CN100516140C - Method for preparing strontium-barium titanate/polymide dielectric adjustable composite material thick film - Google Patents
Method for preparing strontium-barium titanate/polymide dielectric adjustable composite material thick film Download PDFInfo
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- CN100516140C CN100516140C CNB2007100178894A CN200710017889A CN100516140C CN 100516140 C CN100516140 C CN 100516140C CN B2007100178894 A CNB2007100178894 A CN B2007100178894A CN 200710017889 A CN200710017889 A CN 200710017889A CN 100516140 C CN100516140 C CN 100516140C
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Abstract
The invention discloses the preparation methods of a barium strontium titanate / polyimide dielectric with the materials of adjustable thick composite, uses polyimide as a precursor; Selecting the barium strontium titanate powder dielectric ceramics (Ba1-xSrx) TiO3 as dielectric adjustable phase, polyimide precursors and the surface treatment of barium strontium titanate dielectric ceramic powder mixed in proportion, by using a high-energy or ordinary ball milling way to make them adequately scattered and get mixed thick-film paste;Using conventional spin-coating process, dipping - carrying process or extension of thick slurry will be mixed in the pre-treatment of the coating material on the substrate, and then coating on the substrate material after the heat treatment process and follow-up process can be get Barium strontium titanate / polyimide dielectric adjustable thick composite materials. This invention need a low processing temperature (=< 350 degree C), the minimum curing temperature is less than 160 degree C.
Description
Technical field
The invention belongs to the manufacture technology of composite material scope, particularly a kind of preparation method of strontium-barium titanate/polymide dielectric adjustable composite material thick film.
Background technology
Along with phased array radar is widely used in various types of detections and tracking system, become the emphasis of research as the key part-phase shifter of phased array radar.With respect to present widely used ferrite and PIN diode, with strontium-barium titanate (Ba
1-xSr
xTiO
3, be called for short BST) and for the ferroelectric material phase shifter of representative receives publicity day by day with its cheap cost, excellent performance and simple technology, become the focus of phase shifter investigation of materials.In numerous ferroelectric phase shifter candidate materials, strontium-barium titanate is with its higher dielectric constant (ε
r＞2000,1MHz) and the adjustable rate of bigger dielectric (＞40%, 1KHz, 5V/um) etc. characteristic is subjected to paying close attention to widely.For phase shifter, require the phase shift material will have moderate relative permittivity, be beneficial to the circuit coupling; Low dielectric loss is beneficial to improve quality factor; High dielectric tuning is to reduce operating voltage; Little temperature factor is to prevent characteristics such as frequency drift.For pure strontium-barium titanate material, and its higher preparation temperature (＞1400 ℃), higher dielectric loss (＞1%, 1MHz) and too high specific inductivity, limited its application on ferroelectric phase shifter.
In order to improve the performance of strontium-barium titanate, people have carried out extensive studies.For the specific inductivity that reduces strontium-barium titanate with improve dielectric loss, have the investigator with magnesium oxide as second phase, the matrix of strontium-barium titanate is advanced in doping, prepares magnesium oxide/strontium-barium titanate complex phase ceramic, but still has preparation temperature height (＞1200 ℃) and the little shortcoming of change in dielectric constant.In order to reduce the burn-back temperature, there is the investigator to mix the burn-back auxiliary agent, as burn-back auxiliary agents such as vanadium oxide, boron oxide or nonexs, but cooling-down effect is not obvious, still has to adopt valuable platinum electrode, makes preparation cost improve.In order to reduce the operating voltage of phase shifter, have the investigator that strontium-barium titanate is prepared into form of film, but complex process is difficult to large-scale industrialization production and can not stand bigger power, and its application is restricted.
Inorganic/organic composite material, because it has kept the characteristic of inorganic materials function phase, can also have the peculiar operational characteristic of polymkeric substance, as the performances such as processing characteristics of lower technological temperature, excellence, realize the function leap of 1+1＞2, and become the focus of research day by day.
In numerous polymkeric substance, polyimide is one of organic polymer material of over-all properties the best.Polyimide (polyimide, abbreviation PI) is the polymkeric substance that a kind of main chain contains the multiple imide group.The excellent combination property of polyimide, high temperature resistant reaching more than 400 ℃, life-time service temperature range-200～300 ℃, specific inductivity 4.0 under the 1kHz, dielectric loss only 0.002～0.005 belongs to F to H class F insulating material F, anti-high radiation, corrosion-resistant, flame resistant does not absorb water, high mechanical strength, also has stronger adhesive capacity, widespread use in aviation, navigation, space, nuclear power, electronic industry.Commercially available polyimide precursor kind is numerous: be polyimide organic solution of solvent etc. as the polyimide coating glue of routine, the standard type polyimide coating glue that is used to chart, photo-sensistive polyimide coating adhesive, low temperature curing type polyimide coating glue with strong polar organic solvent, can select for use according to different requirements.The excellent properties that polyimide had makes its body material as dielectric adjustable composite material become possibility.
How excellent properties and strontium-barium titanate had than high dielectric adjustable in conjunction with polyimide had, prepare a kind of have low synthesis temperature, lower specific inductivity and dielectric loss, certain dielectric adjustable, the simple composite material thick film of technology are research work highly significant.
