristic to make has extremely important status and application widely in modern radar and micro-wave communication technology.Realize the device of frequency and phase modulated in the microwave current circuit, mainly comprise GaAs volticap, MEMS (micro electro mechanical system) (MEMS) device, ferrite-tuned device and dielectric adjustable device.The dielectric adjustable device utilizes the specific inductivity of part dielectric material to have the electric field tunable characteristic that changes with extra electric field, comes the frequency or the phase place of modulated electromagnetic wave, makes voltage-controlled microwave frequency device.For example medium electronically controlled phase shifter, electricity are transferred matching network, electrically tunable filter, voltage-controlled oscillator, losser, amplitude modulator, derailing switch, limiter etc.Adopt the dielectric adjustable microwave device of voltage modulated integrated easily, can constitute microwave hybrid integrated circuit with microwave tube, microstrip line etc., device size reaches a millimeter magnitude, and have that tuning response speed is fast, power capacity is big, volume and advantage such as power consumption is little, operating temperature range is wide.The dielectric material with adjustable has wide application prospect in microwave device.Dielectric adjustable microwave device is compared with semiconductor variable capacitance diode, and dielectric adjustable microwave device has higher controllability, and governing speed is very fast, though diode tuning device tuning range is big, loss is big under high frequency, power capacity is low.Though the loss of MEMS microwave device is lower, response speed is slow, has limited its application in the microwave tunable arrangement.Ferrite device cost height, big power consumption, bulky.Transfer the dielectric adjustable microwave device of dielectric material based on electricity, its cost only is about 1/10 of Ferrite Material device, in phased array antenna, the ferroelectric lens structure of dielectric material is transferred in use based on electricity, the number of phase shifter can be dropped to m+n (m by m * N, n is respectively the ranks number of array antenna), can reduce the cost of phased array antenna greatly.In addition, ferrite device loss when 1~2GHz is bigger, is not suitable for cellular based communication, and is difficult to make two dimensional structure, thereby can't realize integrated.
Microwave-tuned application to the dielectric material performance demands mainly aspect three of specific inductivity, tuning rate and the dielectric losses.1, microwave-tuned requirement on devices material has moderate relative permittivity on the low side under microwave frequency, particularly, and in the 30-1500 scope.This is that too high specific inductivity causes too high loss because most of ferroelectric losses all increase with the increase of specific inductivity.In addition, low-k is realized impedance matching easily.2, specific inductivity tuning rate (abbreviation tuning rate) is to weigh the index of the specific inductivity of material with the extra electric field changing capability.The specific inductivity of electronic tuning material changes with external electric field, so tuning rate is the function of external electric field.General electric field is strong more, and tuning rate is big more, and still, too high electric field can reduce the reliability of device.Tuning rate is directly connected to the tuning capability of microwave-tuned device, and under certain electric field, tuning rate is the bigger the better.3, in the alternating electromagnetic field, owing to there is dielectric loss in the factors such as polarization relaxation of medium.The dielectric loss of material is low more, and the insertion loss of device is just more little, and quality factor (Q value) is also high more.Therefore dielectric loss is the smaller the better, wishes tangent loss tan δ<0.008 under microwave frequency in the practicality.Except that above three main aspects, the dielectric material performance also is an important factor with variation of temperature, requires the dielectric properties index temperature influence of material the smaller the better.
Strontium-barium titanate BST (the Ba of perovskite structure
xSr
1-xTiO
3) basic ferroelectric material is the present maximum class dielectric adjustable microwave medium material of research.BST base ferroelectric material tuning rate height, yet reducing with the thickness of film, the specific inductivity of bst thin film sharply descends, in plate condenser Pt/BST/Pt/Si structure, the typical dielectric constant values of bst thin film is 200~500, and the typical dielectric constant values of BST stupalith is 10000.The chemical ingredients deviation of film, the interfacial effect of electrode, and stress and polar tight coupling seriously influence the performance of ferroelectric membranc.And its dielectric loss is also bigger, and the loss of the minimum of report is 0.005 (tan δ usually〉0.01).And microwave device requires dielectric material to have lower dielectric loss, and dielectric loss is low more, and the insertion loss of device is just more little.For mode of resonance microwave devices such as electrically tunable filter, voltage-controlled oscillator dielectric material, dielectric loss requires lower.Therefore, BST base ferroelectric material will move towards to use and also should solve the big basic problem of dielectric loss.
