WO2012163071A1 - 制备非均匀介电常数介质基板的方法、制备超材料功能板的方法及超材料 - Google Patents

制备非均匀介电常数介质基板的方法、制备超材料功能板的方法及超材料 Download PDF

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WO2012163071A1
WO2012163071A1 PCT/CN2011/084453 CN2011084453W WO2012163071A1 WO 2012163071 A1 WO2012163071 A1 WO 2012163071A1 CN 2011084453 W CN2011084453 W CN 2011084453W WO 2012163071 A1 WO2012163071 A1 WO 2012163071A1
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barium titanate
metamaterial
dielectric constant
powder
ferroelectric
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PCT/CN2011/084453
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English (en)
French (fr)
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刘若鹏
缪锡根
赵治亚
李春来
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深圳光启高等理工研究院
深圳光启创新技术有限公司
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Priority claimed from CN 201110146258 external-priority patent/CN102476950B/zh
Priority claimed from CN 201110216318 external-priority patent/CN102476957B/zh
Application filed by 深圳光启高等理工研究院, 深圳光启创新技术有限公司 filed Critical 深圳光启高等理工研究院
Publication of WO2012163071A1 publication Critical patent/WO2012163071A1/zh

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    • C—CHEMISTRY; METALLURGY
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/62605—Treating the starting powders individually or as mixtures
    • C04B35/6261—Milling
    • C04B35/62615—High energy or reactive ball milling
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
    • C04B35/468—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates
    • C04B35/4682—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates based on barium titanates based on BaTiO3 perovskite phase
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01Q—ANTENNAS, i.e. RADIO AERIALS
    • H01Q1/00—Details of, or arrangements associated with, antennas
    • H01Q1/36—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith
    • H01Q1/38—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith formed by a conductive layer on an insulating support
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01Q—ANTENNAS, i.e. RADIO AERIALS
    • H01Q15/00—Devices for reflection, refraction, diffraction or polarisation of waves radiated from an antenna, e.g. quasi-optical devices
    • H01Q15/0006—Devices acting selectively as reflecting surface, as diffracting or as refracting device, e.g. frequency filtering or angular spatial filtering devices
    • H01Q15/0086—Devices acting selectively as reflecting surface, as diffracting or as refracting device, e.g. frequency filtering or angular spatial filtering devices said selective devices having materials with a synthesized negative refractive index, e.g. metamaterials or left-handed materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3206—Magnesium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3213—Strontium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
    • C—CHEMISTRY; METALLURGY
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint

Definitions

  • the present invention relates to the field of metamaterials, and in particular to a dielectric substrate of a metamaterial, a metamaterial functional panel, and a metamaterial.
  • the metamaterial is generally formed by laminating a plurality of metamaterial functional panels or by other regular arrays.
  • the metamaterial functional panel comprises a dielectric substrate and a plurality of artificial microstructures arrayed on the dielectric substrate, and the existing metamaterial dielectric substrate is a uniform material.
  • Organic or inorganic substrates such as FR4, TP 1 and the like.
  • the plurality of artificial microstructures of the array on the dielectric substrate have specific electromagnetic characteristics and can generate electromagnetic response to an electric field or a magnetic field.
  • the metamaterials can be presented in various kinds. Electromagnetic properties not found in general materials, such as convergence, divergence, and deflection of electromagnetic waves.
  • the existing dielectric substrate as a fixed substrate of an artificial microstructure, does not have a unique response to an electric field or a magnetic field because of its uniform dielectric constant and magnetic permeability as a whole, that is, for the entire metamaterial, the dielectric substrate is not With electromagnetic modulation.
  • the dielectric substrate can be made to include a plurality of substrate units, and a non-uniform distribution of dielectric constant can be achieved by selecting a suitable material for each substrate unit.
  • a suitable material for each substrate unit due to the material selection range, the material selected for each substrate unit does not reach the predetermined requirements well, and the dielectric constant is difficult to control.
  • the conventional metamaterials are generally prepared by a method of arranging metal microstructures on an organic resin substrate, and the dielectric substrate is made of an organic resin material, so that the overall dielectric constant is small and cannot meet the application requirements.
  • the artificial microstructure of the metal material has the disadvantage of being easily detached and having a complicated structure.
  • the superstructure of the array metal microstructure on the existing organic resin substrate is suitable for electromagnetic waves in the microwave frequency band, and has a particularly large loss for high frequency such as infrared and visible light bands.
  • the invention overcomes the shortcomings of the lack of function of the dielectric substrate of the prior supermaterial, and provides a method for preparing a non-uniform dielectric constant dielectric substrate; further, providing a ceramic material as a dielectric substrate, and a barium titanate non-ferroelectric
  • the invention relates to a method for preparing an artificial microstructure of a metamaterial functional board; finally, the invention also provides a metamaterial, which changes the local dielectric constant of the metamaterial by changing a local material of the dielectric substrate, so that the metamaterial is functionally obtained.
  • a method of preparing a non-uniform dielectric constant dielectric substrate comprises the steps of:
  • the barium titanate powder and the non-ferroelectric powder are uniformly mixed in different proportions, and then sintered at a high temperature to obtain a barium titanate non-ferroelectric ceramic material having different dielectric constants;
  • steps c and d Repeat steps c and d to sequentially prepare other substrate units, and finally combine the respective substrate units to obtain a metamaterial dielectric substrate.
  • the step a further comprises: the barium titanate powder itself has a different dielectric constant by controlling the ratio of bismuth to bismuth in the barium titanate powder, and the step b further comprises obtaining a ratio of the dielectric constant to the ratio of ⁇ to ⁇ .
  • the relationship, step c further comprises determining the ratio of bismuth to bismuth in the barium titanate powder used to prepare the substrate unit based on the relationship of the dielectric constant to the ratio of ⁇ to ⁇ .
  • the non-ferroelectric is magnesium oxide, aluminum oxide or silicon oxide.
  • a method of preparing a metamaterial functional panel comprises the steps of:
  • the barium titanate powder and the non-ferroelectric powder are uniformly mixed in different proportions, and then sintered at a high temperature to obtain a barium titanate non-ferroelectric ceramic material having different dielectric constants; b. determining the dielectric constant of the barium titanate non-ferroelectric ceramic material, and obtaining a relationship between the dielectric constant and the ratio of barium titanate to non-ferroelectric;
  • the artificial microstructure is printed on the ceramic dielectric substrate by a ceramic paste by a screen printing method, and the ceramic dielectric substrate and the artificial microstructure are sintered at a high temperature to obtain a metamaterial functional plate.
  • the e step further comprises: controlling the printing of the artificial microstructures in different regions of the ceramic dielectric substrate, wherein the ratio of the barium titanate powder to the non-ferroelectric powder in the ceramic slurry used in the different regions is different.
  • the step a further comprises the barium titanate powder itself having a different dielectric constant by controlling the ratio of cerium to cerium in the barium titanate powder.
  • step b further comprises obtaining a relationship of the dielectric constant with respect to the ratio of ⁇ to ⁇ .
  • the step c further comprises determining the ratio of bismuth to bismuth in the barium titanate powder used to prepare the artificial microstructure based on the relationship of the dielectric constant to the ratio of bismuth to bismuth.
  • the non-ferroelectric is magnesium oxide, aluminum oxide or silicon dioxide.