By literature search, still find no the document and the patent that duplicate with the present invention, the document that some that retrieve are related to the present invention, mainly be in the strontium-barium titanate material, to add comprehensive dielectric properties that low-loss materials such as magnesium oxide improve the strontium-barium titanate material to improve its adaptability in device application, not find any report of polymer-based carbon strontium-barium titanate matrix material dielectric adjustable.Below be the reference related to the present invention that the applicant retrieves:
1.A.K.Tagantsev，V.O.Sherman，K.F.Astafiev，J.Venkatesh，N.Setter，Ferroelectric?materials?for?microwave?tunable?application，Journal?ofElectroceramics，11，5-6(2003)。
2.S.G.Lu，Z.K.Xu，Haydn?Chen，Tunability?and?relaxor?properties?offerroelectric?barium?stannate?titante?ceramics.Applied?physics?letters，85，5319-5321(2004)。
3.Antonio?Feteira，Derek?C.Sinclair，Ian?M.Reaney，YoshitakaSomiya，Michael?T，Lanagan，BaTiO
3-based?ceramics?for?tunable?microwaveapplications，Journal?of?the?America?ceramics?society，87(6)，1082-1087(2004)。
4.V.O.Sherman，A.K.Tagantsev，N.Setter，D.Iddles，T.Price，Ferroelectric-dielectric?tunable?composites，Journal?of?applied?physics，99，074104(2006)。
5.YH.Zhang，ZM.Dang，John?H.Xin，Walid?A.Daoud，JH.Ji，YY.Liu，etc，Dielectric?properties?of?polyimide-mica?hybrid?films，Macromolecular?RapidCommunications，26，1473-1477(2005)。
6.SH.Xie，BK.Zhu，XZ.Wei，ZK.Xu，YY.Xu，Polyimide/BaTiO
3composites?with?controllable?dielectric?properties，36，1152-1157(2005)。
7.S.S.Gevorgian，EL.Kollberg，Do?we?really?need?ferroelectrics?inparaelectric?phase?only?in?electrically?controlled?microwave?devices？，IEEETransactions?on?microwave?theory?techniques，49，2117-2124(2001)。
8.B.Su，T.W.Button，Interactions?between?barium?strontium?titannte(BST)thick?films?and?alumina?substrates，Journal?of?the?European?CeramicSociety，21，2777-2781(2001)。
9.C.M.Ditum，T.W.Button，Screen?printed?barium?strontium?titanntefilms?for?microwave?applications，Journal?of?the?European?Ceramic?Society，23，2693-2697(2003)。
10.S.Y.Lee，T.Y.Tseng，Electrical?and?dielectric?behavior?of?MgO?dopedBa
0.7Sr
0.3TiO
3?thin?films?on?Al
2O
3?substrate.Applied?physics?letters，11，1797-1799(2001)。
11.SH.Xiang，MS.Guo，XH.Sun，T.Liu，MY.Li，XZ.Zhao，Tunable，low?loss?Bi
1.5Zn
1.0Nb
1.5O
7/Ba
0.6Sr
0.4TiO
3/Bi
1.5Zn
1.0Nb
1.5O
7?sandwich?films.Applied?physics?letters?89，212907(2006)。
12.Y.Zheng，C.H.Woo，B.Wang，Z.Y.Zhu，Ferroelectric?rods?withadjustable?dielectric?tenability，Applied?physics?letters，90，092905(2007)。
Summary of the invention
Defective or deficiency at strontium-barium titanate material existence in the above-mentioned background technology, the objective of the invention is to, a kind of preparation method of strontium-barium titanate/polymide dielectric adjustable composite material thick film is provided, this method with polyimide organic medium with excellent properties as the dielectric phase, but select for use barium-strontium titanate-based pottery as the dielectric phase modulation, but design and prepared the dielectric adjustable thick film of the low-temperature heat treatment of different composite structure and recombining process with the adjustable rate of higher dielectric.This method is by after being mixed in proportion polyimide precursor and surface treated strontium-barium titanate dielectric tunable medium ceramic powder, mix by blending equipment, adopt suitable technology to be coated on the base material again, adopt suitable thermal treatment temp, obtain the even or regular dielectric adjustable composite material thick film that is dispersed in the polyimide organic medium of strontium-barium titanate powder.
Strontium-barium titanate/polymide dielectric of the present invention is adjustable inorganic/organic composite material thick film, not only have the lower thermal treatment temp of polyimide, very high dielectric strength, the chemical stability of excellence and good characteristics such as adhesive capacity, and the higher characteristics of the adjustable rate of barium-strontium titanate ceramic dielectric have been kept, greatly reduce specific inductivity, dielectric loss and the thermal treatment temp of matrix material simultaneously, improve the electrical qualities factor of barium-strontium titanate-based dielectric tunable medium pottery, and can on different substrates, form compact dielectric adjustable composite material thick film.
Strontium-barium titanate/polymide dielectric adjustable composite material of the present invention and thick film thereof, have following characteristics: processing temperature low (≤350 ℃), minimum solidification value can obtain the strong thick film of densification, zero defect and adhesive power less than 160 ℃ on dissimilar substrates; According to different material designs, relative permittivity has the regulation range (ε of broad
r=3.5～200), its under the test frequency of 1MHz, little (tan δ≤2 * 10 of dielectric loss
-2); Big (the ρ of insulation resistance
v〉=10
12Ω cm), high energy stands the electric field of 500KV/cm; According to the difference of composite structure, the manually cutting of the adjustable rate of dielectric, under the electric field of 350KV/cm, the adjustable rate of the dielectric of composite material thick film reaches as high as 20%.But characteristics such as technology is simple, practical wide, electric property excellence that the dielectric adjustable composite material thick film of this low-temperature heat treatment has are a kind of novel dielectric adjustable composite materials that has broad prospect of application.
The technical solution that realizes above-mentioned task is: a kind of preparation method of strontium-barium titanate/polymide dielectric adjustable composite material thick film, it is characterized in that, and comprise the following steps:
Select for use polyimide as presoma;
Select barium strontium titanate medium ceramic powder (Ba for use
1-xSr
x) TiO
3But as the dielectric phase modulation, wherein, x=0.2～0.7, the solid content of strontium-barium titanate is 5wt%～90wt%;
Get 100 parts in strontium-barium titanate powder after the fragmentation, drying is 24 hours under 110 ℃, the acrylic acid solution that then dried ceramic powder is added 2～5 parts, supersound process is 1 hour in 50～100 parts dehydrated alcohol, and the barium-strontium titanate ceramic powder surface is handled by vinylformic acid;
Polyimide precursor and surface treated barium strontium titanate medium ceramic powder are mixed in proportion, adopt the mode of general milling or high-energy ball milling to make it abundant dispersion, obtain mixing thick film ink;
Adopting conventional spin coating proceeding, dipping-czochralski process or casting technique will mix thick film ink is coated on the pretreated base material, then the base material after applying is heat-treated technology and subsequent treatment process, can obtain strontium-barium titanate/polymide dielectric adjustable composite material thick film.