The niobic acid bismuth zinc BZN (Bi of bismuthino pyrochlore structure
1.5ZnNb
1.5O
7) material also has specific inductivity electric field tunable characteristic, its outstanding advantage is that dielectric loss is lower.But this dielectric material tuning rate is low, and electric field the height (〉 2MV/cm that requires).Low tuning rate, too high electric field require to have limited the application of this material.In order to strengthen the dielectric tuning performance of BZN material, the method for report is normally introduced strong polar compound, for example Ti
4+Ionic replacement part Nb
5+Ion is because Ti
4+The polarizability of ion under electric field action is strong, thereby increases the tuning rate of BZN material.But, because the introducing of polar compound can cause the increase of dielectric loss simultaneously.
Summary of the invention
Technical problem to be solved by this invention, be exactly the research of passing through the dielectric tuning mechanism of bismuthino pyrochlore structure niobic acid bismuth Zinc material, and based on deep understanding to the tuning mechanism of bismuthino pyrochlore structure class dielectric material, propose to strengthen the imagination and the embodiment of bismuthino pyrochlore structure class dielectric material tuning characteristic, and a kind of microwave-tuned dielectric material and preparation method thereof that is used for is provided in view of the above.
The present invention solve the technical problem, and the technical scheme of employing is, is used for microwave-tuned bismuth-based dielectric material, and described dielectric material has the bismuthino pyrochlore structure, and chemical constitution is Bi
1.5MNb
1.5O
7Wherein, M is the divalent metallic cation, it is characterized in that, described M ionic radius is less than the Zn ionic radius;
Concrete, described M ion is the Mg ion, described dielectric material chemical formula is Bi
1.5MgNb
1.5O
7
Be used for microwave-tuned bismuth-based dielectric material preparation method, it is characterized in that, may further comprise the steps:
A, batching: with analytically pure Bi
2O
3, Nb
2O
5With the weighing in 0.75: 1: 0.75 in molar ratio of MgO powder and mix;
B, base: adopt ceramic processes such as ball milling, oven dry, pre-burning, secondary ball milling, oven dry, granulation, moulding, preparation any surface finish, densification, flawless ceramic green;
C, binder removal: described ceramic green is put into sintering oven, slowly be warming up to 350~550 ℃ of insulation for some time;
D, sinter molding: after continuing slowly to be warming up to 900~1100 ℃ of insulation for some time, cool to room temperature with the furnace and take out, obtain niobic acid bismuth magnesium pottery.
The invention has the beneficial effects as follows that dielectric material dielectric tuning rate height, dielectric loss are low, are the excellent dielectric materials that is used for voltage-controlled microwave frequency components and parts.
Description of drawings
Fig. 1 is B in the burnt green stone of bismuthino
2O
6Structural representation;
Fig. 2 is A in the burnt green stone of bismuthino
2O ' crossover network structural representation;
Fig. 3 is a bismuthino pyrochlore structure synoptic diagram;
Fig. 4 is that A position positively charged ion departs from the equilibrium theory of tide synoptic diagram in the burnt green stone of bismuthino;
Fig. 5 is an O ' ion deflection equilibrium theory of tide synoptic diagram in the burnt green stone of bismuthino;
Fig. 6 is an embodiment stupalith X ray diffracting spectrum;
Fig. 7 is the X ray diffracting spectrum that the embodiment ceramic material becomes film;
Fig. 8 is that the embodiment ceramic material becomes specific inductivity and the damage curve of film under different frequency;
Fig. 9 is that the embodiment ceramic material becomes film under the 100kHz frequency, and specific inductivity and loss are with the curve of electric field change.