  • the step d further comprises a step of grinding the barium titanate powder and the magnesium oxide powder, and after the grinding, the barium titanate powder and the non-ferroelectric powder are uniformly mixed according to a certain ratio.
  • a metamaterial includes a plurality of arrays of metamaterial functional panels, the metamaterial functional panel comprising a ceramic dielectric substrate and a plurality of artificial microstructures arrayed on the ceramic dielectric substrate, wherein the metamaterial functional panel comprises Barium titanate non-ferroelectric ceramic material.
  • the material of the ceramic dielectric substrate is a barium titanate non-ferroelectric ceramic material.
  • the material of the artificial microstructure is a barium titanate non-ferroelectric ceramic material.
  • the ceramic dielectric substrate comprises a plurality of substrate units; the barium titanate in the different substrate units has a different ratio of barium titanate to non-ferroelectric.
  • the ceramic dielectric substrate has a plurality of regions; in the artificial microstructured barium titanate non-ferroelectric ceramic material in different regions, the ratio of barium titanate to non-ferroelectric is different.
  • the non-ferroelectric is magnesium oxide, aluminum oxide or silicon oxide.
  • the dielectric substrate comprises a substrate unit having a plurality of return structures or a toroidal structure.
  • the artificial microstructure is a metal artificial microstructure.
  • the artificial microstructure is of the I-shaped or I-formed type.
  • metamaterials are composed of a plurality of super-material functional plate arrays.
  • the artificial microstructure and the dielectric substrate on which it is located can be regarded as the basic components of the super-material function board.
  • the structural unit, the nature of the metamaterial functional board, is mainly determined by the electromagnetic properties and array laws of a plurality of basic structural units.
  • the electromagnetic properties of a single basic structural unit are mainly determined by the equivalent dielectric constant and equivalent magnetic permeability of the basic structural unit, and the equivalent dielectric constant and equivalent magnetic permeability of a single basic structural unit are determined by the artificial microstructure and
  • the dielectric substrate on which it is located is determined jointly.
  • metamaterial functional panels change the equivalent dielectric constant and equivalent magnetic permeability of a single basic structural unit by changing the structure or size of the artificial microstructure. Finally, a plurality of basic structural units are subjected to a certain law. Arrangement allows the metamaterial function panel to form certain electromagnetic properties, such as electromagnetic modulation for electromagnetic wave convergence, divergence, deflection, and translation.
  • the present invention firstly adopts a metamaterial dielectric substrate composed of a plurality of substrate units, and then, by preparing a composite ceramic material, each substrate unit has a predetermined dielectric constant size, and the present invention adopts the present invention.
  • a composite ceramic material is prepared by doping a non-ferroelectric material in barium titanate (Ba x Siv x Ti0 3 ).
  • barium titanate is a ferroelectric material having a high dielectric constant at room temperature.
  • the dielectric constant can be up to 600.
  • the dielectric constant of barium titanate itself can be adjusted by adjusting the ratio of yttrium and lanthanum.
  • titanium can be significantly reduced after incorporating a non-ferroelectric composite ceramic material.
  • the dielectric constant of the acid bismuth allows the adjustment of the dielectric constant over a wide range.
  • magnesium oxide (MgO) as an example, as a non-ferroelectric, the dielectric constant is not dependent on temperature, about 9 at normal temperature, dielectric loss less than 104, doping MgO in barium titanate, etc.
  • Non-ferroelectrics can make the crystal grains of barium titanate smaller, increase the density of ceramics, and more importantly, can significantly reduce the dielectric constant of barium titanate, which is beneficial to achieve impedance matching of metamaterial micro-structure units. At the same time, it also reduces the microwave dielectric loss of barium titanate.
  • the method for preparing a non-uniform dielectric constant dielectric substrate by the present invention can arbitrarily and flexibly design the dielectric constant of the dielectric substrate as a whole, thereby further enriching the functional application of the metamaterial.
  • the flexible design of the dielectric constant the impedance matching of the artificial microstructure in the metamaterial can be realized. It also has the advantage of reducing the dielectric loss of the dielectric substrate.
  • the special property of the dielectric constant of the barium titanate non-ferroelectric ceramic material is utilized, and the ratio of the barium titanate to the non-ferroelectric body is changed to
  • the dielectric constant of the barium titanate non-ferroelectric ceramic material prepared by the method is precisely controlled, and the artificial microstructure is prepared on the ceramic substrate.
  • the metamaterial, the dielectric substrate and the artificial microstructure obtained by the method of the invention are both On the one hand, the ceramic material overcomes the shortcomings of the existing super-materials having a small dielectric constant and being easy to fall off.
  • the present invention uses a barium titanate non-ferroelectric ceramic material to fabricate a microstructure, for high frequencies such as infrared,
  • the visible light band and the like have extremely low loss, and at the same time, precise control of the dielectric constant of the artificial microstructure can be realized, and the dielectric constant control can be realized not only by the complicated structural design of the artificial microstructure.
  • Figure 1 Flow chart of a method for preparing a non-uniform dielectric constant dielectric substrate.
  • Figure 2 is a schematic view of the structure of the metamaterial.
  • Figure 3 is a plan view of Embodiment 1 of the dielectric substrate.
  • Figure 4 a cross-sectional view taken along line A-A of Figure 3.
  • Figure 5 is a plan view of Embodiment 2 of the dielectric substrate.
  • Figure 6 is a B-B cross-sectional view.
  • FIG. 7 Flow chart of Example 1 of the method for preparing a metamaterial functional board.
  • Figure 8 Flow chart of Example 2 of the method for preparing a metamaterial functional board.
  • the barium titanate powder and the non-ferroelectric powder are uniformly mixed in different proportions, and then sintered at a high temperature to obtain a barium titanate non-ferroelectric ceramic material having different dielectric constants;
  • b determining the dielectric constant of the barium titanate non-ferroelectric ceramic material, and obtaining a relationship between the dielectric constant and the ratio of barium titanate to non-ferroelectric;
  • C determining a dielectric constant of a substrate unit in the metamaterial dielectric substrate according to a predetermined requirement of the metamaterial, and determining a substrate for preparing the substrate unit according to a relationship between a dielectric constant and a ratio of barium titanate to a non-ferroelectric composition a ratio of barium titanate powder to non-ferroelectric powder;
  • steps c and d Repeat steps c and d to sequentially prepare other substrate units, and finally combine the respective substrate units to obtain a metamaterial dielectric substrate.
  • the metamaterial functional panel 100 includes a dielectric substrate 101 and a plurality of artificial microstructures 102 arrayed on the dielectric substrate.
  • the artificial microstructures 102 are located therewith.
  • the dielectric substrate can be viewed as a metamaterial basic structural unit, similar to a crystal lattice in a crystal.
  • Figure 1 shows the microstructure of a metamaterial.
  • the actual metamaterial is an array of basic structural units of the order of the number of molecules of matter according to an artificially designed arrangement.
  • the structure of the artificial microstructure 102 in Fig. 1 is a "work" type structure, and as a specific embodiment, an artificial word derivative type can also be employed.
  • the dielectric substrate of the metamaterial of the present invention comprises a substrate unit having a plurality of composite ceramic materials, the composite ceramic material is a barium titanate non-ferroelectric ceramic material, and the barium titanate non-ferroelectric ceramic material in different substrate units has Different barium titanate ratios are compared with non-ferroelectrics. Since the barium titanate non-ferroelectric ceramic material in different substrate units has different ratios of barium titanate to non-ferroelectric, the dielectric constant of the dielectric substrate is non-uniformly distributed.