The micro-wave dielectric that adopts the present invention to make is adjustable, the novel inorganic/organic micro-wave dielectric adjustable composite material and the thick film thereof of very low temperature thermal treatment, low-k and low-dielectric loss, through the analysis and test of testing apparatuss such as X-ray diffraction (XRD), particle-size analyzer, scanning electronic microscope (SEM), electric impedance analyzer, determine to have following characteristics:
1, the thermal treatment temp of thick film is the highest is no more than 360 ℃, minimumly reaches 160 ℃.Phase structure is the strontium-barium titanate phase and polyimide composite structure mutually that presents cubic perovskite structure.
2, the thickness of composite material thick film is 4um～100um, and the smooth flawless of surfacing can be combined closely with substrate of different nature.
3, the wide (ε of composite material thick film relative permittivity regulation range
r=3.5～200,1MHz), little (tan δ＜2 * 10 of dielectric loss
-2, 1MHz), the big (ρ of insulation resistance
v〉=10
12Ω cm), the dielectric strength height (＞400KV/cm), relatively the adjustable rate of dielectric reaches as high as 20%, (350KV/cm).
4, technology is simple, and may be used on the substrate of different nature, and can realize by the mode of photoetching corrosion graphically, and then the adjustable components and parts of preparation dielectric.
Preparation technology of the present invention is simple, and is convenient, and processing parameter is convenient to control, realizes by the laboratory small-scale production to big industrial transition easily.
Description of drawings
Fig. 1 adopts the coventional type polyimide coating glue as polyimide precursor and high-energy ball milling Ba among the embodiment 3
0.6Sr
0.4TiO
3But powder is as the dielectric phase modulation, uses high-energy ball milling to be mixed with the microtexture photo of the composite material thick film that forms, (a) surface topography wherein, (b) cross-section morphology.
Fig. 2 adopts the coventional type polyimide coating glue as polyimide precursor and high-energy ball milling Ba among the embodiment 3
0.6Sr
0.4TiO
3But powder uses high-energy ball milling to be mixed with the dielectric properties of the composite material thick film that forms and the relation of frequency as the dielectric phase modulation.
Fig. 3 adopts the coventional type polyimide coating glue as polyimide precursor and high-energy ball milling Ba among the embodiment 3
0.6Sr
0.4TiO
3But powder is as the dielectric phase modulation, use high-energy ball milling to be mixed with the dielectric properties of the composite material thick film that forms and the relation of bias voltage, wherein (a) is the dielectric properties under 1MHz of HP4294 electric impedance analyzer test and the relation of bias voltage, (b) is the dielectric properties under 10kHz of HP4284LCR test and the relation of bias voltage.
Fig. 4 adopts the coventional type polyimide coating glue as polyimide precursor and high-energy ball milling Ba among the embodiment 3
0.6Sr
0.4TiO
3But powder uses high-energy ball milling to be mixed with the dielectric properties of the composite material thick film that forms and the relation of temperature as the dielectric phase modulation.
The present invention is further illustrated for specific embodiment that provides below in conjunction with the contriver.
Embodiment
The preparation method of strontium-barium titanate/polymide dielectric adjustable composite material thick film of the present invention, design philosophy from matrix material, with polyimide organic medium mutually as dielectric with excellent dielectric properties and low thermal treatment temp, but with barium-strontium titanate-based pottery with the adjustable rate of higher dielectric as the dielectric phase modulation, but the design and prepared different composite structure and recombining process low-temperature heat treatment dielectric adjustable thick film and carried out deep research, after polyimide precursor and surface treated strontium-barium titanate dielectric tunable medium ceramic powder are mixed in proportion, mix by blending equipment, adopt suitable process deposits again on base material, adopt suitable thermal treatment process, obtain the even or regular dielectric adjustable composite material thick film that is dispersed in the polyimide organic medium of strontium-barium titanate powder.
Low temperature of the present invention synthesizes microwave adjustable dielectric barium strontium titanate/composite polyimide material thick film preparation method, and the prescription of its raw material is formed (by weight) and is:
Barium-strontium titanate powder: the strontium-barium titanate solid content is 5%～90%
Polyimide precursor: 100% of barium-strontium titanate powder quality
Acrylic acid solution: 2%～5% of barium-strontium titanate powder quality
Dehydrated alcohol: about 50 times of the acrylic acid solution quality.
Wherein: polyimide organic solution that polyimide can be the polyimide coating glue of commercially available routine, the standard type polyimide coating glue that is used to chart, photo-sensistive polyimide coating adhesive, low temperature curing type polyimide coating glue and is solvent with strong polar organic solvent etc. has the flowable liquid of certain viscosity.Strontium-barium titanate dielectric tunable medium pottery is (Ba
1-xSr
x) TiO
3(BST), wherein x=0.2～0.7 is prepared from by traditional solid reaction process; Strontium-barium titanate powder median size after the fragmentation is 100nm～1um.
Low temperature synthesizes microwave adjustable dielectric barium strontium titanate/composite polyimide material thick film, and the preparation method is as follows:
Step 1: polyimide precursor adopts commercially available polyimide precursor solution or contains the organic solvent of polyimide.
Step 2: with barium carbonate, Strontium carbonate powder and titanium dioxide is raw material, prepares barium-strontium titanate ceramic according to traditional solid reaction process, again through the barium-strontium titanate ceramic powder of broken acquisition particle diameter less than 1 micron.