Embodiment
Chemical constitution is Bi
1.5MNb
1.5O
7The bismuthino pyrochlore structure of (M is the divalent metallic cation) has A
2B
2O
7Chemical general formula, M positively charged ion of half and Bi ion occupy the A position, second half M positively charged ion and Nb ion occupy the B position.For example, at cube Bi of bismuthino pyrochlore structure
1.5ZnNb
1.5O
7In, the Zn ion of half occupies the A position, and second half Zn ion occupies the B position.Jiao Lvshi is a very big compounds of group, and it has Fd3m space point group, and its structure cell comprises 88 atoms, is cubic structure.A
2B
2O
7Pyrochlore structure often is described to B
2O
6.A
2O ', this structure is to be made of the grid that 2 parts are interted mutually.Part 1 B
2O
6Be octahedral a kind of arrangement that the angle connects, each octahedra and another octahedra angle altogether is the center (see figure 1) with B position positively charged ion; Part 2 A
2O ' is the tetrahedral structure (see figure 2) that high symmetry, angle connect, and tetrahedral straight line key is<110〉direction, and occupy passage in octahedra the arrangement, two portions are formed the one-piece construction (see figure 3) together.B
2O
6Octahedra grid is by [BO
6] octahedral { the 111} face is formed, and these faces have surrounded trilateral and rhombohedral ring respectively; These faces are called as " hexagonaltungsten bronze " (HTB) layer.O ' ion is arranged in the huge space that the HTB layer surrounds, and around 4 A positively charged ions, forms [A around it
4O '] tetrahedron.Around the A positively charged ion eight O ions are arranged, wherein six O ions belong to [BO
6] octahedron, these six O ions have constituted a folding hexagonal ring, and remaining two O ' ions and A ion have been formed O '-A-O ' chain jointly, and this chain is vertical mutually with hexagonal rings.In the bismuthino pyrochlore structure, the ion that radius is bigger occupies the A position, and the less ion of radius occupies the B position.
In the bismuthino pyrochlore structure, because the interaction between A position positively charged ion and the O ' ion, these ions are all transferred to low symmetric position (seeing Fig. 4, Fig. 5), and the cationic nearest neighbour in A position is six and forms cyclic O ion and two O ' ions.Big ball of white and the big ball of grey are respectively O ion and O ' ion among Fig. 4 and Fig. 5, and the black bead is an A position positively charged ion.Each A positively charged ion at random occupy 6 positions, these positions are along perpendicular to three<112〉direction of O '-A-O ' chain, these positions mark with the black bead in Fig. 4, they are bound in the HTB layer.O ' ion then is displaced to around it freely<all 12 equilibrium theory of tide on 110〉direction.Fig. 4 has marked 12 ideal positions of O ' ionic.The direction of O '-A-O ' chain is perpendicular to [111] face.We can clearly find out A ion and O ' ionic sense of displacement among Fig. 5.A ion and O ' ion deflection ideal equilibrium theory of tide cause O '-A-O ' chain to bend.
Based on the understanding to bismuthino pyrochlore structure material crystals structure, we have studied the dielectric tuning mechanism of such material.We think, in bismuthino pyrochlore structure material, just because of the displacement stochastic distribution constructional feature of A2O ' network in the crystal, have caused the dielectric tunable characteristic of such material.A position ion makes this class material have higher dielectric constant at the polarization response of the random site motion that departs from ideal position, under electric field action, the ionic random motion is orderly from unordered change, make " soft mode " harden, specific inductivity diminishes, and the variation of specific inductivity has produced the dielectric tuning characteristic.Be similar among the perovskite structural material BST, owing to Ti ion deflection oxygen octahedra central motion produces the dielectric tuning characteristic that spontaneous polarization causes.
Further, based on research and the understanding to the tuning mechanism of bismuthino pyrochlore structure dielectric material, we propose to strengthen the imagination and the scheme of such dielectric material tuning performance---improve its dielectric tuning performance by the polarization response that strengthens A position ion random motion.Particularly, introduce the ion of small radii in the A position, can strengthen the ionic random motion of A position, increase mobility, strengthen the polarization response under its electric field action, realize improving the purpose of its dielectric tuning performance.As improvement, can select ionic radius less than Zn ionic element, as the Zn ion in the replacement niobic acid bismuth zinc such as Mg, Cu, Fe, Co at niobic acid bismuth Zinc material.
Embodiment
This example adopts the Zn in Mg replacement niobic acid bismuth zinc (BZN) material, and the preparation chemical constitution is Bi
1.5MgNb
1.5O
7(BMN) niobic acid bismuth magnesium material.Mg in this material
2+Ion has the Zn of ratio
2+Less radius, this material of inference should have the dielectric tuning rate high than the BZN material.Adopt the method for rf magnetron sputtering to prepare the BMN film this material, the dielectric properties of research BMN film, finding that this BMN thin-film material has dielectric tuning rate height, characteristics that dielectric loss is low, is a kind of excellent dielectric material that is used for voltage-controlled microwave frequency components and parts.