  • the dielectric substrate 101 is designed to include a plurality of returning substrate units 103.
  • the plan view of the dielectric substrate is shown in FIG. 3.
  • FIG. 4 is a cross-sectional view taken along line AA of FIG. 3, wherein each of the returning substrate units 103 is made of different barium titanate.
  • Magnesium oxide ceramic materials, the dielectric constant of various barium titanate magnesia ceramic materials increases from the periphery to the center, and different barium titanate magnesia ceramic materials are represented by different packing densities in Fig. 4, wherein the packing density Large means that the dielectric constant is large, and small packing density means that the dielectric constant is small.
  • the equivalent dielectric constant and equivalent of a single basic structural unit Since the electromagnetic properties of a single basic structural unit are mainly determined by the equivalent dielectric constant and equivalent magnetic permeability of the basic structural unit, the equivalent dielectric constant and equivalent of a single basic structural unit The magnetic permeability is determined by the artificial microstructure 102 and the dielectric substrate 101 in which it is disposed. Therefore, when the respective deformed substrate units 103 are made of different barium titanate magnesia ceramic materials, the dielectric substrate 101 is changed. The dielectric constants in the respective different shaped substrate units 103, the equivalent dielectric constants of the basic structural units in the respective returning substrate units 103 will also be changed according to the different returning substrate units 103 thereof, and finally the metamaterials will be changed.
  • the functional panel 100 has different dielectric constant distributions in different regions.
  • the barium titanate powder and the magnesium oxide powder are uniformly mixed in different proportions, and then sintered at a high temperature to obtain a barium titanate magnesia ceramic material having different dielectric constants;
  • the dielectric constant of the substrate unit in the middle of the metamaterial substrate is determined to be the largest, and the ratio of the dielectric constant to the ratio of barium titanate to magnesium oxide is The relationship determines the ratio of barium titanate powder to magnesium oxide powder used to prepare the most intermediate substrate unit;
  • the dielectric substrate 101 is designed to include a plurality of circular substrate units 103, a plan view of the dielectric substrate is shown in FIG. 5, and FIG. 6 is a cross-sectional view taken along line AA of FIG. 5, wherein each ring
  • the substrate unit 103 adopts different barium titanate silicon oxide ceramic materials, and the dielectric constant of various barium titanate silicon oxide ceramic materials decreases from the periphery to the center, and different titanic acids are represented by different packing densities in FIG.
  • Electromagnetic due to a single basic structural unit The characteristics are mainly determined by the equivalent dielectric constant and equivalent magnetic permeability of the basic structural unit, and the equivalent dielectric constant and equivalent magnetic permeability of the single basic structural unit are determined by the artificial microstructure 102 and the dielectric substrate on which it is located. 101 is jointly determined. Therefore, when each of the substrate units 103 is made of a different barium titanate silicon oxide ceramic material, the dielectric constant in each of the different substrate units 103 on the dielectric substrate 101 is changed, and the respective substrate units 103 are The equivalent dielectric constant of the basic structural unit will also be changed depending on the substrate unit 103 to which it belongs, eventually causing the metamaterial functional board 100 to have different dielectric constant distributions in different regions.
  • the barium titanate powder itself has different dielectric constants, and the barium titanate powder and the silicon oxide powder are uniformly mixed in different proportions, and then sintered at a high temperature. , obtaining a barium titanate silicon oxide ceramic material having different dielectric constants;
  • the dielectric constant of the substrate unit in the middle of the metamaterial substrate determines the dielectric constant of the substrate unit in the middle of the metamaterial substrate, according to the relationship between the dielectric constant and the ratio of ⁇ to ⁇
  • the relationship between the electric constant and the ratio of barium titanate to silicon oxide determines the ratio of bismuth to antimony in the barium titanate powder used for preparing the most intermediate substrate unit and the ratio of barium titanate powder to silicon oxide powder;
  • steps c and d to sequentially obtain other annular substrate units, so that the dielectric constants of the other annular substrate units are increased from the center to the outer circumference, and finally the respective substrate units are combined to obtain a metamaterial dielectric substrate. .
  • the size and number of the annular substrate unit 104 in this embodiment can be as needed. Arbitrarily designed to meet the electromagnetic properties of metamaterials.
  • the dielectric constants of the respective annular substrate units 104 are alternately arranged in this embodiment only as a specific example for convenience of the description of the present invention.
  • the dielectric constant of each of the circular substrate units 104 is arranged in a row. The law of the cloth also needs to be determined according to the predetermined electromagnetic properties of the metamaterial.
  • the gist of the present invention is also to provide a design path for the electromagnetic properties of the metamaterial by using different materials of the respective annular substrate units 104, and through the design approach
  • the design of the artificial microstructure of the super-material function board is combined to achieve the purpose of expanding the functional design path of the super material.
  • the preparation method of the metamaterial functional board can be seen in FIGS. 7 and 8. Method for preparing metamaterial functional board embodiment 1
  • a method for preparing a metamaterial functional board the flow chart of the preparation method of this embodiment refers to FIG. 7, and includes the following steps:
  • the barium titanate powder and the magnesium oxide powder are uniformly mixed in different proportions, and then sintered at a high temperature of 1300-140 CTC to obtain a barium titanate magnesia ceramic material having different dielectric constants;
  • the artificial microstructure is printed on the ceramic dielectric substrate by the screen printing method by using the ceramic slurry prepared above, and the ceramic dielectric substrate and the artificial microstructure are sintered at a high temperature to obtain a metamaterial functional plate.
  • the method of screen printing is: first making a screen printing screen, by coating on the frame
  • the photosensitive paste forms a photosensitive film on the frame, and then the shape and arrangement array of the artificial microstructure are transferred to the frame by the developing method, and dried to obtain a screen printing screen; then the ceramic is poured into one end of the screen printing screen.
  • Slurry using a squeegee to apply a certain pressure to the ceramic slurry on the screen printing screen, while moving toward the other end of the screen printing screen, the ceramic slurry is squeezed from the mesh of the graphic part by the squeegee during the movement
  • an artificial microstructure of the ceramic paste material is formed on the ceramic dielectric substrate.
  • the binder in the ceramic slurry is burned off, the solvent is volatilized, and on the other hand, the barium titanate powder and The magnesium oxide powder is sintered to form a barium titanate magnesia ceramic material, and is bonded to the ceramic dielectric substrate, and the artificial microstructure is stably and firmly fixed to the ceramic dielectric substrate.
  • the metamaterial functional plates prepared by the above method are combined according to a predetermined arrangement rule such as lamination, cross arrangement, etc. to form a metamaterial.
  • a predetermined arrangement rule such as lamination, cross arrangement, etc.
  • the dielectric substrate and the artificial microstructure are both ceramic materials, the existing supermaterials are overcome.
  • the dielectric constant is small and easy to fall off.
  • precise control of the dielectric constant of the artificial microstructure can be achieved, and the dielectric constant control can be realized not only by the complicated structural design of the artificial microstructure.
  • a method for preparing a metamaterial functional panel the flow chart of the preparation method of the embodiment is shown in FIG. 8, and includes the following steps:
  • the barium titanate powder and the silica powder are uniformly mixed in different proportions, and then sintered at a high temperature of 1300-140 CTC to obtain a barium titanate silica ceramic material having different dielectric constants while changing the titanic acid.