Step 3: get 100 parts in strontium-barium titanate powder after the fragmentation, drying is 24 hours under 110 ℃, the acrylic acid solution that then dried ceramic powder is added 2～5 parts, supersound process is 1 hour in 50～100 parts dehydrated alcohol, and the ceramic powder surface is handled by vinylformic acid.
Step 4: the strontium-barium titanate powder after the surface treatment is joined in the polyimide precursor, adopt the mode of general milling or high-energy ball milling to make it abundant dispersion, obtain stable mixing thick film ink.
Step 5: adopt spin coating proceeding, dipping-czochralski process or casting technique to be coated on the pretreated substrate, adopt certain composite structure,, obtain having the composite material thick film of dielectric adjustable by proper heat treatment technology and subsequent technique.
The composite structure of above-mentioned strontium-barium titanate/polymide dielectric adjustable composite material thick film has following three types:
The 0-3 structure: the strontium-barium titanate powder, after heat treatment, obtains the strontium-barium titanate powder and is evenly distributed on composite material thick film in the polyimide matrix within the three-dimensional organic matrix of polyimide with zero dimension dots structure random dispersion;
The 2-2 structure: the thick film ink of different strontium-barium titanate content carries out arranging of lamination cycle by rule, forms a kind of planar layered structures, after heat treatment, obtains a kind of thick film of layered periodic structure;
The 1-3 structure: a kind of thick film ink of strontium-barium titanate content, be parallel to direction of an electric field, be distributed in the different thick film ink three dimensional matrix of another kind of strontium-barium titanate content in the mode of one dimension line style, after Overheating Treatment, obtain the composite material thick film of 1-3 structure.
According to the kind of selected polyimide precursor, the mode by photoetching corrosion realizes graphically, prepares the adjustable components and parts of dielectric to utilize strontium-barium titanate/polymide dielectric adjustable composite material thick film.
Below be the embodiment that the contriver provides; it is to be noted; according to technical scheme of the present invention; following examples can also be enumerated many, and the present invention is not limited to these embodiment, proves according to applicant's lot of experiment results; formula range in the present invention's proposition; all can reach purpose of the present invention, those skilled in the art make some nonessential improvement and adjustment according to above content to the present invention, all belong to protection scope of the present invention.
Embodiment 1:
1, the code name of selecting for use Beijing Bo Mi scientific ﹠ technical corporation to produce is that the common polyimide coating glue of ZKPI-305IID type is as polyimide precursor.
2, adopting conventional solid reaction process to prepare chemical constitution is Ba
0.6Sr
0.4TiO
3The adjustable pottery of strontium-barium titanate dielectric.Detect through XRD, strontium-barium titanate is pure cubic perovskite structure, does not have second and produces mutually.
3, use the mode fragmentation of general milling, ball milling speed is 150 rev/mins, continues ball milling 4 hours, and the medium particle diameter of the barium-strontium titanate powder of preparing is 0.6um.
4, get strontium-barium titanate powder 100g after the fragmentation, in 110 ℃ dry 24 hours down, add the acrylic acid solution of 2～5g afterwards, supersound process is 1 hour in the dehydrated alcohol of 100ml, and the ceramic powder surface is handled by vinylformic acid.
5, with the barium-strontium titanate powder 20g of polyimide precursor 20g and surface preparation, use the mode of general milling to mix, mixing velocity is 150 rev/mins, continues ball milling 4 hours, the composite material thick film slurry that obtains mixing.
6, adopt spin coating proceeding that thick film ink is coated on the aluminum oxide substrate of surface roasting silver uniformly.Spin coating proceeding is to carry out under 3000 rev/mins 30 seconds, at room temperature leave standstill carried out Procuring by 1 hour in 40 minutes after, continue to apply one deck down, triplicate reaches required thickness, finally adopts the ladder-elevating temperature method that polyimide precursor is solidified.
The gained thickness of thick film is 20um, and the surfacing flawless combines closely with substrate.The specific inductivity of thick film is between 120～140, and dielectric loss is less than 2%.Under the bias field of 12KV/cm, the dielectric adjustable of composite material thick film is 2.8%.The highest bias field that stands 400KV/cm.The dielectric temperature characteristic of the dielectric temperature characteristic of thick film and strontium-barium titanate body material is similar.Can prove, utilize strontium-barium titanate/polymide dielectric adjustable composite material thick film to prepare the adjustable components and parts of dielectric.
Embodiment 2:
1, the code name of selecting for use Beijing Bo Mi scientific ﹠ technical corporation to produce is that the common polyimide coating glue of ZKPI-305IID type is as polyimide precursor.
2, adopting conventional solid reaction process to prepare chemical constitution is Ba
0.6Sr
0.4TiO
3The adjustable pottery of strontium-barium titanate dielectric.Detect through XRD, strontium-barium titanate is pure cubic perovskite structure, does not have second and produces mutually.
3, use the mode fragmentation of general milling, ball milling speed is 150 rev/mins, continues ball milling 4 hours, and the medium particle diameter of the barium-strontium titanate powder of preparing is 0.6um.
4, get strontium-barium titanate powder 100g after the fragmentation, in 110 ℃ dry 24 hours down, add the acrylic acid solution of 2～5g afterwards, supersound process is 1 hour in the dehydrated alcohol of 100ml, and the ceramic powder surface is handled by vinylformic acid.
5, with the barium-strontium titanate powder 20g of polyimide precursor 20g and surface preparation, use the mode of general milling to mix, mixing velocity is 150 rev/mins, continues ball milling 4 hours, the composite material thick film slurry that obtains mixing.
6, adopt spin coating proceeding that thick film ink is coated on the aluminum oxide substrate of surface roasting silver uniformly.Spin coating proceeding is to carry out under 3000 rev/mins 30 seconds, at room temperature leave standstill carried out Procuring by 1 hour in 40 minutes after, continue to apply one deck down, triplicate reaches required thickness, finally adopts the ladder-elevating temperature method that polyimide precursor is solidified.