The dielectric film preparation process is as follows:
1, the preparation of niobic acid bismuth magnesium stupalith.
Preparation Bi
1.5MgNb
1.5O
7Stupalith adopts solid phase reaction method.With analytically pure Bi
2O
3, Nb
2O
5With the weighing in 0.75: 1: 0.75 in molar ratio of MgO powder and mix; Through ceramic processes such as ball milling, oven dry, pre-burning, secondary ball milling, oven dry, granulation, moulding, preparation any surface finish, densification, flawless BMN ceramic green; These green compact are put into sintering oven, slowly be warming up to 350~550 ℃ of insulations and for some time carry out binder removal; After continuing then slowly to be warming up to 900~1100 ℃ of insulation for some time, make its solid state reaction abundant, cool to room temperature with the furnace and take out, obtain niobic acid bismuth magnesium pottery.The binder removal processing parameter that this example is recommended is: slowly be warming up to 450 ℃ of insulation 24h down; The sintering parameter is: slowly be warming up to 1000 ℃ and be incubated 3 hours down, cool to room temperature with the furnace and take out.
Fig. 6 is the X ray diffracting spectrum of this stupalith, and this BMN stupalith has the green stone crystalline structure of cube Jiao as can be seen.
2, the preparation of niobic acid bismuth magnesium film material.
As target, adopt radio frequency magnetron sputtering method the niobic acid bismuth magnesium stupalith of above-mentioned steps preparation at the Al of Pt electrode that has been covered
2O
3Ceramic substrate (is expressed as Pt/Al
2O
3) going up preparation niobic acid bismuth magnesium film, processing condition such as table 1 are listed, and typical process condition such as table 2 are listed.
Bi
1.5MgNb
1.5O
7Structure, dielectric and the tuning performance of niobic acid bismuth magnesium material.
Fig. 7 is the X ray diffracting spectrum that adopts the BMN film of radio frequency magnetron sputtering method preparation, shows that this BMN film and BMN ceramic target have the green stone crystalline structure of same cube Jiao.
Fig. 8 is the spectrum characteristic that adopts the BMN thin-film dielectric performance of radio frequency magnetron sputtering method preparation.The result shows that the specific inductivity of this thin-film material has good frequency stability, changes with frequency change hardly.Specific inductivity is about 86, is fit to very much microwave application.Simultaneously, dielectric loss is extremely low, in the Validity Test scope of testing tool (Agilent 4284A) (<100kHz), dielectric loss is about 0.0018~0.0025.Above-mentioned test result shows that this thin-film material has excellent dielectric properties in the test frequency scope.
The dielectric tuning performance that Fig. 9 is the BMN film that adopts the radio frequency magnetron sputtering method preparation after applying same electric field not.The result shows, under the electric field action of 1.6MV/cm, the specific inductivity of BMN film 86 is reduced to 53 under 0 bias voltage, and the dielectric tuning rate is about 39%, and this tuning performance is better than the BZN thin-film material.
Table 3 has provided dielectric tuning coefficient (β) contrast of the BZN film of BMN and known report best performance, the BMN film of the present invention's preparation as can be seen, and its dielectric tuning coefficient has almost improved an order of magnitude than BZN film.Simultaneously, Fig. 9 also shows, under the different big or small electric field actions, the thin-film dielectric loss remains in 0.002~0.004 the extremely low scope.
Above result shows that chemical constitution is Bi
1.5MgNb
1.5O
7Niobic acid bismuth magnesium material have dielectric tuning rate height, characteristics that dielectric loss is low, be a kind of excellent dielectric material that is used for voltage-controlled microwave frequency components and parts.
Table 1
Substrate (Pt/Al
2O
3) temperature
|
Room temperature~900 ℃ |
Sputtering pressure |
0.1~30Pa |
Sputtering atmosphere |
Ar+O
2 |
Table 2
Substrate (Pt/Al
2O
3) temperature
|
600℃ |
Sputtering pressure |
3Pa |
Sputtering atmosphere |
Ar:O
2=85:15
|
Table 3
Material |
The strength of electric field that applies (MV/cm) |
Dielectric tuning factor beta (J/C
4m
5)
|
Bi
1.5MgNb
1.5O
7 |
1.6 |
2.78×10
10 |
Bi
1.5ZnNb
1.5O
7 |
2.4 |
3.47×10
9 |