  • the ratio of bismuth to bismuth in the bismuth powder causes the barium titanate powder itself to have a different dielectric constant;
  • the ratio of the artificial microstructured barium titanate powder to the silica powder, and the enthalpy and bismuth in the barium titanate powder for preparing the artificial microstructure is determined according to the relationship between the dielectric constant and the ratio of bismuth to bismuth. proportion;
  • the artificial micro-structure is printed on the ceramic dielectric substrate by the screen printing method by using the ceramic slurry prepared above, and the artificial micro-structure is printed by using the ceramic slurry with different ratios in different regions of the ceramic dielectric substrate, By controlling the ratio of barium titanate powder to silica powder in the ceramic slurry used in different regions, the non-uniform distribution of the dielectric constant of the artificial microstructure is realized, and finally the ceramic dielectric substrate and the artificial microstructure are at a high temperature. Under sintering, a metamaterial functional board is produced.
  • the screen printing method is as follows: First, a screen printing screen is prepared, a photosensitive film is formed on the frame by coating the photosensitive paste on the frame, and then the shape and arrangement array of the artificial microstructure are transferred to the developing method by the developing method. On the frame, and drying, to obtain a screen printing screen; then pour the ceramic slurry on one end of the screen printing screen, apply a certain pressure to the ceramic slurry on the screen printing screen with the squeegee, and simultaneously screen the screen At the other end of the movement, the ceramic slurry is pressed by the squeegee from the mesh of the image portion onto the ceramic dielectric substrate during movement to form an artificial microstructure of the ceramic slurry material.
  • the binder in the ceramic slurry is burned off, the solvent is volatilized, and on the other hand, the barium titanate powder and The silica powder is sintered to form a barium titanate silica ceramic material, and is bonded to the ceramic dielectric substrate, and the artificial microstructure is stably and firmly fixed to the ceramic dielectric substrate.
  • the metamaterial functional plates prepared by the above method are combined according to a predetermined arrangement rule such as lamination, cross arrangement, etc. to form a metamaterial.
  • a predetermined arrangement rule such as lamination, cross arrangement, etc.
  • the dielectric substrate and the artificial microstructure are both ceramic materials, the existing supermaterials are overcome.
  • the dielectric constant is small and easy to fall off.
  • precise control of the dielectric constant of the artificial microstructure can be achieved, and the dielectric constant control can be realized not only by the complicated structural design of the artificial microstructure.
  • the paper substrate unit or the circular substrate unit in the present invention are only In one embodiment, the shape of the area of the substrate unit can be arbitrarily designed as needed.