The gained thickness of thick film is 40um, and the surfacing flawless combines closely with substrate.The specific inductivity of thick film is between 160～180, and dielectric loss is less than 4%.Under the bias field of 10KV/cm, the dielectric adjustable of composite material thick film is 5%.The highest bias field that stands 400KV/cm.The dielectric temperature characteristic of the dielectric temperature characteristic of thick film and strontium-barium titanate body material is similar.Can prove, utilize strontium-barium titanate/polymide dielectric adjustable composite material thick film to prepare the adjustable components and parts of dielectric.
Embodiment 3:
1, the code name of selecting for use Beijing Bo Mi scientific ﹠ technical corporation to produce is that the common polyimide coating glue of ZKPI-305IID type is as polyimide precursor.
2, adopting conventional solid reaction process to prepare chemical constitution is Ba
0.6Sr
0.4TiO
3The adjustable pottery of strontium-barium titanate dielectric.Detect through XRD, strontium-barium titanate is pure cubic perovskite structure, does not have second and produces mutually.
3, use the mode fragmentation of high-energy ball milling, ball milling 4 hours, the medium particle diameter of the barium-strontium titanate powder of preparing are 0.1um.
4, get strontium-barium titanate powder 100g after the fragmentation, in 110 ℃ dry 24 hours down, add the acrylic acid solution of 2～5g afterwards, supersound process is 1 hour in the dehydrated alcohol of 100ml, and the ceramic powder surface is handled by vinylformic acid.
5,, use the mode of high-energy ball milling to mix ball milling 4 hours, the composite material thick film slurry that obtains mixing with the barium-strontium titanate powder 20g of polyimide precursor 20g and surface preparation.
6, adopt spin coating proceeding that thick film ink is coated on the aluminum oxide substrate of surface roasting silver uniformly.Spin coating proceeding is to carry out under 3000 rev/mins 30 seconds, at room temperature leave standstill carried out Procuring in 40 minutes to one hour after, continue to apply one deck down, repeats twice and reaches required thickness, finally adopt the ladder-elevating temperature method to make polyimide precursor curing.
The gained thickness of thick film is 15um, and the surfacing flawless combines closely with substrate, as shown in Figure 1.The specific inductivity of thick film is between 120～140, and dielectric loss is less than 2%, as shown in Figure 2.Under the bias field of 15KV/cm, the dielectric adjustable of composite material thick film is 3%, as shown in Figure 3.The highest bias field that stands 400KV/cm, the adjustable rate of the dielectric of composite material thick film can reach 20%.The dielectric temperature characteristic of the dielectric temperature characteristic of thick film and strontium-barium titanate body material is similar, as shown in Figure 4.Can prove, utilize strontium-barium titanate/polymide dielectric adjustable composite material thick film to prepare the adjustable components and parts of dielectric.
Embodiment 4:
1, the code name of selecting for use Beijing Bo Mi scientific ﹠ technical corporation to produce is that the common polyimide coating glue of ZKPI-305IID type is as polyimide precursor.
2, adopting conventional solid reaction process to prepare chemical constitution is Ba
0.7Sr
0.3TiO
3The adjustable pottery of strontium-barium titanate dielectric.Detect through XRD, strontium-barium titanate is pure cubic perovskite structure, does not have second and produces mutually.
3, use the mode fragmentation of high-energy ball milling, the medium particle diameter of the barium-strontium titanate powder of preparing is 0.1um.
4, get strontium-barium titanate powder 100g after the fragmentation, in 110 ℃ dry 24 hours down, add the acrylic acid solution of 2～5g afterwards, supersound process is 1 hour in the dehydrated alcohol of 100ml, and the ceramic powder surface is handled by vinylformic acid.
5,, use the mode of high-energy ball milling to mix ball milling 4 hours, the composite material thick film slurry that obtains mixing with the barium-strontium titanate powder 20g of polyimide precursor 20g and surface preparation.
6, adopt spin coating proceeding that thick film ink is coated on the aluminum oxide substrate of surface roasting silver uniformly.Spin coating proceeding is to carry out under 3000 rev/mins 30 seconds, at room temperature leave standstill carried out Procuring to 1 hour in 40 minutes after, continue to apply one deck down, triplicate reaches required thickness, finally adopts the ladder-elevating temperature method that polyimide precursor is solidified.
The gained thickness of thick film is 30um, and the surfacing flawless combines closely with substrate.The specific inductivity of thick film is between 140～160, and dielectric loss is less than 5%.Under the bias field of 12KV/cm, the dielectric adjustable of composite material thick film is 3%.The highest bias field that stands 400KV/cm.The dielectric temperature characteristic of the dielectric temperature characteristic of thick film and strontium-barium titanate body material is similar.Can prove, utilize strontium-barium titanate/polymide dielectric adjustable composite material thick film to prepare the adjustable components and parts of dielectric.
Embodiment 5:
1, the code name of selecting for use Beijing Bo Mi scientific ﹠ technical corporation to produce is that the common polyimide coating glue of ZKPI-305IID type is as polyimide precursor.
2, adopting conventional solid reaction process to prepare chemical constitution is Ba
0.6Sr
0.4TiO
3The adjustable pottery of strontium-barium titanate dielectric.Detect through XRD, strontium-barium titanate is pure cubic perovskite structure, does not have second and produces mutually.
3, use the mode fragmentation of high-energy ball milling, the medium particle diameter of the barium-strontium titanate powder of preparing is 0.1um.
4, get strontium-barium titanate powder 100g after the fragmentation, in 110 ℃ dry 24 hours down, add the acrylic acid solution of 2～5g afterwards, supersound process is 1 hour in the dehydrated alcohol of 100ml, and the ceramic powder surface is handled by vinylformic acid.
5,, use the mode of high-energy ball milling to mix ball milling 4 hours, the composite material thick film slurry that obtains mixing with the barium-strontium titanate powder 20g of polyimide precursor 20g and surface preparation.