  • the artificial microstructure in the present invention is an I-shaped or a split ring type, and may also be a derivative-type or a split-ring-derived type.

Abstract

本发明提供一种制备非均匀介电常数介质基板的方法，利用钛酸锶钡非铁电体陶瓷材料介电常数的特殊性质，通过改变钛酸锶钡与非铁电体的配比来对由二者制备的钛酸锶钡非铁电体陶瓷材料的介电常数进行精确控制，能在整体上对介质基板的介电常数进行任意灵活的设计，进而使超材料具有更为丰富的功能应用。本发明还提供了一种超材料功能板的制备方法。由本发明所述方法制得的超材料，介质基板和人造微结构均为陶瓷材料，一方面克服了现有超材料整体介电常数小，容易脱落的缺点，另一方面，能实现对人造微结构介电常数的精确控制，而不仅仅通过人造微结构的复杂结构设计来实现介电常数的控制。

Description

制备非均匀介电常数介质基板的方法、 制备超材料功能板的方法及超材料 【技术领域】
本发明涉及超材料领域， 具体地涉及超材料的介质基板、超材料功能板 以及超材料。
【背景技术】
超材料一般由多个超材料功能板层叠或按其他规律阵列组合而成，超材 料功能板包括介质基板以及阵列在介质基板上的多个人造微结构，现有超材 料的介质基板为均一材料的有机或无机基板， 如 FR4、 TP 1等等。 阵列在介 质基板上的多个人造微结构具有特定的电磁特性，能对电场或磁场产生电磁 响应， 通过对人造微结构的结构和排列规律进行精确设计和控制， 可以使超 材料呈现出各种一般材料所不具有的电磁特性， 如能汇聚、发散和偏折电磁 波等。
现有的介质基板作为人造微结构的固定基板，由于整体上具有均一的介 电常数和磁导率， 所以对电场或磁场不会产生特有的响应， 即对整个超材料 而言， 介质基板不具有电磁调制功能。
为使介质基板能的不同区域具有预定的介电常数分布，可以通过将介质 基板做成包括有多个基板单元，通过为每个基板单元选择合适的材料可以实 现介电常数的非均匀分布， 但是， 受材料选择范围的影响， 为每个基板单元 选择的材料并不能很好地达到预定的要求， 其介电常数的大小不易控制。
另外，现有超材料一般采用在有机树脂基板上阵列金属微结构的方法来 制备， 介质基板采用的有机树脂材料， 所以整体的介电常数较小， 不能满足 应用要求。 同时， 金属材料的人造微结构具有容易脱落和结构复杂的缺点。 现有的有机树脂基板上阵列金属微结构的超材料， 适用于微波频段的电磁 波， 而对于高频如红外、 可见光频段等其具有特别大的损耗。
【发明内容】 本发明克服现有超材料的介质基板缺乏功能作用的缺点，提供一种制备 非均匀介电常数介质基板的方法； 另外， 提供一种以陶瓷材料为介质基板， 以钛酸锶钡非铁电体陶瓷材料制造人造微结构的超材料功能板制备方法；最 后， 本发明还提供一种的超材料， 通过改变介质基板局部材料来改变超材料 的局部介电常数， 使超材料在功能上得到应用拓展。
根据本发明的一个主要方面，制备非均匀介电常数介质基板的方法包括 以下步骤：
a.将钛酸锶钡粉末与非铁电体粉末按不同比例混合均匀，然后在高温下 烧结， 得到具有不同介电常数的钛酸锶钡非铁电体陶瓷材料；
b.测定钛酸锶钡非铁电体陶瓷材料的介电常数，得到介电常数相对钛酸 锶钡与非铁电体配比的关系；
c.根据超材料的预定需求确定超材料介质基板中某一基板单元的介电 常数大小，根据介电常数相对钛酸锶钡与非铁电体配比的关系确定用于制备 该基板单元的钛酸锶钡粉末与非铁电体粉末的配比；
d.将钛酸锶钡粉末与非铁电体粉末按确定的用于制备该基板单元的钛 酸锶钡粉末与非铁电体粉末的配比混合均匀，再装入用于成型该基板单元的 模具内， 然后在高温下烧结， 制得该基板单元；
e.重复步骤 c和 d依次制得其他基板单元，最终将各个基板单元组合得 到超材料介质基板。
优选地， a步骤中还包括通过控制钛酸锶钡粉末中锶与钡的比例使钛酸 锶钡粉末自身具有不同的介电常数， b步骤还包括得到介电常数相对锶与钡 的比例的关系， c步骤还包括根据介电常数相对锶与钡的比例的关系确定用 于制备该基板单元的钛酸锶钡粉末中锶与钡的比例。
优选地， 非铁电体为氧化镁、 氧化铝或氧化硅。
优选地， 该方法还包括一对钛酸锶钡粉末与氧化镁粉末的烘干步骤。 根据本发明的另一个主要方面， 超材料功能板的制备方法包括以下步 骤：
a.将钛酸锶钡粉末与非铁电体粉末按不同比例混合均匀，然后在高温下 烧结， 得到具有不同介电常数的钛酸锶钡非铁电体陶瓷材料； b.测定钛酸锶钡非铁电体陶瓷材料的介电常数，得到介电常数相对钛酸 锶钡与非铁电体配比的关系；
C.根据超材料的预定需求确定超材料介质基板上人造微结构的介电常 数大小，根据介电常数相对钛酸锶钡与非铁电体配比的关系确定用于制备该 人造微结构的钛酸锶钡粉末与非铁电体粉末的配比；
d.将钛酸锶钡粉末与非铁电体粉末按确定的配比混合均匀，加入粘结剂 和丙酮， 制得陶瓷浆料；
e.通过丝网印刷的方法以陶瓷浆料在陶瓷介质基板印刷出人造微结构， 将陶瓷介质基板和人造微结构在高温下烧结， 制得超材料功能板。
优选地， e步骤还包括： 控制在陶瓷介质基板的不同区域分别印刷出人 造微结构，各个不同区域采用的陶瓷浆料中钛酸锶钡粉末与非铁电体粉末的 配比不同。
优选地， a步骤中还包括通过控制钛酸锶钡粉末中锶与钡的比例使钛酸 锶钡粉末自身具有不同的介电常数。
优选地， b步骤还包括得到介电常数相对锶与钡的比例的关系。
优选地， c步骤还包括根据介电常数相对锶与钡的比例的关系确定用于 制备人造微结构的钛酸锶钡粉末中锶与钡的比例。
优选地， 非铁电体为氧化镁、 氧化铝或二氧化硅。
优选地， d步骤中还包括对钛酸锶钡粉末与氧化镁粉末的研磨步骤， 研 磨后将钛酸锶钡粉末与非铁电体粉末按确定的配比混合均匀。
根据本发明的又一个主要方面， 超材料包括多个阵列的超材料功能板， 超材料功能板包括陶瓷介质基板以及阵列在陶瓷介质基板上的多个人造微 结构， 其中， 超材料功能板包含钛酸锶钡非铁电体陶瓷材料。
优选地， 陶瓷介质基板的材料为钛酸锶钡非铁电体陶瓷材料。
优选地， 人造微结构的材料为钛酸锶钡非铁电体陶瓷材料。
优选地， 陶瓷介质基板包括多个基板单元； 不同基板单元中的钛酸锶钡 非铁电体陶瓷材料具有不同的钛酸锶钡与非铁电体配比。
优选地， 陶瓷介质基板具有多个区域； 不同区域内人造微结构的钛酸锶 钡非铁电体陶瓷材料中钛酸锶钡与非铁电体的配比不同。 优选地， 非铁电体为氧化镁、 氧化铝或氧化硅。
优选地， 介质基板包括有多个回形结构或圆环形结构的基板单元。
优选地， 人造微结构为金属人造微结构。
优选地， 人造微结构为工字型或工字衍生型。
超材料作为一种对电磁波具有特殊响应和调制特性的新材料，是由多个 超材料功能板阵列组合而成，人造微结构及其所在的介质基板可看作是组成 超材料功能板的基本结构单元，超材料功能板的性质主要取决于多个基本结 构单元的电磁性质和阵列规律。单个基本结构单元的电磁特性主要由该基本 结构单元的等效介电常数和等效磁导率决定，而单个基本结构单元的等效介 电常数和等效磁导率又由人造微结构及其所在的介质基板所共同决定。现有 对超材料功能板的设计都是通过改变人造微结构的结构或大小来改变单个 基本结构单元的等效介电常数和等效磁导率，最后将多个基本结构单元按照 一定的规律进行排布， 可以使超材料功能板形成某些特定的电磁特性， 如对 电磁波的汇聚、 发散、 偏折和平移等电磁调制功能。