6, adopt spin coating proceeding that thick film ink is coated on the aluminum oxide substrate of surface roasting silver uniformly.Spin coating proceeding is to carry out under 3000 rev/mins 30 seconds, at room temperature leave standstill carried out Procuring by 1 hour in 40 minutes after, continue to apply one deck down.First and third and five layer is pure polyimide precursor, the second layer and four layers of thick film ink for preparing, and the stratiform 2-2 composite structure of formation A-B-A-B-A finally adopts the ladder-elevating temperature method that polyimide precursor is solidified.
The gained thickness of thick film is 40um, and the surfacing flawless combines closely with substrate.The specific inductivity of thick film is between 40～80, and dielectric loss is less than 1%.Under the bias field of 100KV/cm, the dielectric adjustable of composite material thick film about 2%.The highest bias field that stands 400KV/cm.The dielectric temperature characteristic of the dielectric temperature characteristic of thick film and strontium-barium titanate body material is similar.Can prove, utilize strontium-barium titanate/polymide dielectric adjustable composite material thick film to prepare the adjustable components and parts of dielectric.
Embodiment 6:
1, the code name of selecting for use Beijing Bo Mi scientific ﹠ technical corporation to produce is that the common polyimide coating glue of ZKPI-305IID type is as polyimide precursor.
2, adopting conventional solid reaction process to prepare chemical constitution is Ba
0.6Sr
0.4TiO
3The adjustable pottery of strontium-barium titanate dielectric.Detect through XRD, strontium-barium titanate is pure cubic perovskite structure, does not have second and produces mutually.
3, use the mode fragmentation of high-energy ball milling, ball milling 4 hours, the medium particle diameter of the barium-strontium titanate powder of preparing are 0.1um.
4, get strontium-barium titanate powder 100g after the fragmentation, in 110 ℃ dry 24 hours down, add the acrylic acid solution of 2～5g afterwards, supersound process is 1 hour in the dehydrated alcohol of 100ml, and the ceramic powder surface is handled by vinylformic acid.
5,, use the mode of high-energy ball milling to mix ball milling 4 hours, the composite material thick film slurry that obtains mixing with the barium-strontium titanate powder 20g of polyimide precursor 20g and surface preparation.
6, adopt dipping-czochralski process that thick film ink is coated on the aluminum oxide substrate of surface roasting silver uniformly.Pull rate is 50cm/ minute, at room temperature leave standstill carried out Procuring by 1 hour in 40 minutes after, continue to apply one deck down, triplicate reaches required thickness, finally adopts the ladder-elevating temperature method that polyimide precursor is solidified.
The gained thickness of thick film is 50um, and the surfacing flawless combines closely with substrate.The specific inductivity of thick film is between 110～130, and dielectric loss is less than 3%.Under the bias field of 8KV/cm, the dielectric adjustable of composite material thick film is 2%.The highest bias field that stands 400KV/cm.The dielectric temperature characteristic of the dielectric temperature characteristic of thick film and strontium-barium titanate body material is similar.Can prove, utilize strontium-barium titanate/polymide dielectric adjustable composite material thick film to prepare the adjustable components and parts of dielectric.
Embodiment 7:
1, the code name of selecting for use Beijing Bo Mi scientific ﹠ technical corporation to produce is that ZKPI-310 type low temperature curing type polyimide coating glue is as polyimide precursor.
2, adopting conventional solid reaction process to prepare chemical constitution is Ba
0.6Sr
0.4TiO
3The adjustable pottery of strontium-barium titanate dielectric.Detect through XRD, strontium-barium titanate is pure cubic perovskite structure, does not have second and produces mutually.
3, use the mode fragmentation of high-energy ball milling, ball milling 4 hours, the medium particle diameter of the barium-strontium titanate powder of preparing are 0.1um.
4, get strontium-barium titanate powder 100g after the fragmentation, in 110 ℃ dry 24 hours down, add the acrylic acid solution of 2～5g afterwards, supersound process is 1 hour in the dehydrated alcohol of 100ml, and the ceramic powder surface is handled by vinylformic acid.
5,, use the mode of high-energy ball milling to mix ball milling 4 hours, the composite material thick film slurry that obtains mixing with the barium-strontium titanate powder 20g of polyimide precursor 20g and surface preparation.
6, adopt casting technique that thick film ink is coated in the common copper-clad plate uniformly.Curtain coating speed is for for 50cm/ minute, at room temperature leave standstill carried out Procuring by 1 hour in 40 minutes after, adopt low temperature ladder-elevating temperature method, under 180 ℃ solidification value, polyimide precursor is solidified.
The gained thickness of thick film is 50um, and the surfacing flawless combines closely with substrate.The specific inductivity of thick film is between 110～130, and dielectric loss is less than 3%.Under the bias field of 25KV/cm, the dielectric adjustable of composite material thick film is 5%.The highest bias field that stands 400KV/cm.The dielectric temperature characteristic of the dielectric temperature characteristic of thick film and strontium-barium titanate body material is similar.Can prove, utilize strontium-barium titanate/polymide dielectric adjustable composite material thick film to prepare the adjustable components and parts of dielectric.
Embodiment 8:
1, select for use standard type polyimide coating glue that code name that Beijing Bo Mi scientific ﹠ technical corporation produces can be used for charting for the ZKPI-305IID-2 type as polyimide precursor.
2, adopting conventional solid reaction process to prepare chemical constitution is Ba
0.6Sr
0.4TiO
3The adjustable pottery of strontium-barium titanate dielectric.Detect through XRD, strontium-barium titanate is pure cubic perovskite structure, does not have second and produces mutually.
3, use the mode fragmentation of high-energy ball milling, ball milling 4 hours, the medium particle diameter of the barium-strontium titanate powder of preparing are 0.1um.
4, get strontium-barium titanate powder 100g after the fragmentation, in 110 ℃ dry 24 hours down, add the acrylic acid solution of 2～5g afterwards, supersound process is 1 hour in the dehydrated alcohol of 100ml, and the ceramic powder surface is handled by vinylformic acid.
5,, use the mode of high-energy ball milling to mix ball milling 4 hours, the composite material thick film slurry that obtains mixing with the barium-strontium titanate powder 20g of polyimide precursor 20g and surface preparation.
6, adopt spin coating proceeding that thick film ink is coated on the aluminum oxide substrate of surface roasting silver uniformly.Spin coating proceeding is to carry out under 3000 rev/mins 30 seconds, at room temperature leave standstill carried out Procuring by 1 hour in 40 minutes after, continue to apply one deck down, triplicate reaches required thickness.
7, under 110 ℃ temperature, dried by the fire 40 minutes.Behind the surface-coated photoresist material of thick film, carry out preliminary drying, exposure, development and post bake according to normal photoetching process.Afterwards, use the NaOH aqueous solution etching 30 seconds of 1-2%, place the acetum 10 seconds of 0.5-1% after etching finishes immediately, used deionized water rinsing then 10 minutes, removes residual etching agent and neutralizing agent, dry subsequently.Use commercial acetone stripping photolithography glue-line afterwards.Adopt the ladder-elevating temperature method at last, make the thick film imidization complete.
The gained thickness of thick film is 25um, and the surfacing flawless combines closely with substrate.The specific inductivity of thick film is between 110～130, and dielectric loss is less than 3%.Under the bias field of 25KV/cm, the dielectric adjustable of composite material thick film is 3%.The highest bias field that stands 400KV/cm.The dielectric temperature characteristic of the dielectric temperature characteristic of thick film and strontium-barium titanate body material is similar.Can prove, utilize strontium-barium titanate/polymide dielectric adjustable composite material thick film to prepare the adjustable components and parts of dielectric.
Embodiment 9:
1, the code name of selecting for use Beijing Bo Mi scientific ﹠ technical corporation to produce is that ZKPI-520 type photo-sensistive polyimide coating adhesive is as polyimide precursor.
2, adopting conventional solid reaction process to prepare chemical constitution is Ba
0.6Sr
0.4TiO
3The adjustable pottery of strontium-barium titanate dielectric.Detect through XRD, strontium-barium titanate is pure cubic perovskite structure, does not have second and produces mutually.
3, use the mode fragmentation of high-energy ball milling, ball milling 4 hours, the medium particle diameter of the barium-strontium titanate powder of preparing are 0.1um.
4, get strontium-barium titanate powder 100g after the fragmentation, in 110 ℃ dry 24 hours down, add the acrylic acid solution of 2～5g afterwards, supersound process is 1 hour in the dehydrated alcohol of 100ml, and the ceramic powder surface is handled by vinylformic acid.
5,, use the mode of high-energy ball milling to mix ball milling 4 hours, the composite material thick film slurry that obtains mixing with the barium-strontium titanate powder 20g of polyimide precursor 20g and surface preparation.
6, adopt spin coating proceeding that thick film ink is coated on the aluminum oxide substrate of surface roasting silver uniformly.Spin coating proceeding is to carry out under 3000 rev/mins 30 seconds, at room temperature leave standstill carried out Procuring in 40 minutes to one hour after, continue to apply one deck down, triplicate reaches required thickness.
7, this polyimide precursor does not need the surface-coated photoresist material to get final product photoetching corrosion, can carry out preliminary drying, exposure, development, post bake, rinsing and back baking according to normal photoetching process.Adopt the ladder-elevating temperature method at last, make the thick film imidization complete.
The gained thickness of thick film is 25um, and the surfacing flawless combines closely with substrate.The specific inductivity of thick film is between 110～130, and dielectric loss is less than 3%.Under the bias field of 25KV/cm, the dielectric adjustable of composite material thick film is 3%.The highest bias field that stands 400KV/cm.The dielectric temperature characteristic of the dielectric temperature characteristic of thick film and strontium-barium titanate body material is similar.
Embodiment 10:
1, selecting commercially available polyimide powder for use is solute, and selecting strong polar organic solvent dimethyl formamide for use is solvent, and under the effect of magnetic agitation, formation contains the organic solution of polyimide as polyimide precursor.
2, adopting conventional solid reaction process to prepare chemical constitution is Ba
0.6Sr
0.4TiO
3The adjustable pottery of strontium-barium titanate dielectric.Detect through XRD, strontium-barium titanate is pure cubic perovskite structure, does not have second and produces mutually.
3, use the mode fragmentation of general milling, ball milling speed is 150 rev/mins, continues ball milling 4 hours, and the medium particle diameter of the barium-strontium titanate powder of preparing is 0.6um.
4, get strontium-barium titanate powder 100g after the fragmentation, in 110 ℃ dry 24 hours down, add the acrylic acid solution of 2～5g afterwards, supersound process is 1 hour in the dehydrated alcohol of 100ml, and the ceramic powder surface is handled by vinylformic acid.
5, with the barium-strontium titanate powder 20g of polyimide precursor 20g and surface preparation, use the mode of general milling to mix, mixing velocity is 150 rev/mins, continues ball milling 4 hours, the composite material thick film slurry that obtains mixing.
6, adopt spin coating proceeding that thick film ink is coated on the aluminum oxide substrate of surface roasting silver uniformly.Spin coating proceeding is to carry out under 3000 rev/mins 30 seconds, at room temperature leave standstill carried out Procuring by 1 hour in 40 minutes after, continue to apply one deck down, triplicate reaches required thickness.Insulation is 4 hours under 150 ℃ temperature, evaporates organic solvent, can form composite material thick film.