本发明为拓展超材料功能板的功能设计方式，首先采用具有多个基板单 元组成的超材料介质基板，然后通过制备复合陶瓷材料的方法使各个基板单 元具有预定的介电常数大小， 本发明采用在钛酸锶钡 （BaxSivxTi03) 中掺入 非铁电体的方法制备复合陶瓷材料， 首先， 钛酸锶钡是一种铁电体， 具有很 高的介电常数， 在常温下的介电常数可达 600， 同时， 通过调节锶和钡的比 例可以调节钛酸锶钡自身的介电常数， 其次， 在掺入非铁电体制得复合陶瓷 材料后， 可以显著地降低钛酸锶钡的介电常数， 实现在大范围内进行介电常 数的调节。 以氧化镁 （MgO ) 为例， 作为一种非铁电体， 其介电常数对于温 度的依赖不明显， 常温下约为 9， 介电损耗小于 104， 在钛酸锶钡中掺杂 MgO 等非铁电体， 可以使钛酸锶钡的晶粒变小， 提高陶瓷致密度， 更重要的是可 以显著降低钛酸锶钡的介电常数，从而有利于实现超材料微结构单元的阻抗 匹配， 同时也降低钛酸锶钡的微波介电损耗。
通过本发明制备非均匀介电常数介质基板的方法能在整体上对介质基 板的介电常数进行任意灵活的设计， 进而使超材料具有更为丰富的功能应 用。 通过介电常数的灵活设计， 能实现超材料中人造微结构的阻抗匹配， 同 时也具有降低介质基板微波介电损耗的优点。
而根据本发明提供的制备超材料功能板的方法，利用钛酸锶钡非铁电体 陶瓷材料介电常数的特殊性质，通过改变钛酸锶钡与非铁电体的配比来对由 二者制备的钛酸锶钡非铁电体陶瓷材料的介电常数进行精确控制，进而在陶 瓷基板上制备人造微结构， 由本发明所述方法制得的超材料， 介质基板和人 造微结构均为陶瓷材料， 一方面克服了现有超材料整体介电常数小， 容易脱 落的缺点，另一方面，本发明采用钛酸锶钡非铁电体陶瓷材料来制造微结构， 对于高频如红外、 可见光频段等其具有极低的损耗， 同时， 还能实现对人造 微结构介电常数的精确控制，而不仅仅通过人造微结构的复杂结构设计来实 现介电常数的控制。
【附图说明】
图 1， 制备非均匀介电常数介质基板的方法流程图。
图 2， 超材料的结构示意图。
图 3， 介质基板的实施例 1的平面视图。
图 4， 图 3的 A-A剖视图。
图 5， 介质基板的实施例 2的平面视图。
图 6， 图 5的 B-B剖视图。
图 7， 超材料功能板的制备方法的实施例 1的流程图。
图 8， 超材料功能板的制备方法的实施例 2的流程图。
【具体实施方式】
下面结合附图和实施例对本发明进行详细说明。
本发明制备非均匀介电常数介质基板的方法流程图参看附图 1， 包括以 下步骤：
a.将钛酸锶钡粉末与非铁电体粉末按不同比例混合均匀，然后在高温下 烧结， 得到具有不同介电常数的钛酸锶钡非铁电体陶瓷材料；
b.测定钛酸锶钡非铁电体陶瓷材料的介电常数，得到介电常数相对钛酸 锶钡与非铁电体配比的关系； C .根据超材料的预定需求确定超材料介质基板中某一基板单元的介电 常数大小，根据介电常数相对钛酸锶钡与非铁电体配比的关系确定用于制备 该基板单元的钛酸锶钡粉末与非铁电体粉末的配比；
d.将钛酸锶钡粉末与非铁电体粉末按确定的用于制备该基板单元的钛 酸锶钡粉末与非铁电体粉末的配比混合均匀，再装入用于成型该基板单元的 模具内， 然后在高温下烧结， 制得该基板单元；
e.重复步骤 c和 d依次制得其他基板单元，最终将各个基板单元组合得 到超材料介质基板。
超材料的结构示意图参看附图 2， 包括多个层叠超材料功能板 100， 超 材料功能板 100包括介质基板 101以及阵列在介质基板上的多个人造微结构 102， 人造微结构 102与其所在的介质基板可以看成一个超材料基本结构单 元， 类似于晶体中的晶格。 附图 1表示的是超材料微观结构， 实际的超材料 是由物质分子数数量级的基本结构单元按照人为设计的排布规律阵列而成。 附图 1中的人造微结构 102的结构为 "工"字型结构， 作为具体实施方式， 还可以采用工字衍生型。本发明的超材料的介质基板包括有多个复合陶瓷材 料的基板单元， 复合陶瓷材料为钛酸锶钡非铁电体陶瓷材料， 不同基板单元 中的钛酸锶钡非铁电体陶瓷材料具有不同的钛酸锶钡与非铁电体配比。由于 不同基板单元中的钛酸锶钡非铁电体陶瓷材料具有不同的钛酸锶钡与非铁 电体配比， 所以介质基板的介电常数呈非均匀的分布。下面结合实施例对本 发明进行详细说明。 介质基板实施例 1
将介质基板 101设计为包括有多个回形基板单元 103， 介质基板的平面 视图参看附图 3， 图 4为图 3的 A-A剖视图， 其中， 各个回形基板单元 103 采用不同的钛酸锶钡氧化镁陶瓷材料，各种钛酸锶钡氧化镁陶瓷材料的介电 常数大小由外围向中心递增，图 4中用不同填充密度表示了不同的钛酸锶钡 氧化镁陶瓷材料， 其中， 填充密度大的表示介电常数大， 填充密度小的表示 介电常数小。由于单个基本结构单元的电磁特性主要由该基本结构单元的等 效介电常数和等效磁导率决定，而单个基本结构单元的等效介电常数和等效 磁导率又由人造微结构 102及其所在的介质基板 101所共同决定， 所以， 当 各个回形基板单元 103采用不同的钛酸锶钡氧化镁陶瓷材料时，相当于改变 了介质基板 101上各个不同回形基板单元 103内的介电常数，各个回形基板 单元 103 内的基本结构单元的等效介电常数随着其所属回形基板单元 103 的不同也将被改变，最终使超材料功能板 100在不同区域内具有不同的介电 常数分布。
本实施例制备非均匀介电常数介质基板的方法包括以下步骤：
a.将钛酸锶钡粉末与氧化镁粉末按不同比例混合均匀，然后在高温下烧 结， 得到具有不同介电常数的钛酸锶钡氧化镁陶瓷材料；
b.测定钛酸锶钡氧化镁陶瓷材料的介电常数，得到介电常数相对钛酸锶 钡与氧化镁配比的关系；
c.根据超材料预定的介电常数大小由外围向中心递增的变化规律，确定 超材料介质基板最中间的基板单元的介电常数最大，根据介电常数相对钛酸 锶钡与氧化镁配比的关系确定用于制备最中间的基板单元的钛酸锶钡粉末 与氧化镁粉末的配比；
d.将钛酸锶钡粉末与氧化镁粉末按确定的用于制备最中间的基板单元 的钛酸锶钡粉末与氧化镁粉末的配比混合均匀，再装入用于成型该基板单元 的模具内， 然后在高温下烧结， 制得最中间的方形基板单元；
e.重复步骤 c和 d依次制得其他各回形基板单元，使制得的其他各回形 基板单元的介电常数由中心向外周递减，最终将各个基板单元组合得到超材 料介质基板。 介质基板实施例 2
作为本发明的另一种变形，将介质基板 101设计为包括有多个圆环形基 板单元 103， 介质基板的平面视图参看附图 5， 图 6为图 5的 A-A剖视图， 其中， 各个圆环形基板单元 103采用不同的钛酸锶钡氧化硅陶瓷材料， 各种 钛酸锶钡氧化硅陶瓷材料的介电常数大小由外围向中心递减，图 6中用不同 填充密度表示了不同的钛酸锶钡氧化硅陶瓷材料， 其中， 填充密度大的表示 介电常数大， 填充密度小的表示介电常数小。 由于单个基本结构单元的电磁 特性主要由该基本结构单元的等效介电常数和等效磁导率决定，而单个基本 结构单元的等效介电常数和等效磁导率又由人造微结构 102 及其所在的介 质基板 101所共同决定， 所以， 当各个基板单元 103采用不同的钛酸锶钡氧 化硅陶瓷材料时，相当于改变了介质基板 101上各个不同基板单元 103内的 介电常数，各个基板单元 103内的基本结构单元的等效介电常数随着其所属 基板单元 103的不同也将被改变，最终使超材料功能板 100在不同区域内具 有不同的介电常数分布。
本实施例制备非均匀介电常数介质基板的方法包括以下步骤：
a. 通过控制钛酸锶钡粉末中锶与钡的比例使钛酸锶钡粉末自身具有不 同的介电常数， 将钛酸锶钡粉末与氧化硅粉末按不同比例混合均匀， 然后在 高温下烧结， 得到具有不同介电常数的钛酸锶钡氧化硅陶瓷材料；
b.测定钛酸锶钡氧化硅陶瓷材料的介电常数，得到介电常数相对锶与钡 的比例的关系以及介电常数相对钛酸锶钡与氧化硅配比的关系；
c.根据超材料预定的介电常数大小由外围向中心递减的变化规律，确定 超材料介质基板最中间的基板单元的介电常数大小，根据介电常数相对锶与 钡的比例的关系以及介电常数相对钛酸锶钡与氧化硅配比的关系确定用于 制备最中间的基板单元的钛酸锶钡粉末中锶与钡的比例以及钛酸锶钡粉末 与氧化硅粉末的配比；
d.将钛酸锶钡粉末与氧化硅粉末按确定的用于制备最中间的基板单元 的钛酸锶钡粉末与氧化硅粉末的配比混合均匀， 在用高能球研磨机研磨 6 小时， 在 80 ° C温度下烘干， 之后过筛 140/200/250， 在 1000 ° C预烧 2小 时后， 再次用高能球研磨研磨 16-24小时， 再加入 4%wt的聚乙烯醇粘合剂
( PVA ) 和丙酮， 用磁搅拌器充分搅拌至粘合剂和丙酮挥发， 将混合粉末放 入根据基板单元形状设计的模具中压制成型，置于微波腔在 1300 ° C-1400 ° C烧结 1小时， 最后自然冷却， 制得最中间的圆形基板单元；
e.重复步骤 c和 d依次制得其他各圆环形基板单元，使制得的其他各圆 环形基板单元的介电常数由中心向外周递增，最终将各个基板单元组合得到 超材料介质基板。
应当理解，本实施例中圆环形基板单元 104的大小和数量可以根据需要 任意设计， 以满足超材料的电磁特性要求。 并且， 本实施例中各个圆环形基 板单元 104 的介电常数大小交替排列只是为了便于说明本发明而例举的特 例， 具体实施时， 各个圆环形基板单元 104的介电常数大小的排布规律也需 要根据预定的超材料电磁特性而定，本发明的要旨也在于通过各个圆环形基 板单元 104采用不同的材料为超材料的电磁特性提供一种设计途径，并通过 该设计途径与超材料功能板上人造微结构排布规律的设计进行组合，以达到 扩展超材料的功能设计途径的目的。 超材料功能板的制备方法可以参见图 7和图 8。 超材料功能板制备方法实施例 1
一种超材料功能板的制备方法， 本实施例制备方法的流程图参看附图 7， 包括以下步骤：
a.将钛酸锶钡粉末与氧化镁粉末按不同比例混合均匀， 然后在 1300- 140CTC的高温下烧结， 得到具有不同介电常数的钛酸锶钡氧化镁陶瓷 材料；
b.测定钛酸锶钡氧化镁陶瓷材料的介电常数，得到介电常数相对钛酸锶 钡与氧化镁配比的关系， 由于钛酸锶钡粉末与氧化镁粉末的配比不同时， 高 温烧结得到的钛酸锶钡氧化镁陶瓷材料介电常数呈现出不同，所以经过实验 测定， 可以得到介电常数相对钛酸锶钡与氧化镁配比的对应关系；
c.根据超材料的预定需求确定超材料介质基板上人造微结构的介电常 数大小，根据介电常数相对钛酸锶钡与氧化镁配比的关系确定用于制备该人 造微结构的钛酸锶钡粉末与氧化镁粉末的配比；
d.将钛酸锶钡粉末与氧化镁粉末按确定的配比混合均匀，加入粘结剂聚 乙烯醇和溶剂丙酮， 制得陶瓷浆料；
e.通过丝网印刷的方法以上述制得的陶瓷浆料在陶瓷介质基板印刷出 人造微结构， 将陶瓷介质基板和人造微结构在高温下烧结， 制得超材料功能 板。
步骤 e中， 丝网印刷的方法是： 首先制作丝印网版， 通过在网框上涂覆 感光浆使网框上形成感光膜，然后将人造微结构的形状和排列阵列通过显影 的方法转移到网框上， 并进行干燥， 制得丝印网版； 然后在丝印网版的一端 倒入陶瓷浆料， 用刮印板给丝印网版上的陶瓷浆料施加一定的压力， 同时朝 丝印网版的另一端移动，陶瓷浆料在移动中被刮板从图文部分的网孔中挤压 到陶瓷介质基板上， 形成陶瓷浆料材料的人造微结构。
步骤 e 中， 陶瓷介质基板与陶瓷浆料材料的人造微结构在高温下烧结 时， 一方面陶瓷浆料中的粘结剂被烧掉， 溶剂被挥发， 另一方面， 钛酸锶钡 粉末与氧化镁粉末经烧结形成钛酸锶钡氧化镁陶瓷材料，同时与陶瓷介质基 板相粘结， 人造微结构被稳定牢固地固定到了陶瓷介质基板上。
将上述方法制得的超材料功能板按照预定的排布规律如层叠、交叉排列 等进行组合，形成超材料，一方面由于介质基板和人造微结构均为陶瓷材料， 克服了现有超材料整体介电常数小， 容易脱落的缺点， 另一方面， 能实现对 人造微结构介电常数的精确控制，而不仅仅通过人造微结构的复杂结构设计 来实现介电常数的控制。 超材料功能板制备方法实施例 2
一种超材料功能板的制备方法， 本实施例制备方法的流程图参看附图 8， 包括以下步骤：
a.将钛酸锶钡粉末与二氧化硅粉末按不同比例混合均匀， 然后在 1300- 140CTC的高温下烧结， 得到具有不同介电常数的钛酸锶钡二氧化硅陶 瓷材料，同时改变钛酸锶钡粉末中锶与钡的比例使钛酸锶钡粉末自身具有不 同的介电常数；
b.测定钛酸锶钡氧化镁陶瓷材料的介电常数，得到介电常数相对钛酸锶 钡与二氧化硅配比的关系， 由于钛酸锶钡粉末与二氧化硅粉末的配比不同 时， 高温烧结得到的钛酸锶钡二氧化硅陶瓷材料介电常数呈现出不同， 所以 经过实验测定， 可以得到介电常数相对钛酸锶钡与二氧化硅配比的对应关 系， 同时， 得到介电常数相对锶与钡的比例的关系；
c.根据超材料的预定需求确定超材料介质基板上人造微结构的介电常 数大小，根据介电常数相对钛酸锶钡与二氧化硅配比的关系确定用于制备该 人造微结构的钛酸锶钡粉末与二氧化硅粉末的配比， 同时， 根据介电常数相 对锶与钡的比例的关系确定用于制备人造微结构的钛酸锶钡粉末中锶与钡 的比例；
d.将钛酸锶钡粉末与二氧化硅粉末按确定的配比混合均匀，在用高能球 研磨机研磨 6小时，在 80 ° C温度下烘干，之后过筛 140/200/250，在 1000 ° C预烧 2小时后， 再次用高能球研磨研磨 16-24小时， 再加入 4%wt的聚乙 烯醇粘合剂 （PVA ) 和丙酮， 制得陶瓷浆料；
e.通过丝网印刷的方法以上述制得的陶瓷浆料在陶瓷介质基板印刷出 人造微结构，控制在陶瓷介质基板的不同区域分别采用具有不同配比的陶瓷 浆料印刷出人造微结构，通过控制各个不同区域采用的陶瓷浆料中钛酸锶钡 粉末与二氧化硅粉末的配比， 来实现人造微结构介电常数大小的非均匀分 布， 最后将陶瓷介质基板和人造微结构在高温下烧结， 制得超材料功能板。
步骤 e中， 丝网印刷的方法是： 首先制作丝印网版， 通过在网框上涂覆 感光浆使网框上形成感光膜，然后将人造微结构的形状和排列阵列通过显影 的方法转移到网框上， 并进行干燥， 制得丝印网版； 然后在丝印网版的一端 倒入陶瓷浆料， 用刮印板给丝印网版上的陶瓷浆料施加一定的压力， 同时朝 丝印网版的另一端移动，陶瓷浆料在移动中被刮板从图文部分的网孔中挤压 到陶瓷介质基板上， 形成陶瓷浆料材料的人造微结构。
步骤 e 中， 陶瓷介质基板与陶瓷浆料材料的人造微结构在高温下烧结 时， 一方面陶瓷浆料中的粘结剂被烧掉， 溶剂被挥发， 另一方面， 钛酸锶钡 粉末与二氧化硅粉末经烧结形成钛酸锶钡二氧化硅陶瓷材料，同时与陶瓷介 质基板相粘结， 人造微结构被稳定牢固地固定到了陶瓷介质基板上。