The gained thickness of thick film is 30um, and the surfacing flawless combines closely with substrate.The specific inductivity of thick film is between 120～140, and dielectric loss is less than 2%.Under the bias field of 12KV/cm, the dielectric adjustable of composite material thick film is 2%.The highest bias field that stands 200KV/cm.The dielectric temperature characteristic of the dielectric temperature characteristic of thick film and strontium-barium titanate body material is similar.Can prove, utilize strontium-barium titanate/polymide dielectric adjustable composite material thick film to prepare the adjustable components and parts of dielectric.
Claims (10)
1. the preparation method of a strontium-barium titanate/polymide dielectric adjustable composite material thick film is characterized in that, comprises the following steps:
Select for use polyimide as presoma;
Select barium strontium titanate medium ceramic powder (Ba for use
1-xSr
x) TiO
3But as the dielectric phase modulation, wherein, x=0.2～0.7, the solid content of strontium-barium titanate is 5wt%～90wt%;
Get 100 parts in strontium-barium titanate powder after the fragmentation, drying is 24 hours under 110 ℃, the acrylic acid solution that then dried ceramic powder is added 2～5 parts, supersound process is 1 hour in 50～100 parts dehydrated alcohol, and the barium-strontium titanate ceramic powder surface is handled by vinylformic acid;
Polyimide precursor and surface treated barium strontium titanate medium ceramic powder are mixed in proportion, adopt the mode of general milling or high-energy ball milling to make it abundant dispersion, obtain mixing thick film ink;
Adopting conventional spin coating proceeding, dipping one czochralski process or casting technique will mix thick film ink is coated on the pretreated base material, then the base material after applying is heat-treated technology and subsequent treatment process, can obtain strontium-barium titanate/polymide dielectric adjustable composite material thick film.
2. as right 1 described method, it is characterized in that described polyimide precursor is standard type polyimide coating glue, photo-sensistive polyimide coating adhesive, low temperature curing type polyimide coating glue or the polyimide organic solution that is used to chart.
3. require described method as claim 1, it is characterized in that, the preparation of barium strontium titanate medium ceramic powder is: with barium carbonate, Strontium carbonate powder and titanium dioxide is raw material, by (Ba
1-xSr
x) TiO
3, x=0.2～0.7 proportioning; Prepare barium-strontium titanate ceramic according to traditional solid reaction process, again through the barium-strontium titanate ceramic powder of broken acquisition particle diameter less than 1 micron.
4. method as claimed in claim 3 is characterized in that: the crumbling method of strontium-barium titanate is general milling or high-energy ball milling.
5. the method for claim 1, it is characterized in that: described spin coating proceeding is to carry out 30 seconds under the state that per minute 3000 changes, thick film ink is coated on the pretreated substrate, at room temperature leave standstill carried out Procuring by 1 hour in 40 minutes after, one deck is until reaching required thickness under continuing to apply, the final ladder-elevating temperature method that adopts is heat-treated, and at minimum 140 ℃, the highest being no more than under 360 ℃ the temperature polyimide precursor is solidified.
6. the method for claim 1, it is characterized in that, described dipping-czochralski process is that thick film ink is coated on the pretreated substrate, at room temperature left standstill 40 minutes to 1 hour, after carrying out Procuring, continue to apply down that one deck finally adopts the ladder-elevating temperature method to heat-treat until reaching required thickness, polyimide precursor is solidified at minimum 140 ℃, the highest being no more than under 360 ℃ the temperature.
7. the method for claim 1, it is characterized in that, described casting technique is that thick film ink is coated on the pretreated substrate, at room temperature leave standstill carried out Procuring by 1 hour in 40 minutes after, one deck is until reaching required thickness under continuing to apply, the final ladder-elevating temperature method that adopts is heat-treated, and at minimum 140 ℃, the highest being no more than under 360 ℃ the temperature polyimide precursor is solidified.
8. the method for claim 1 is characterized in that, the composite structure of described strontium-barium titanate/polymide dielectric adjustable composite material thick film has following three types:
The 0-3 structure: the strontium-barium titanate powder, after heat treatment, obtains the strontium-barium titanate powder and is evenly distributed on composite material thick film in the polyimide matrix within the three-dimensional organic matrix of polyimide with zero dimension dots structure random dispersion;
The 2-2 structure: the thick film ink of different strontium-barium titanate content carries out arranging of lamination cycle by rule, forms a kind of planar layered structures, after heat treatment, obtains a kind of thick film of layered periodic structure;
The 1-3 structure: a kind of thick film ink of strontium-barium titanate content, be parallel to direction of an electric field, be distributed in the different thick film ink three dimensional matrix of another kind of strontium-barium titanate content in the mode of one dimension line style, after Overheating Treatment, obtain the composite material thick film of 1-3 structure.
9. the method for claim 1 is characterized in that, described base material is aluminum oxide substrate or the silicon chip that common copper-clad plate, conventional ceramic substrate, the roasting of cleaning surfaces has electrode.
10. the method for claim 1, it is characterized in that, described subsequent technique is according to the kind of selected polyimide precursor, and the mode by photoetching corrosion realizes graphically, prepares the adjustable components and parts of dielectric to utilize strontium-barium titanate/polymide dielectric adjustable composite material thick film.
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| CN103036052B (en) * | 2011-09-30 | 2016-06-29 | 深圳光启高等理工研究院 | The preparation method of a kind of medium substrate and Meta Materials |
| CN106696410B (en) * | 2016-12-15 | 2018-08-07 | 陕西科技大学 | A kind of method that the tape casting prepares stratiform barium ferrite/RGO composite wave-suction materials |
| CN107139371B (en) * | 2017-06-22 | 2019-03-26 | 合肥通用机械研究院有限公司 | Microwave forming method for Thermocurable polyimide plate |
| CN111925540B (en) * | 2020-08-01 | 2022-08-19 | 江西师范大学 | High dielectric constant nano perovskite CsPbX 3 Polyimide composite membrane and preparation method thereof |
| CN111875798B (en) * | 2020-08-01 | 2022-11-01 | 江西师范大学 | High dielectric constant CsPbX3rGO/polyimide composite membrane and preparation method thereof |
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