将上述方法制得的超材料功能板按照预定的排布规律如层叠、交叉排列 等进行组合，形成超材料，一方面由于介质基板和人造微结构均为陶瓷材料， 克服了现有超材料整体介电常数小， 容易脱落的缺点， 另一方面， 能实现对 人造微结构介电常数的精确控制，而不仅仅通过人造微结构的复杂结构设计 来实现介电常数的控制。 最后需要说明的是，本发明中的回形基板单元或圆环形基板单元均只是 具体实施方式之一， 基板单元的区域形状可以根据需要进行任意设计。而作 为具体实施方式， 本发明中的人造微结构为工字型或开口环型， 也可以为工 字衍生型或开口环衍生型。
在上述实施例中， 仅对本发明进行了示范性描述， 但是本领域技术人员 在阅读本专利申请后可以在不脱离本发明的精神和范围的情况下对本发明 进行各种修改。

Claims

权 利 要 求 书
1、 一种制备非均匀介电常数介质基板的方法， 用于使超材料介质基板 的多个基板单元具有预定的介电常数， 包括以下步骤：
a.将钛酸锶钡粉末与非铁电体粉末按不同比例混合均匀，然后在高温下 烧结， 得到具有不同介电常数的钛酸锶钡非铁电体陶瓷材料；
b.测定钛酸锶钡非铁电体陶瓷材料的介电常数，得到介电常数相对钛酸 锶钡与非铁电体配比的关系；
c.根据超材料的预定需求确定超材料介质基板中某一基板单元的介电 常数大小，根据介电常数相对钛酸锶钡与非铁电体配比的关系确定用于制备 该基板单元的钛酸锶钡粉末与非铁电体粉末的配比；
d.将钛酸锶钡粉末与非铁电体粉末按确定的用于制备该基板单元的钛 酸锶钡粉末与非铁电体粉末的配比混合均匀，再装入用于成型该基板单元的 模具内， 然后在高温下烧结， 制得该基板单元；
e.重复步骤 c和 d依次制得其他基板单元，最终将各个基板单元组合得 到超材料介质基板。
2、 根据权利要求 1所述的制备非均匀介电常数介质基板的方法， 其特 征在于，所述 a步骤中还包括通过控制所述钛酸锶钡粉末中锶与钡的比例使 所述钛酸锶钡粉末自身具有不同的介电常数，所述 b步骤还包括得到介电常 数相对锶与钡的比例的关系，所述 c步骤还包括根据介电常数相对锶与钡的 比例的关系确定用于制备该基板单元的钛酸锶钡粉末中锶与钡的比例。
3、 根据权利要求 1或 2所述的制备非均匀介电常数介质基板的方法， 其特征在于： 所述非铁电体为氧化镁、 氧化铝或氧化硅。
4、 根据权利要求 3所述的制备非均匀介电常数介质基板的方法， 其特 征在于： 还包括一对所述钛酸锶钡粉末与氧化镁粉末的烘干步骤。
5、 一种超材料功能板的制备方法， 其特征在于， 所述制备方法包括以 下步骤：
a.将钛酸锶钡粉末与非铁电体粉末按不同比例混合均匀，然后在高温下 烧结， 得到具有不同介电常数的钛酸锶钡非铁电体陶瓷材料； b.测定钛酸锶钡非铁电体陶瓷材料的介电常数，得到介电常数相对钛酸 锶钡与非铁电体配比的关系；
C .根据超材料的预定需求确定超材料介质基板上人造微结构的介电常 数大小，根据介电常数相对钛酸锶钡与非铁电体配比的关系确定用于制备该 人造微结构的钛酸锶钡粉末与非铁电体粉末的配比；
d.将钛酸锶钡粉末与非铁电体粉末按确定的配比混合均匀，加入粘结剂 和丙酮， 制得陶瓷浆料；
e.通过丝网印刷的方法以所述陶瓷浆料在陶瓷介质基板印刷出人造微 结构， 将陶瓷介质基板和人造微结构在高温下烧结， 制得超材料功能板。
6、 根据权利要求 5所述的超材料功能板的制备方法， 其特征在于， 所 述 e步骤还包括：控制在所述陶瓷介质基板的不同区域分别印刷出人造微结 构，各个不同区域采用的陶瓷浆料中钛酸锶钡粉末与非铁电体粉末的配比不 同。
7、根据权利要求 5或 6所述的超材料功能板的制备方法， 其特征在于， 所述 a 步骤中还包括通过控制所述钛酸锶钡粉末中锶与钡的比例使所述钛 酸锶钡粉末自身具有不同的介电常数。
8、 根据权利要求 7所述的超材料功能板的制备方法， 其特征在于， 所 述 b步骤还包括得到介电常数相对锶与钡的比例的关系。
9、 根据权利要求 8所述的超材料功能板的制备方法， 其特征在于， 所 述 c 步骤还包括根据介电常数相对锶与钡的比例的关系确定用于制备人造 微结构的钛酸锶钡粉末中锶与钡的比例。
10、 根据权利要求 5所述的超材料功能板的制备方法， 其特征在于： 所 述非铁电体为氧化镁、 氧化铝或二氧化硅。
1 1、 根据权利要求 5所述的超材料功能板的制备方法， 其特征在于： 所 述 d步骤中还包括对所述钛酸锶钡粉末与氧化镁粉末的研磨步骤，研磨后将 钛酸锶钡粉末与非铁电体粉末按确定的配比混合均匀。
12、 一种超材料， 包括多个阵列的超材料功能板， 所述超材料功能板包 括陶瓷介质基板以及阵列在陶瓷介质基板上的多个人造微结构， 其中， 所述 超材料功能板包含钛酸锶钡非铁电体陶瓷材料。
13、 根据权利要求 12所述的超材料， 其特征在于： 所述陶瓷介质基板 的材料为钛酸锶钡非铁电体陶瓷材料。
14、 根据权利要求 12所述的超材料， 其特征在于： 所述人造微结构的 材料为钛酸锶钡非铁电体陶瓷材料。
15、 根据权利要求 13所述的超材料， 其特征在于： 所述陶瓷介质基板 包括多个基板单元；不同基板单元中的钛酸锶钡非铁电体陶瓷材料具有不同 的钛酸锶钡与非铁电体配比。
16、 根据权利要求 14所述的超材料， 其特征在于： 所述陶瓷介质基板 具有多个区域；不同区域内人造微结构的钛酸锶钡非铁电体陶瓷材料中钛酸 锶钡与非铁电体的配比不同。
17、 根据权利要求 12所述的超材料， 其特征在于： 所述非铁电体为氧 化镁、 氧化铝或氧化硅。
18、 根据权利要求 12所述的超材料， 其特征在于： 所述介质基板包括 有多个回形结构或圆环形结构的基板单元。
19、 根据权利要求 12所述的超材料， 其特征在于： 所述人造微结构为 金属人造微结构。
20、 根据权利要求 12所述的超材料， 其特征在于： 所述人造微结构为 工字型或工字衍生型。
PCT/CN2011/084453 2011-06-01 2011-12-22 制备非均匀介电常数介质基板的方法、制备超材料功能板的方法及超材料 WO2012163071A1 (zh)

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CN101517474A (zh) * 2006-05-13 2009-08-26 卢森特技术有限公司 基于超材料的非线性光学装置
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CN101863154A (zh) * 2010-06-17 2010-10-20 天津大学 多层梯度钛酸锶钡介电陶瓷材料及制备方法

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US20010035543A1 (en) * 1999-03-08 2001-11-01 Advanced Technology Materials, Inc. Confinement of E-fields in high density ferroelectric memory device structures
CN101517474A (zh) * 2006-05-13 2009-08-26 卢森特技术有限公司 基于超材料的非线性光学装置
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